EP4069797A1 - Michael-additions-härtendes kunstharz für die chemische befestigungstechnik - Google Patents

Michael-additions-härtendes kunstharz für die chemische befestigungstechnik

Info

Publication number
EP4069797A1
EP4069797A1 EP20820070.9A EP20820070A EP4069797A1 EP 4069797 A1 EP4069797 A1 EP 4069797A1 EP 20820070 A EP20820070 A EP 20820070A EP 4069797 A1 EP4069797 A1 EP 4069797A1
Authority
EP
European Patent Office
Prior art keywords
synthetic resin
acrylate
resin system
component
bisphenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20820070.9A
Other languages
German (de)
English (en)
French (fr)
Inventor
Christian Weinelt
Martin Vogel
Ursula LINK-PFAFF
Hannah GEHRING
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fischerwerke GmbH and Co KG
Original Assignee
Fischerwerke GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fischerwerke GmbH and Co KG filed Critical Fischerwerke GmbH and Co KG
Publication of EP4069797A1 publication Critical patent/EP4069797A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B11/00—Connecting constructional elements or machine parts by sticking or pressing them together, e.g. cold pressure welding
    • F16B11/006—Connecting constructional elements or machine parts by sticking or pressing them together, e.g. cold pressure welding by gluing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B13/00—Dowels or other devices fastened in walls or the like by inserting them in holes made therein for that purpose
    • F16B13/14—Non-metallic plugs or sleeves; Use of liquid, loose solid or kneadable material therefor
    • F16B13/141—Fixing plugs in holes by the use of settable material
    • F16B13/142—Fixing plugs in holes by the use of settable material characterised by the composition of the setting material or mixture
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00715—Uses not provided for elsewhere in C04B2111/00 for fixing bolts or the like
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/13—Morphological aspects
    • C08G2261/135—Cross-linked structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/60—Glass transition temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/62—Mechanical aspects
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/76—Post-treatment crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the invention relates to a synthetic resin system for chemical fastening technology, in particular for fastening anchoring means in boreholes, which contains a reaction resin based on ⁇ , ⁇ -unsaturated compounds, a reaction resin based on compounds containing CH-acidic methylene groups, and a catalyst, as well as its use and further aspects (embodiments) of the invention mentioned below.
  • Radically curing systems are characterized by rapid low-temperature curing (e.g. - 10 ° C), but show a relatively high shrinkage ("shrinkage") and not very high pull-out values.
  • Systems based on epoxy amine show a significantly slower curing rate at low temperatures (e.g. ⁇ + 5 ° C), but have significantly less shrinkage and significantly higher pull-out values.
  • the object of the present invention is to provide a synthetic resin system which allows rapid low-temperature curing as in the case of free-radically polymerizable Systems with significantly higher pull-out values as in polyaddition-curing systems (epoxy-amine) combined.
  • Another object for preferred aspects of the present invention is the provision of a fastening compound in the form of a synthetic resin system, which avoids ingredients that are highly hazardous to health and preferably does not require labeling.
  • US 4217396 also describes crosslinked acrylate-acetoacetate polymers for use as floor coatings.
  • the acetoacetates used are exclusively diacetoacetates, which in combination with polyfunctional acrylates form the floor coating.
  • the crosslinking index used in the examples is 2.9.
  • US 4602 061 describes a paint composition curable at room temperature, which consists of an ⁇ , ß-unsaturated carbonyl compound and a compound with activated CH groups (such as oligomers or polymeric esters containing malonate groups).
  • the paint composition cures quickly and without the application of heat and has excellent hardness.
  • the crosslinking indices used in the compositions range from 2.0 to 2.7.
  • the American patent application US 2005/0081995 A1 is based on an adhesive composition which consists of at least one Michael donor, at least one Michael acceptor and at least one anion of a Michael donor.
  • the adhesive composition is used to make adhesive strips and has a crosslinking index in the range from 2.0 to 2.2.
  • the invention relates to a synthetic resin system which comprises the following components: a) reaction resin based on ⁇ , ⁇ -unsaturated compounds, b) reaction resin which contains compounds bearing CH-acidic methylene groups, and c) a catalyst.
  • the synthetic resin system is preferably multi-component, in particular two-component, designed, preferably as a multi-component, such as two-component kit.
  • the invention also relates to the use of a multi-component, in particular two-component synthetic resin system composed as just described as an adhesive, in particular for fastening anchoring means in substrates such as masonry or concrete, or for fastening fibers, scrims, fabrics or composites for Reinforcement of structures.
  • Corresponding methods and methods for grouting anchoring elements in holes or crevices in which a multi-component, in particular two-component, synthetic resin system according to the invention is used for mortaring (gluing) anchoring means, the synthetic resin system and an anchoring means one after the other, in particular first the synthetic resin system, then the anchoring means, or (at least substantially) simultaneously, are introduced into a hole or a gap in a substrate (also in a cracked substrate, such as cracked concrete), or mixed forms, each with partial introduction, form an embodiment of the invention.
  • a synthetic resin system based on components a), b) and c) combines the advantages that can be found on the one hand in radical curing and on the other hand in chemical fastening systems curing by polyaddition, although no radical curing is involved. This is surprising insofar as the reaction taking place here has never been used in a synthetic resin system for chemical fastening technology.
  • the Michael addition is known from the field of coatings, especially for floor coatings (see the above-mentioned corresponding Patents). Since the forces occurring in the borehole are completely different from those of a (floor) coating, it was not obvious to those skilled in the field of fastening technology for anchors to carry the Michael addition between ⁇ , ⁇ -unsaturated compounds and CH-acidic methylene groups To consider compounds as a synthetic resin system for chemical fastening systems for use. In the borehole - viewed macroscopically - enormous shear stresses occur in the event of an axial load, which the system has to withstand, whereas a (floor) coating should withstand rather high compressive strengths and abrasion strengths.
  • the inventors have also surprisingly found that a synthetic resin system based on a Michael addition also has a high performance in the borehole when using highly functionalized starting materials.
  • the inventors were also able to determine that the higher the crosslinking index, the higher the pull-out values from concrete. This is surprising insofar as the European patent application EP 3299432 A1 teaches on pages 2 and 3 that the polymerisation shrinkage increases with an increasing proportion of functional groups (here (meth) acrylate groups) and the load-bearing behavior of the chemical composite dowel is significantly impaired as a result.
  • the invention relates to a synthetic resin system which comprises the following components: a) reaction resin based on a, ß-unsaturated compounds with an average functionality> 2 b) reaction resin which contains CH-acidic methylene group-bearing compounds with an average functionality> 4, and c) a catalyst.
  • crosslinking density for the cured product is based on a crosslinking index in the range of 3.0 or higher, the crosslinking index IV generally being determined using the following formula:
  • - ni is the amount of substance (number) of the corresponding groups of molecule i of the overall system
  • - fi is the respective (possibly mean in the case of mixtures) functionality of the reactive molecules, taking into account the number of possible reactions with a potential reactant; Two-component system) so that, according to the invention, the amount of excess reactive groups of a component should preferably not deviate by more than 20% from the stoichiometrically correct amount, preferably by less than 10%, even more preferably by less than 0.5%, and where full implementation is accepted.
  • the crosslinking index is thus also a theoretically determined (mean) variable which can be obtained or determined from the data Ai, ni and fi or corresponding information for the methods for determining reactive groups (for example, commercially available or known to those skilled in the art according to methods known to the person skilled in the art) ) Educts is determined.
  • the person skilled in the art can readily understand that a wide variety of crosslinking indices can be achieved by mixing compounds with different functionalities in suitable ratios to one another (see also the above formula).
  • the subject of the present invention is thus in a further embodiment of the invention a synthetic resin system which comprises the following components: a) reaction resin based on a, ß-unsaturated compounds with an average functionality> 2 b) reaction resin which contains CH-acidic methylene group-bearing compounds with an average Functionality> 4, and c) a catalyst, characterized in that the crosslinking index of the synthetic resin system is> 3. It was also found that a synthetic resin system based on components a), b) and c) fulfills the criteria applicable for usability under construction site conditions.
  • proportions or content data in percent mean weight percent (“% by weight”) or the relative weight proportion, unless otherwise stated, based on all ingredients of a synthetic resin system according to the invention (without packaging material), unless otherwise stated or evident.
  • Consist (d) of 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 “consist (d) of”, which is a final list of when it is used means listed components or features. In embodiments of the invention, “include” or “comprise” may be replaced by “consist (d) of”.
  • the average functionality of the ⁇ , ⁇ -unsaturated compounds is> 2, in particular> 2 to 20 or preferably up to 18, in particular 2.05 to 20 or preferably up to 18, preferably 2.1 to 20,.
  • the average functionality of the compound bearing CH-acidic methylene groups is> 4, in particular> 4 to 12, preferably up to 7, in particular 4.05 to 12, preferably up to 7, preferably 4.1 to 12, preferably to 7.
  • the crosslinking index of the synthetic resin system is> 3, preferably> 3 to 6, in particular 3.1 to 6, more preferably 3.5 to 6, more preferably 4 to 6, especially 4.1 to 4.3.
  • the ⁇ , ⁇ -unsaturated compound in a reaction resin based on ⁇ , ⁇ -unsaturated compounds, can generally be an ethylenically unsaturated compound in which the carbon double bond is activated by an electron-withdrawing group (for example a carbonyl group in a-position).
  • Acrylic-functional alkoxysilanes or organopolysiloxanes are also possible (cf. WO2006 / 087079 A1), such as acrylatomethyl-trimethoxysilane, -methyldimethoxysilane, -dimethylmethoxysilane, -triethoxysilane or -methyldiethoxysilane, acrylamidomethyl-trimethoxysilane, -methyl-silane, methoxysilane, acrylamidomethyl-trimethoxysilane, -methyl-di-methoxysilane, acrylamidomethyl-trimethoxysilane , or -methyl- dimethylethoxysilane.
  • a reaction resin based on ⁇ , ⁇ -unsaturated compounds can also be understood to mean a polyester resin based on maleic, fumaric or itaconic acid, or in each case their anhydride.
  • Polyester, polyurethane, polyether and / or alkyd resins which carry activated, ethylenically unsaturated groups are also to be understood as such reaction resins.
  • Acrylates (particularly preferred), fumarates, itaconates and maleates, especially those identified as preferred in the present disclosure, are preferred reactive resins.
  • the compounds mentioned can also be present as mixtures of two or more thereof.
  • Mono-acrylates are also possible. However, because of their chain-breaking effect, these are less preferred or are present as admixtures with di- or polyacrylates.
  • Commercially available acrylates and / or fumarates, maleates or itaconates can be used. Examples of representatives of the mono-acrylates are tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate and / or cyclic trimethylolpropane formalacrylate.
  • the more preferred mono-acrylates include acrylated amines, available from Sartomer, for example.
  • the monoacrylates, fumarates, maleates and / or itaconates can also be mixed with di- or polyacrylates, fumarates, maleates and / or itaconates.
  • a, b-unsaturated compounds with a biogenic component (characterized by the 14 C content, which is higher relative to the total carbon content than with fossil materials) belong to the preferred compounds of this class, i.e.
  • epoxidized soybean oil acrylate 1,10-decanediol diacrylate, tetrahydrofuryl acrylate, isobornyl acrylate, sorbitol acrylate, lauryl (meth) acrylate, benhenyl acrylate, propoxylated glycerol triacrylate, pentaerythritol, triacrylate, pentaerythritol, triacrylate, pentaerythritol, acrylate, pentaerythritol, pentaacrylate, pentaacrylate, methacrylate, pentaacrylate, pentaacrylate, pentaacrylate, pentaacrylate , pentaacrylate , acrylated fusel oil, or biogenic glycerol triacrylate or such in which at least the acrylate component is biogenic.
  • Biogenic urethane acrylates (obtainable, for example, by reaction of isocyanates (such as: Desmodur Eco N 7300) with an acrylate containing OH groups, such as hydroxyethyl, hydroxypropyl, hydroxybutyl or pentaerythritol tri-acrylate, and polyester acrylate resins, e.g. tetrafunctional polyester acrylates).
  • isocyanates such as: Desmodur Eco N 7300
  • an acrylate containing OH groups such as hydroxyethyl, hydroxypropyl, hydroxybutyl or pentaerythritol tri-acrylate
  • polyester acrylate resins e.g. tetrafunctional polyester acrylates
  • the proportion of bio-based carbon is carried out on the basis of ASTM 6866 (Standard Test Method for Determining the Biobased Content of Solid, Liquid and Gaseous Samples Using Radiocarbon Analysis, using the 14 C content (ASTM International, D6866: 2008 Method A).
  • acrylates are mentioned above and below, this also includes, alternatively or in combination, the corresponding methacrylates (in the case of the more specific, to be realized by adding (“meth” before “acrylate”).
  • methacrylates in the case of the more specific, to be realized by adding (“meth” before “acrylate”).
  • a mixture of two or more (in particular the abovementioned) ⁇ , ⁇ -unsaturated compounds is also possible.
  • the proportion of the reaction resin based on ⁇ , ⁇ -unsaturated compounds is preferably 1 to 80% by weight, in particular 2 to 60% by weight.
  • a reaction resin which contains (one or more) CH-acidic methylene groups (activated methylene groups) is in particular one of malonic acid or malonic acid esters, such as malonic acid dimethyl ester, malonic acid di-ethyl ester, malonic acid di-n-propyl ester, malonic acid diisopropyl ester, malonic acid dibutyl ester -di (2-ethylhexyl) ester or malonic acid dilauryl ester; Cyanoacetic acid esters such as 2-ethylhexyl cyanoacetate, butyl cyanoacetate, octyl cyanoacetate, 2-methoxyethyl cyanoacetate; Diones such as pentane-2,4-dione, hexane-2,4-dione, heptane-2,4-dione, 1-methoxy-2,4-pentanedione, 1-phenyl-1,3-but
  • the reaction resin bearing CH-acidic methylene groups is very particularly preferably an acetoacetate with at least 2 or more acetoacetate groups.
  • the acetoacetates can be aliphatic, heteroaliphatic, cyclic, heterocyclic, cycloaliphatic and / or araliphatic.
  • the proportion of the CH-acidic compound (s) is preferably 1 to 80% by weight, in particular 2 to 60% by weight.
  • CH-acidic compounds with methylene groups are, since they carry two hydrogens, to be regarded as mono- or difunctional.
  • the methylene groups are to be regarded as difunctional for the Michael addition and the calculation of the crosslinking index.
  • One (or two or more) selected from the following catalysts can advantageously be included as a catalyst for a synthetic resin system according to the invention:
  • Strongly basic catalysts especially with a pKa of 11 or higher
  • alkali metal hydroxides e.g. sodium or potassium hydroxide
  • alkali metal alkoxides e.g.
  • quaternary ammonium compounds e.g. tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium carbonate
  • tertiary amines e.g. diazabicyclooctane (also referred to as DABCO) and guanicidines / amidines (e.g. tetramethylguanidines) 5.4.0] undec-7-en, 1,5-diazabicyclo [4.3.0.] Non-5-en
  • silicates e.g. sodium silicate
  • metal oxides e.g. calcium oxide
  • phosphine catalysts e.g.
  • tricyclohexylphosphine (particularly preferred) , Tricylopentylphosphine, tri-n-hexylphosphine, tris (2,4,4-trimethylpentyl) phosphine, tris (2-ethylhexyl) phosphine, tri-n-octylphosphine (particularly preferred), tri-n-decylphosphine, tri-n-dodecylphosphine (particularly preferred), tristearylphosphine and triphenylphosphine.
  • a further suitable catalyst (resulting after mixing the components of a synthetic resin system according to the invention) is a mixture of an epoxide (with epoxy groups as (preferably as low molecular weight) glycidyl esters, glycidyl ethers, such as the diglycidyl ether of bisphenol A, or epoxidation products of alpha-olefins) with one or several tertiary amines (in particular triethylenediamine, Mannich reaction products, or the acrylated amines already mentioned above (available from Sartomer)), as described in EP 0 326723 (hereinafter also referred to as epoxy / tert-amine catalysts).
  • epoxy groups as (preferably as low molecular weight) glycidyl esters, glycidyl ethers, such as the diglycidyl ether of bisphenol A, or epoxidation products of alpha-olefins)
  • tertiary amines in particular triethylenediamine,
  • the epoxide can advantageously be accommodated in the component with the ⁇ , ⁇ -unsaturated compound or the CH-acidic compound or both, the tertiary amine in the component with the ⁇ , ⁇ -unsaturated compound.
  • Salts of strong bases such as tetramethylguanidine, DABCO (1,8-diazabicyclo (5.4.0) undec-7-en) or quaternary ammonium hydroxides can also be used be added, for example divided in such a way that the starch-base part is contained in one component (preferably not the one with the CH-acidic compound), the epoxide is contained in another component.
  • the ingredients react when mixed and form a strong catalytically active base.
  • Possible catalysts are also carbon dioxide-blocked strong bases, such as quaternary alkyl ammonium bi- or alkyl carbonates, which are, however, less preferred because they release CO2, except for applications where this is not bothersome or even desirable, for example heat-insulating coatings.
  • It can also contain two or more of the catalysts mentioned.
  • the catalysts are preferably added in 0.01 to 15% by weight, in particular 0.1 to 10% by weight.
  • a multi-component kit is to be understood as meaning, in particular, a two-component kit (preferably a two-component kit, preferably a two- or furthermore multi-chamber device, in which the components that are reactive to one another are contained in such a way that they cannot lead to undesired reactions during storage, preferably so that the reactive components do not come into contact with each other before use.
  • Cartridges are possible. However, cartridges or foil bags with two or more chambers, or containers such as buckets or tubs with several chambers or sets (e.g.
  • containers are particularly suitable of two or more such containers, with two or more components of the respective curable synthetic resin system, in particular two components, each spatially separated from one another as a kit or set, in which the contents, after mixing or mixing, are applied to the application site (in particular by means of devices for A.
  • the multi-component kit can also include a device for emptying (for example a pressure pistol), but this can preferably also be made up or offered (for example for multiple use) independently of the kit.
  • the reactive constituents of a synthetic resin system according to the invention (this primarily means constituents a), b) and c) are distributed among the components of the multicomponent system, in particular multicomponent kits, that mutually reactive constituents prior to use (especially during manufacture, storage and Transport) do not come into contact with one another (the components are separated from one another in a reaction-inhibiting manner).
  • mutually reactive constituents prior to use especially during manufacture, storage and Transport
  • the components are separated from one another in a reaction-inhibiting manner.
  • components a) and b) are contained in one component (K1), while component c) alone or together with a non-reactive solvent / diluent / plasticizer and / or adhesion promoter in another ( Component (K2) which is immiscible in the storage state, ie separated) is included, it being possible for one or more further additional ingredients to be optionally present in each case.
  • the catalyst is an epoxy / tert-amine catalyst, this is also divided between the two components.
  • components a), b) and the epoxy part of an epoxy / tert-amine catalyst are contained in one component (K1), and component c) together with the tert - Amine part of an epoxy / tert-amine catalyst in another component (K2), it being possible for one or more additional ingredients to be optionally present here as well.
  • a synthetic resin system according to the invention preferably contains one or more other additives, in particular selected from fillers, rheological aids, thixotropic agents, plasticizers, coloring additives and adhesion promoters, as well as solvents and / or reactive thinners.
  • Customary rheological aids which cause thixotropy can be used as thixotropic agents, such as pyrogenic silica, bentonites, alkyl and methyl celluloses, castor oil derivatives or the like. They can be added, for example, in a proportion by weight of 0.01 to 50% by weight, in particular 0.5 to 20% by weight, for example 0.1 to 5% by weight.
  • conventional fillers with a fine e.g. medium grain d50 at 50 ⁇ m or less, in particular at 40 ⁇ m or less, preferably at 30 ⁇ m or less, preferably at 25 ⁇ m or less, e.g.
  • preferably at 20 ⁇ m or less can be used preferably at 10 pm or less, primarily 5 pm or less, first and foremost 1 pm or less) or larger medium grain size, in particular chalk, sand, quartz sand, quartz powder, rock flour, glass, porcelain, corundum, ceramics, silicates, Clays, barite, aluminum hydroxide, calcium carbonate or the like, which can be added as powder, in granular form or in the form of shaped bodies, use, or others, such as kernel or shell meal from plants, which increases the biogenic carbon content, such as olive kernel flour, coconut shell flour or also walnut shell flour, or hydraulic fillers such as gypsum, quicklime or cement (for example clay or Portland cement), water glasses or active aluminum hydroxides, ode r Mixtures of two or more thereof, wherein the fillers can furthermore or in particular also be silanized.
  • medium grain size in particular chalk, sand, quartz sand, quartz powder, rock flour, glass, porcelain, corundum, ceramics, silicates
  • the fillers can be present in one or more components of a multi-component synthetic resin 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 70% by weight (with the encasing material destroyed when anchoring elements are introduced (e.g. shattered glass or shattered plastic), for example shards from cartridges, as filler can be credited or preferably will).
  • the proportion of fillers is preferably 0 to 90% by weight, for example 10 to 70% by weight (with the encasing material destroyed when anchoring elements are introduced (e.g. shattered glass or shattered plastic), for example shards from cartridges, as filler can be credited or preferably will).
  • the mean grain d50 is defined as the grain size at which 50% by weight of the particles is smaller than the specified particle size d50.
  • determining the d50 e.g. by means of classifying grading curves with sieves or for example (especially for smaller particles with a diameter of less than 1 ⁇ m) by laser granulometry.
  • the medium grain size may correspond to the manufacturer's specifications.
  • silane coupling agents with functional groups such as mercapto, epoxy, vinyl, or halogen, such as g-ureidopropyltrimethoxysilane, N-vinylbenzyl-y-aminopropyltriethoxysilane, g-mercaptopropyltrimethoxysilane, g-mercaptopropyl-triethoxysilane, g-mercapto-propyl-triethoxy-methoxysilane, g-mercapto-propyl-triethoxy-methoxysilane, Mercaptopropylmethyldimethoxysilane, g-glycidyloxypropyltrimethoxysilane, g-glycidylpropyltriethoxysilane, g-glycidyloxypropylmethyldimethoxysilane, ß- (3,4-epoxycyclohexyl) et
  • functional groups such as mercap
  • additives can also be added, such as plasticizers, non-reactive diluents, flexibilizers, stabilizers, rheological aids, wetting agents and dispersants, coloring additives such as dyes or especially pigments, for example for different coloring of the components for better control of their mixing, or the like, or a mixture of two or more thereof.
  • coloring additives such as dyes or especially pigments, for example for different coloring of the components for better control of their mixing, or the like, or a mixture of two or more thereof.
  • 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.
  • Alcohols such as 2-propanol, 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, 1,2-propanediol, 1,4-butanediol, ethylene glycol, hexylene glycol, ethoxylated bisphenol A, such as the company's Dianoie Seppic; Polyols such as polyether polyols and / or polyester polyols such as Voranoie from Dow Chemical Company; Esters, such as tris (2-ethylhexyl) -0-acetyl citrate, triethyl citrate, acetyl tri butyl citrate, glycerol triacetate, isodecyl benzoate, 2,2,4-trimethyl-1,3-pentanediol di-isobutyrate, DBE - dibasic esters, 1,2 -Cyclohexanedicarboxylic
  • a biogenic, non-reactive diluent (diluent) which is liquid as such at the application temperature is to be understood as meaning in particular one which occurs as such (in unmixed form) at room temperature or in the range from 0 to 30 ° C. in liquid form.
  • diluent is a vegetable oil, such as castor oil, linseed oil, epoxidized linseed oil or also corresponding hydroxylated and hydroxyalkylated oils (e.g.
  • polyether polyester polyols or polyester polyols such as corresponding Merginols® from Hobum Oleochemicals GmbH, Hamburg, Germany), soybean oil, epoxidized soybean oil or rapeseed oil, or also fatty acid alkyl esters ("biodiesel”), such as fatty acid methyl esters, eg rapeseed methyl ester or soybean oil methyl ester. Castor oil is particularly preferred.
  • biogenic polyol in particular biogenic glycerine and / or biogenic 1,4-butanediol, in particular of vegetable origin, can be used.
  • Non-reactive means that under normal application conditions there is no or only a negligible chemical reaction of the liquid diluent with the reactive system, ie the components that polymerize and initiate the polymerization.
  • Alkyl preferably denotes a linear or mono- or multiply branched saturated (acyclic) hydrocarbon radical with up to 20 carbon atoms, for example C C -C -alkyl, in particular C 1 -C 4 -alkyl, such as in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , tert-butyl, or the like.
  • CrC4-alkyl the number 1-4 always refers to the alkyl group itself (and does not include adjacent parts of the molecule, such as -carbonyl or -carbonylmethyl).
  • drill holes are made in a horizontally lying concrete test specimen (concrete type C20 / 25) with a hammer drill and a hammer drill.
  • the drill holes are cleaned with a hand blower and a hand brush.
  • the drill holes 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 24 hours at room temperature, the threaded rod is pulled until failure while measuring the failure load.
  • the gel time is determined from a 30 g mixture in a plastic beaker at 23 ° C. by means of manual stirring. When the gelation point is reached, the previously liquid mixture becomes highly viscous and gel-like, which is noticeable through the formation of lumps. At this point, the clock started after the test started will be stopped. The gel time can be read off directly.
  • Tg onset or glass transition temperature
  • Example 1 Compositions and pull-out tests from concrete of synthetic resin systems according to the invention
  • Example 2 Compositions and pull-out tests from concrete with different TMPTA ratios
  • Table 3 shows that despite the deviation from the optimal mixing ratio (B2.4 - determined with DSC based on ISO 11357-2 (2013)) the bond stress remains relatively constant.
  • Example 3 Compositions and pull-out tests with different catalysts and screening catalyst content
  • Table 4 below shows the constituents used and the determined bond stresses of synthetic resin systems according to the invention, in which the type and amount of catalysts used are varied.
  • Table 4 shows that all strongly basic compounds can be used as catalysts for the synthetic resin systems according to the invention.
  • Table 4 also shows that the gel time varies with the aid of the amount of catalyst used or can be adjusted to a desired gel time.
  • Table 4 also shows that the synthetic resin systems according to the invention can combine the advantages of the systems previously used in chemical fastening technology: rapid curing as in the case of radically curing systems, with the high bond stresses of epoxy systems. This is confirmed by the gel times and bond stresses determined.
  • Example 4 Compositions and pull-out tests at low temperatures and reference tests
  • Example 5 Compositions and pull-out tests after different curing times
  • Table 7 shows mixtures of different acrylates and their bond stresses determined in the pull-out test, as well as their onset and glass transition temperatures.
  • Table 7 shows that all acrylates can be used in the synthetic resin systems according to the invention.
  • the listed onset or glass transition temperature which is a measure of the heat resistance of the respective system, shows that the synthetic resin systems according to the invention are suitable for use under construction site conditions (depending on the weather, high temperatures can occur here) and even the injection mortar FIS EM 390 Outperform S ® in the 2nd run.
  • Example 7 Compositions and pull-out tests with different crosslinking indices
  • the synthetic resin systems according to the invention should have a certain crosslinking index. This differs greatly from the networking indices used for (floor) coatings from the prior art.
  • the following table 8 is intended to show this.
  • Table 8 shows that the bond tension increases as the crosslinking index of the synthetic resins according to the invention increases.
  • Table 8 also shows that the glass transition temperature (an important parameter for a fastening system because it represents an indirect measure of the heat resistance) also increases with the increasing crosslinking index. For this reason, the synthetic resins according to the invention should have a crosslinking index of> 3.
  • Example 8 Cartridge formulation for pull-out tests
  • a 150 ml cartridge with a volume ratio of 7: 1 is filled from the components listed in Table 9 and subjected to a setting test according to the aforementioned methods for determining parameters for “pull-out tests from concrete”. In this case, component A is filled into the larger part of the volume.
  • the bond stress determined is 28 N / mm 2 .

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  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Epoxy Resins (AREA)
EP20820070.9A 2019-12-04 2020-12-01 Michael-additions-härtendes kunstharz für die chemische befestigungstechnik Pending EP4069797A1 (de)

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DE102019133063 2019-12-04
DE102020128717.8A DE102020128717A1 (de) 2019-12-04 2020-11-02 Michael-Additions-härtendes Kunstharz für die chemische Befestigungstechnik
PCT/EP2020/084011 WO2021110622A1 (de) 2019-12-04 2020-12-01 Michael-additions-härtendes kunstharz für die chemische befestigungstechnik

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US4217396A (en) 1979-05-10 1980-08-12 Armstrong Cork Company Acrylate-acetoacetate polymers useful as protective agents for floor coverings
ZA852044B (en) 1984-03-29 1985-11-27 Akzo Nv Liquid coating composition curable at ambient temperature
EP0326723B1 (en) 1988-02-01 1993-03-24 Rohm And Haas Company Method for reacting two components, compositions, coating compositions and uses thereof
DE4111828A1 (de) 1991-04-11 1992-10-15 Basf Ag Patrone fuer die chemische befestigungstechnik
US8013068B2 (en) * 2003-01-02 2011-09-06 Rohm And Haas Company Michael addition compositions
DE102005007320A1 (de) 2005-02-17 2006-08-24 Consortium für elektrochemische Industrie GmbH Durch Michael Additionsreaktion härtbare Zusammensetzungen
EP2357162B1 (en) 2010-02-11 2012-09-05 HILTI Aktiengesellschaft Resin mortar suitable for construction purposes, especially for chemical anchoring
EP2829524A1 (de) * 2013-07-24 2015-01-28 HILTI Aktiengesellschaft Harzmischung, Reaktionsharz-Mörtel, Mehrkomponenten-Mörtelsystem und deren Verwendung
DE102015003221A1 (de) * 2014-04-11 2015-10-15 Fischerwerke Gmbh & Co. Kg CH-Acide Verbindungen und Metallsalze als Härtesystem, entsprechende Harzzusammensetzungen unter anderem für die Befestigungstechnik
JP6837991B2 (ja) * 2015-04-17 2021-03-03 オールネックス・ネザーランズ・ビー．ブイ．Ａｌｌｎｅｘ Ｎｅｔｈｅｒｌａｎｄｓ Ｂ．Ｖ． フロアコーティング組成物
EP3299432A1 (de) 2016-09-26 2018-03-28 HILTI Aktiengesellschaft Zweikomponenten-mörtelmasse und deren verwendung

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DE102020128717A1 (de) 2021-06-10

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