EP3158011A1 - Fire-retardant composition and use thereof - Google Patents

Abstract

Described is a fire-retardant composition comprising a component A which contains a multifunctional Michael acceptor having at least two electron-deficient multiple carbon bonds per molecule as a functional Michael acceptor group, further comprising a component B which contains a multifunctional Michael donor having at least two thiol groups per molecule as a functional Michael donor group, and comprising a component C which contains at least one ablative fire-retardant additive. The claimed composition makes it possible to apply, in a simple and rapid manner, coatings that have the layer thickness required for the particular fire resistance rating, the layer thickness being reduced to a minimum but nevertheless achieving a great fireproofing effect. The claimed composition is particularly suitable for fire protection, especially as a coating for cables and cable routes, in order to increase the fire resistance rating.

Description

 Fire protection composition and its use

DESCRIPTION

The present invention relates to a composition, in particular an ablative composition containing a thiol-En-based binder, and their use for fire protection, in particular for the coating of components such as supports, beams, trusses, insulation systems, e.g. Soft bulkheads, cables, cable bundles or cable trays to increase the fire resistance duration.

In fires cable trays form special danger spots for several reasons.

On the one hand occurs in fires of plastic insulated cables intensive smoke emission under emission harmful, z.T. toxic substances. On the other hand, a fire can spread rapidly along cable trays and the fire can spread

Be moved to a location far from the original source of fire.

In cable systems also has the problem that these cables by thermal

Exposure or burn-off the effect of the insulation decreases and can occur due to a short circuit, an interruption of the current flow and thus the cables are destroyed or dysfunctional.

Electrical cables and lines are often laid in corridors and subdivided from there into adjacent rooms. These corridors serve in case of fire as escape and rescue routes, which are unusable in fires of cable installations by smoke and toxic fumes, with z. B. burning PVC releases highly corrosive gases. Cable masses are thus used in particular in industrial construction, in power plants, in hospitals, large and administrative buildings and in general Buildings with a high installation density pose a considerable risk potential. The cable insulation in these buildings is often the relevant fire load and cause long-lasting fires with fire chamber temperatures in unfavorable cases up to over 1000 ° C. For the reasons mentioned, cable ducts should be given special attention with regard to fire protection measures.

In order to prevent these hazards of the lack of functionality of the cables and the strong fire load increase by the cables at least temporarily, it is known to spatially separate the cables by non-combustible building materials of building material class A1 or A2, in which the cables. be installed in installation and / or function maintenance channels. However, this requires a lot of work. In addition, a high space requirement is caused by complex constructions, which in addition to the weight of the cable tray still have to consider the weight of the installation and / or functional maintenance channels. These cables and cable trays are often wrapped with insulating materials, such as alumina-silica mats or mineral wool mats. To achieve adequate fire protection, the material must be very thick. However, this causes problems in terms of the distances between the protected object and adjacent or superposed objects. In addition, these materials cause problems in normal operation due to their thermal insulating properties. One of these problems is referred to as "current carrying capacity reduction." This means that the heat generated by electrical cables in the conduit or cable race can no longer be dissipated in the area of the insulation, resulting in the safe current operating level allowed in these cables is reduced or that the cables are overheated These disadvantages make this type of fire protection very inflexible with regard to their field of application.

To avoid these disadvantages, it is also known to apply coatings for the protection of electrical cables which intumesce in the event of fire under the influence of heat, i. foam and thus form an insulating layer or absorb heat through physical and chemical processes and thus have a cooling effect.

With intumescent coatings it is possible to prevent the participation of cables in the fire for 30 minutes or longer. Such coated cables are often laid on cable trays. However, it has been shown that with vertical or inclined arrangement of the cable trays and a completely foamed Insulating agent can not prevent the spread of fire without additional measures. During heating, the cables deform so much between the cable clamps that the layer forming the insulating layer tears open and partially flakes off. Forming foam also dissolves from the cables and falls off. When the cables have been laid, the cables in the area of the clamp constructions are not fully accessible. This has the consequence that with vertical or inclined arrangement of the cable trays in case of fire in the field of clamp construction only a foam of small thickness is formed, which is no longer sufficient as fire protection for 30 minutes. When laying PVC cables therefore occur again in the case of fire known problems.

It is also known to use flame-retardant or flame-retardant halogen-free cables which are hardly inflammable and low in smoke and have only a low fire propagation. However, these cables are very expensive and are therefore only used under extremely hazardous conditions.

In order to avoid the disadvantages of intumescent coatings, cable trays have been applied to materials which have an ablation effect on the cables and cable supports. act cooling and heat ceramics under heat, as described for example in DE 196 49 749 A1. Herein, a method for forming a fire protection for combustible or heat-sensitive components is described, wherein the components are provided with a coating containing an inorganic material of finely ground hydraulic binders such as calcium silicate, aluminate or ferrite, the Ablativstoffe such as aluminum as a binder - Is added or magnesium hydroxide. Disadvantage of this measure is that on the one hand the application of the material showing the ablation effect is time-consuming and on the other hand, the adhesion of the material to the cables and the cable supports is a problem.

Other coating systems currently on the market which do not have some of the above mentioned disadvantages are one-component coating compositions based on polymer dispersions containing endothermic decomposing compounds. A disadvantage of these coatings on the one hand, the relatively long drying time of the coating and the associated low dry film thickness, since these systems physically, ie by evaporation of the solvent to dry. Therefore, for thicker coatings, several are consecutive following plots, which also makes these systems time- and labor-intensive and therefore uneconomic.

The invention is therefore an object of the invention to provide an ablative-acting coating system of the type mentioned above, which avoids the disadvantages mentioned, which is in particular not solvent or water-based and has a fast curing, due to appropriately tuned viscosity is easy to apply and due to the achievable high degree of filling requires only a small layer thickness.

This object is achieved by the composition according to claim 1. Preferred embodiments are given in the dependent claims.

The invention accordingly provides a fire-retardant composition comprising a constituent A containing a multifunctional Michael acceptor having at least two electron-deficient carbon multiple bonds per molecule, with a constituent B containing a multifunctional Michael donor containing at least two thiol groups per molecule (thiol-functionalized compound), and with a constituent C containing at least one ablative fire-retardant additive.

By means of the composition according to the invention, coatings having the required layer thickness for the respective fire resistance duration can be applied in a simple and fast manner. The advantages achieved by the invention are essentially to be seen in the fact that compared to the solvent or water-based systems with their inherent slow curing times, the working time can be significantly reduced.

Another advantage is that the composition of the invention can have a high degree of filling with the fire protection additives, so that even with thin layers, a large insulating effect is achieved. The possible high degree of filling of the composition can be achieved even without the use of volatile solvents. Accordingly, the cost of materials decreases, which has a favorable effect on material costs, especially in the case of large-area application. This is achieved in particular by the use of a reactive system that does not dry physically, but hardens chemically via an addition reaction. This will endure the Compositions no volume loss by the drying of solvents or water-based systems of water. Thus, in a classical system, a solvent content of about 25% is typical. This means that from a 10 mm wet film only 7.5 mm remain as the actual protective layer on the substrate to be protected. In the composition according to the invention more than 95% of the coating remain on the substrate to be protected.

In case of fire, the binder softens and the resulting fire protection additives decompose depending on the additives used in an endothermic physical or chemical reaction to form water and inert gases, which on the one hand to cool the cable and on the other to dilute the combustible gases or by forming a protective layer, which protects the substrate from heat and oxygen attack, and on the other hand prevents the spread of fire by the burning of the coating.

The compositions of the invention show excellent adhesion to different substrates compared to solvent or water based systems when applied without primer so that they can be used universally and adhere not only to the lines to be protected but also to other substrates.

For a better understanding of the invention, the following explanations of the terminology used herein will be considered meaningful. For the purposes of the invention: a "Michael addition" is generally a reaction between a Michael donor and a Michael acceptor, frequently in the presence of a catalyst, such as a strong base, where a catalyst is not absolutely necessary; Addition is well known and frequently described in the literature, and a "Michael acceptor" is a compound having at least one Michael acceptor Michael functional group containing a Michael active carbon multiple bond, such as a CC double bond or CC triple bond, which is not aromatic, which is electron poor; a compound with two or more Michael-active carbon multiple bonds is used as a multifunctional Michael Acceptor; a Michael acceptor may have one, two, three or more separate Michael functional acceptor groups; each Michael acceptor functional group may have a Michael active carbon multiple bond; the total number of Michael-active carbon multiple bonds on the molecule is the functionality of the Michael acceptor; As used herein, the Michael Acceptor backbone is the other part of the acceptor molecule to which the Michael acceptor functional group may be attached; "electron-deficient" means that the carbon multiple bond in close proximity, ie, usually at the carbon adjacent to the multiple bond, carries electron-withdrawing groups that subtract electron density from the multiple bond, such as C = 0 and / or C = N; Donor "means a compound having at least one Michael donor functional group which is a functional group containing at least one Michael active hydrogen atom which is a hydrogen atom attached to a heteroatom, such as thiols; a compound having two or more Michael-active hydrogen atoms is referred to as a multifunctional Michael donor; a Michael donor may have one, two, three or more separate Michael functional donor groups; each functional Michael donor group can have a Michael active hydrogen atom; the total number of Michael-active hydrogen atoms on the molecule is the functionality of the Michael donor; As used herein, the "donor" framework of the Michael donor is the other part of the donor molecule to which the Michael-donor functional group is attached, and this definition also includes anions of the Michael donors, meaning "ablative" when exposed to elevated temperatures, ie above 200 ° C, such as may occur in the event of fire, a series of chemical and physical reactions take place that require energy in the form of heat, this energy is removed from the environment; this term is used synonymously with the term "endothermic decomposing"; "(meth) acrylic ... / ... (meth) acrylic ..." means that both the "methacryl ... / ... methacryl ..." - as well as the "acrylic ... / .. "acrylic" compounds are to be included; an "oligomer" is a molecule having 2 to 5 repeat units and a "polymer" is a molecule having 6 or more repeat units and may have structures that are linear, branched, star-shaped, tortuous , hyperbranched or crosslinked; polymers may have a single type of repeat unit ("homopolymers") or they may have more than one type of repeat units ("copolymers"). As used herein, "resin" is synonymous with polymer.

In general, it is believed that reacting a Michael donor with a functionality of two will result in a Michael acceptor with a functionality of two to linear molecular structures. Often, molecular structures must be created that are branched and / or crosslinked, requiring the use of at least one ingredient with a functionality greater than two. Therefore, the multifunctional Michael donor or the multifunctional Michael acceptor or both preferably have a functionality greater than two.

According to the invention, the multifunctional Michael acceptor used can be any compound which has at least two functional groups which are Michael acceptors. Each functional group (Michael acceptor) is attached to a scaffold either directly or via a linker.

According to the invention, any compound which has at least two thiol groups as functional Michael donor groups which can add to electron-poor double bonds in a Michael addition reaction (thiol-functionalized compound) can be used as the Michael donor. Each thiol group is attached either directly or via a linker to a scaffold.

The multifunctional Michael acceptor or the multifunctional Michael donor of the present invention may have any of a wide variety of scaffolds, which may be the same or different. According to the invention, the framework is a monomer, an oligomer or a polymer.

In some embodiments of the present invention, the frameworks comprise monomers, oligomers or polymers having a molecular weight (MW) of 50,000 g / mole or less, preferably 25,000 g / mole or less, more preferably 10,000 g / mole or less, even more preferably 5,000 g / mol or less, even more preferably 2,000 g / mol or less, and most preferably 1,000 g / mol or less.

As monomers suitable as skeletons, there may be exemplified alkanediols, alkylene glycols, sugars, polyvalent derivatives thereof or mixtures thereof, and amines such as ethylenediamine and hexamethylenediamine, and thiols. As oligomers or polymers suitable as skeletons, there may be exemplified polyalkylene oxide, polyurethane, polyethylene vinyl acetate, polyvinyl alcohol, polydiene, hydrogenated polydiene, alkyd, alkyd polyester, (meth) acrylic polymer, polyolefin, polyester, halogenated polyolefin, halogenated polyester, polymercaptan , as well as copolymers or mixtures thereof.

In preferred embodiments of the invention, the backbone is a polyhydric alcohol or a polyvalent amine, which may be monomeric, oligomeric or polymeric. More preferably, the backbone is a polyhydric alcohol.

As polyhydric alcohols which are suitable as scaffolds, the following may be mentioned by way of example: alkanediols, such as butanediol, pentanediol, hexanediol, alkylene glycols, such as ethylene glycol, propylene glycol and polypropylene glycol, glycerol, 2- (hydroxymethyl) propane-1,3-diol, 1, 1, 1 -Tris (hydroxymethyl) ethane, 1, 1, 1-trimethylolpropane, di (trimethylolpropane), tricyclodecanedimethylol, 2,2,4-trimethyl-1, 3-pentanediol, bisphenol A, cyclohexanedimethanol, alkoxylated and / or ethoxylated and / or propoxylated derivatives of neopentyl glycol, tetraethylene glycol cyclohexanedimethanol, hexanediol, 2- (hydroxymethyl) propane-1,3-diol, 1,1,1-tris (hydroxymethyl) ethane, 1,1,1-trimethylolpropane and castor oil, pentaerythritol, Sugars, polyvalent derivatives thereof or mixtures thereof.

As linkers, any units which are suitable for linking skeleton and functional group can be used. For thiol-functionalized compounds is the Linker preferably selected from structures (I) to (XI). For Michael acceptors, the linker is preferably selected from structures (XII) to (XIX).

1: binding to the functional group

2: binding to the scaffold

 (VI)

^ ^ ^ YT ^ f

 (VII) (VIII) (IX) (X) 4 <- n <- 10

(XI)

 (XII) (XIII) (XIV) (XV) (XVI) (XVII) (XVIII) (XIX)

Particularly preferred linkers for thiol-functionalized compounds are the structures (I), (II), (III) and (IV). Particularly preferred as a linker for Michael acceptors is structure (XII). For thiol-functionalized compounds, the functional group is the thiol group (-SH).

Particularly preferred thiol-functionalized compounds are esters of α-thioacetic acid (2-mercaptoacetates), β-thiopropionic acid (3-mercaptopropionate) and 3-thiobutyric acid (3-mercaptobutyrates) with monoalcohols, diols, triols, tetraols, pentaols or other polyols and 2 -Hydroxy-3-mercaptopropyl derivatives of monoalcohols, diols, triols, tetraols, pentaols or other polyols. Mixtures of alcohols can also be used as the basis for the thiol-functionalized compound. In this regard, reference is made to WO 99/51663 A1, the contents of which are hereby incorporated by reference.

As particularly suitable thiol-functionalized compounds may be mentioned by way of example: glycol bis (2-mercaptoacetate), glycol bis (3-mercaptopropionate), 1, 2-propylene glycol bis (2-mercaptoacetate), 1, 2-propylene glycol bis (3-mercaptopropionate), 1, 3-propylene glycol bis (2-mercaptoacetate), 1, 3-propylene glycol bis (3-mercaptopropionate), Tris (hydroxymethyl) methane tris (2-mercaptoacetate), tris (hydroxymethyl) methane tris (3-mercaptopropionate), 1,1,1-tris (hydroxymethyl) ethane tris (2-mercaptoacetate), 1,1,1 Tris (hydroxymethyl) ethane tris (3-mercaptopropionate), 1,1,1-trimethylolpropane tris (2-mercaptoacetate), ethoxylated 1,1,1-trimethylolpropane tris (2-mercaptoacetate), propoxylated 1, 1, 1-trimethylolpropane tris (2-mercaptoacetate), 1,1,1-trimethylolpropane tris (3-mercaptopropionate), ethoxylated 1,1,1-trimethylolpropane tris (3-mercaptopropionate), propoxylated trimethylolpropane tris (3-mercaptopropionate ), 1,1,1-trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tris (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (3) mercaptopropionate), pentaerythritol tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), Capcure 3-800 (BASF), GPM-800 (Gabriel Performance Products), Capcure LÖF (BASF), GPM-800LO (Ga briel Performance Products), Parkenz PE-1 (Showa Denko), 2-ethylhexyl thioglycolate, ^'' o-octyl thioglycolate, di (n-butyl) thiodiglycolate, glycol di-3-mercaptopropionate, 1,6-hexanedithiol, ethylene glycol bis ( 2-mercaptoacetate) and tetra (ethylene glycol) dithiol.

The thiol-functionalized compound can be used alone or as a mixture of two or more different thiol-functionalized compounds. For Michael acceptors, a functional group is any group which forms a Michael acceptor in combination with the one linker. Appropriately used as the Michael acceptor is a compound having at least two electron-poor carbon multiple bonds, such as C-C double bonds or C-C triple bonds, preferably C-C double bonds, per molecule as Michael functional acceptor group.

According to a preferred embodiment of the invention, the functional group of the Michael acceptor is a compound having the structure (XX):

in which R ₁ , R ₂ and R _{3 are} each independently of one another hydrogen or organic radicals, such as, for example, a linear, branched or cyclic, if appropriate substituted alkyl group, aryl group, aralkyl group (also called aryl-substituted alkyl group) or alkaryl group (also called alkyl-substituted aryl group), including derivatives and substituted versions thereof, which independently represent additional ether groups, carboxyl groups, carbonyl groups, thiol analogous groups, nitrogen containing groups or combinations thereof.

Some suitable Michael multifunctional acceptors in the present invention include, for example, molecules in which some or all of the structures (XX) are residues of (meth) acrylic acid, fumaric acid or maleic acid, substituted versions, or combinations thereof that are linked via an ester bond to the multifunctional Michael acceptor molecule are attached. A compound having structures (XX) comprising two or more residues of (meth) acrylic acid is referred to herein as "polyfunctional (meth) acrylate". Polyfunctional (meth) acrylates having at least two double bonds which can act as the acceptor in the Michael addition are preferred.

Examples of suitable di (meth) acrylates include, but are not limited to, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated bisphenol A-Di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, resorcinol diglycidyl ether di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 5 Pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated cyclohexane dimethanol di (meth) acrylate, propoxylated cyclohexane dimethanol di (meth) acrylate, aryl urethane di (meth) acrylates, aliph urethane di (meth) acrylate, polyester di (meth) acrylate and mixtures thereof.

Examples of suitable tri (meth) acrylates include, but are not limited to: trimethylolpropane tri (meth) acrylate, trifunctional (meth) acrylic acid s-triazine, glycerol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, propoxylated glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, aryl urethane tri (meth) acrylates, aliphatic urethane tri (meth) acrylates, melamine tri (meth) acrylates , Epoxy novolac tri (meth) acrylates, aliphatic epoxy tri (meth) acrylate, polyester tri (meth) acrylate and mixtures thereof.

Examples of suitable tetra (meth) acrylates include, but are not limited to: di (trimethylolpropane) tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol tetra (meth) acrylate, propoxylated dipentaerythritol tetra (meth) acrylate, arylurethane tetra (meth) acrylates, aliphatic urethane tetra (meth) acrylates, melamine tetra (meth ) acrylates, epoxy novolac tetra (meth) acrylates, polyester tetra (meth) acrylates and mixtures thereof.

It is also possible to use mixtures of the polyfunctional (meth) acrylates with one another.

Also suitable as the multifunctional Michael acceptor are polyfunctional (meth) acrylates in which the backbone is polymeric. The (meth) acrylate groups may be attached to the polymeric backbone in a variety of ways. For example, a (meth) acrylate ester monomer may be attached to a polymerizable functional group through the ester linkage, and this polymerizable functional group may be polymerized with other monomers so as to leave the double bond of the (meth) acrylate group intact. In another example, a polymer may be provided with functional groups (such as a polyester having residual hydroxyl groups) that can be reacted with a (meth) acrylate ester (for example, by transesterification) to give a polymer with (meth). to obtain acrylate side groups. In yet another example, a homopolymer or copolymer comprising a polyfunctional (meth) acrylate monomer (such as trimethylolpropane triacrylate) can be made such that not all acrylate groups react.

In a particularly preferred embodiment of the invention, the Michael-acceptor functional group is a (meth) acrylic acid ester of the aforementioned polyol compounds. Alternatively, Michael acceptors can be used in which the structure (XX) is bonded to the polyol skeleton via a nitrogen atom instead of an oxygen atom, such as (meth) acrylamides.

Mixtures of suitable multifunctional Michael acceptors are also suitable, such as the acrylamides, nitriles, fumaric acid esters and maleimides known to those skilled in the art.

Depending on the functionality of the Michael acceptor and / or the Michael donor, the degree of crosslinking of the binder and thus both the strength of the resulting coating and its elastic properties can be adjusted.

In the composition of the present invention, the relative proportion of multifunctional Michael acceptors to multifunctional Michael donors may be represented by the reactive equivalent ratio, which is the ratio of the number of all functional groups (XX) in the composition to the number of Michael-active hydrogen atoms in the composition is to be characterized. In some embodiments, the reactive equivalent ratio is 0.1 to 10: 1; preferably 0.2 to 5: 1; more preferably 0.3 to 3: 1; even more preferably 0.5 to 2: 1; most preferably 0.75 to 1.25: 1. Although the Michael addition reaction already proceeds without catalyst and curing occurs, a catalyst for the reaction between the Michael acceptor and the Michael donor can be used.

As catalysts, the nucleophiles commonly used for Michael addition reactions, in particular between electron-deficient CC multiple bonds, particularly preferably CC double bonds, and active hydrogen atoms, in particular thiols, can be used, such as trialkylphosphines, tertiary amines, a guanidine base, an alcoholate Tetraorganoammonium hydroxide, an inorganic carbonate or bicarbonate, a carboxylic acid salt or a superbase, a nucleophile such as a primary or a secondary amine or a tertiary phosphine (see, for example, CE Hoyle, AB Lowe, CN Bowman, Cem Soc., Rev. 2010, 39 , 1355-1387), which are known in the art. Suitable catalysts are, for example, triethylamine, ethyl / V, / V-diisopropylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), dimethylaminopyridine (DMAP), tetramethylguanidine (TMG), 1,8-bis (dimethylamino) naphthalene, 2,6-di-hexy / f-butylpyridine , 2,6-lutidine, sodium methoxide, potassium methoxide, sodium ethanolate, potassium ethanolate, potassium he / f-butyl alcoholate, benzyltrimethylammonium hydroxide, potassium carbonate, potassium bicarbonate, sodium or potassium salts of carboxylic acids whose conjugated acid strengths are between pK _a 3 and 1 1, n- Hexylamine, di-n-propylamine, tri-n-octylphosphine, dimethylphenylphosphine, methyldiphenylphosphine and triphenylphosphine.

The catalyst can be used in catalytic amounts or equimolar or in excess.

By adding at least one reactive diluent, the viscosity of the composition can be adjusted or adjusted according to the application properties.

Thus, in one embodiment of the invention, the composition contains other low viscosity compounds as reactive diluents to adjust the viscosity of the composition, if necessary. As a reactive diluent, as a pure substance or in a mixture, low-viscosity compounds can be used, which react with the components of the composition. Examples are allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meth) acrylic esters and thiol-functionalized compounds. Reactive diluents are preferably selected from the group consisting of allyl ethers such as allyl ethyl ether, allyl propyl ether, allyl butyl ether, allyl phenyl ether, allyl benzyl ether, trimethylol propane allyl ether, allyl ester such as allyl acetate, allyl allyl, maleic acid maleate, allyl acetoacetate, vinyl ethers such as butyl vinyl ether, 1,4-butanediol vinyl ether, ie / f Butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 1,4-cyclohexanedimethanol vinyl ether, ethylene glycol vinyl ether, diethylene glycol vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, propyl vinyl ether, ethyl 1-propenyl ether, dodecyl vinyl ether, hydroxypropyl (meth) acrylate, 1, 2

Ethanediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, phenethyl (meth) acrylate, tetrahydrofurfuryl ( meth) acrylate, ethyltriglycol (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, / V, / V-dimethylaminomethyl (meth) acrylate, Acetoacetoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, diethylene glycol di (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and / or tricyclopentadienyl di (meth) acrylate, bisphenol A (meth) acrylate, novolak epoxy di (meth) acrylate, di - [(meth) acryloyl-maleoyl] -tricyclo-5.2.1 .0. ^{2 6} -decane, dicyclopentenyloxyethyl crotonate, 3- (meth) acryloyl-oxymethyltricyclo-5.2.1 .0. ^{6 2} -decane, 3- (meth) cyclopentadienyl (meth) acrylate, isobornyl (meth) acrylate, and decalyl-2- (meth) acrylate. In principle, it is also possible to use other customary compounds having reactive double bonds, alone or in a mixture with the (meth) acrylic acid esters, eg. For example, styrene, α-methylstyrene, alkylated styrenes, such as ie / f-butylstyrene, divinylbenzene and allyl compounds.

The mode of action of the ablative composition according to the invention is based on an endothermic physical and / or chemical reaction, wherein substances which require large amounts of energy when decomposed are contained in the composition. When the cured composition of elevated temperature, such as in the case of fire, is exposed to a fire, a series of chemical and physical processes are initiated. These processes include the release of water vapor, changes in chemical composition, and the formation of non-combustible gases that keep the oxygen needed for combustion away from the surface of the cable. All of these processes require a large amount of energy that is removed from the fire. After the conversion of all organic components is completed, a stable insulating layer of inorganic constituents has formed, which has an additional insulating effect.

According to the invention, the constituent C therefore contains at least one ablative fire protection additive, it being possible to use both individual compounds and a mixture of several compounds as additives.

Appropriately used as ablative fire protection additives such materials that form energy-depleting layers by dehydration, which is embedded as in the form of water of crystallization, and water evaporation. The heat energy that has to be used to split off the water is thereby removed from the fire. Furthermore, such materials are used, which are in heat chemically alter or decompose, vaporize, sublimate or melt in an endothermic reaction. This cools the coated substrates. Often decomposition releases inert, ie non-flammable gases, such as carbon dioxide, which additionally dilute the oxygen in the immediate vicinity of the coated substrate.

Suitable gas-releasing components are hydroxides, such as aluminum hydroxide and magnesium hydroxide and their hydrates, which split off water, and carbonates, such as calcium carbonate, which split off carbon dioxide. Basic carbonates can split off both water and C0 ₂ . Preference is given to a combination of components starting at different temperatures with the gas release. Thus, the elimination of water in aluminum hydroxide begins already at about 200 ° C, whereas the elimination of magnesium hydroxide starts at about 350 ° C, so that the gas separation takes place over a wider temperature range.

Suitable ablative materials, when exposed to heat are water-releasing inorganic hydroxides or hydrates, such as those of sodium, potassium, lithium, barium, calcium, magnesium, boron, aluminum, zinc, nickel, furthermore boric acid and their partially dehydrated derivatives.

Example, the following compounds may be mentioned: LiN0 ₃ -3H ₂ 0, Na ₂ C0 ₃ H ₂ 0 (thermonatrite), Na ₂ C0 ₃ -7H ₂ 0, Na ₂ CO ₃ -10H ₂ O (sodium carbonate), Na ₂ Ca ( C0 ₃ ) ₂ -2H ₂ 0 (pirssonite), Na ₂ Ca (C0 ₃ ) ₂ -5H ₂ 0 (Gaylussite), Na (HC0 ₃ ) Na ₂ C0 ₃ -2H ₂ 0 (Trona), Na ₂ S ₂ 0 ₃ -5H ₂ 0, Na ₂ 0 ₃ Si-5H ₂ 0, KF-2H ₂ 0, CaBr ₂ -2H ₂ 0, CaBr ₂ -6H ₂ 0, CaS0 ₄ -2H ₂ 0 (gypsum), Ca (S0 ₄ ) - _^1/2 H ₂ 0 (bassanite), Ba (OH) ₂ -8 H ₂ 0, Ni (N0 _{3) 2} -6H ₂ 0, Ni (N0 _{3) 2} -4H ₂ 0, Ni (N0 _{3) 2} -2H ₂ 0, Ζη (Ν0 ₃ ) ₂ · 4Η ₂ 0, Ζη (Ν0 ₃ ) ₂ · 6Η ₂ 0, (ΖηΟ) ₂ (Β ₂ 0 ₃ ) ₂ · 3Η ₂ 0, Mg (NO ₃ ) ₂ - 6H ₂ 0 (US 5985013 A), MgS0 ₄ -7H ₂ 0 (EP1069172A), Mg (OH) ₂ , Al (OH) ₃ , ΑΙ (ΟΗ) ₃ · 3Η ₂ 0, AIOOH (boehmite), Al ₂ [S0 ₄ ] ₃ -nH ₂ 0 where n = 14-18 (US 4,462,831 B), optionally mixed with AINH ₄ (SO ₄ ) ₂ -12H ₂ O (US5104917A), KAI (SO ₄ ) ₂ -12H ₂ O (EP1069172A ), CaO-Al ₂ O ₃ -10H ₂ O (nesquehonite), MgC0 ₃ -3H ₂ 0 (Wermlandite), Ca ₂ Mg ₁₄ (Al, Fe) ₄ C0 ₃ (OH) ₄₂ -29H ₂ 0 (thaumasite), Ca ₃ Si (O H) ₆ (S0 ₄ ) (C0 ₃ ) -12H ₂ 0 (artinite), Mg ₂ (OH) ₂ C0 ₃ -H ₂ 0 (ettringite), 3CaO-Al ₂ 0 ₃ -3CaS0 ₄ -32H ₂ 0 (hydromagnesite ), Mg ₅ (OH) ₂ (CO ₃ ) ₄ -4H ₂ O (hydrocalumite), Ca ₄ Al ₂ (OH) ₁₄ -6H ₂ O (hydrotalcite), Mg ₆ Al ₂ (OH) ₁₆ CO ₃ -4H ₂ 0 Alumohydrocalcite, CaAl ₂ (OH) ₄ (C0 ₃ ) ₂ -3H ₂ 0 Scarbroite, Al ₁₄ (C0 ₃ ) ₃ (OH) ₃₆ Hydrogranate, 3CaO-Al ₂ 0 ₃ -6H ₂ 0 Dawsonite, NaAl (OH) C0 ₃ , hydrous zeolites, vermiculite, colemanite, perlite, mica, alkali silicates, borax, modified coals and graphites, silicas.

In a preferred embodiment, the hydrogenated salts are selected from the group consisting of Al ₂ (SO ₄ ) -16-18H ₂ O, NH ₄ Fe (SO ₄ ) ₂ -12H ₂ O, Na ₂ B ₄ O ₇ -10H ₂ O. , NaAl (S0 _{4) 2} -12H ₂ 0, AINH ₄ (S0 _{4) 2} -12-24H ₂ 0, Na ₂ SO ₄ -10H ₂ O, MgS0 ₄ -7H ₂ 0, (NH _{4) 2} S0 ₄ - 12H ₂ 0; KAI (S0 _{4) 2} -12H ₂ 0, Na ₂ Si0 ₃ -9H ₂ 0, Mg (N0 _{2) 2} -6H ₂ 0, Na ₂ C0 ₃ -7H ₂ 0 and mixtures thereof (EP1069172A). Particularly preferred are aluminum hydroxide, Aluminiumhydroxidhydrate, magnesium hydroxide and zinc borate, since they have an activation temperature below 180 ° C.

Optionally, one or more reactive flame retardants may be added to the composition of the invention. Such compounds are incorporated in the binder. An example within the meaning of the invention are reactive organophosphorus compounds, such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives and adducts. Such compounds are described, for example, in S. V Levchik, E. D Weil, Polym. Int. 2004, 53, 1901 -1929 or E.D. Weil, S.V. Levchik (ed.), Flame Retardants for Plastics and Textiles - Practical Applications, Hanser, 2009.

The ablative fire-retardant additive may be included in the composition in an amount of from 5 to 99% by weight, the amount depending substantially on the application form of the composition (spraying, brushing and the like). In order to achieve the best possible isolation, the proportion of ingredient C in the overall formulation is set as high as possible. The proportion of constituent C in the overall formulation is preferably 5 to 85% by weight and more preferably 40 to 80% by weight.

In addition to the ablative additives, the composition may optionally contain conventional auxiliaries, such as solvents, for example xylene or toluene, wetting agents, for example based on polyacrylates and / or polyphosphates, defoamers, such as silicone defoamers, thickeners, such as alginate thickeners, dyes, fungicides, plasticizers, such as chlorine-containing waxes , Binders, flame retardants or various fillers, such as vermiculite, inorganic Fibers, quartz sand, glass microspheres, mica, silica, mineral wool, and the like.

Additional additives such as thickeners, rheology additives and fillers can be added to the composition. As rheology additives, such as anti-settling agents, anti-sagging agents and thixotropic agents, are preferred

Polyhydroxycarboxamides, urea derivatives, salts of unsaturated carboxylic acid esters, alkylammonium salts of acidic phosphoric acid derivatives, ketoximes, amine salts of p-toluenesulfonic acid, amine salts of sulfonic acid derivatives and aqueous or organic solutions or mixtures of the compounds used are used. In addition, rheology additives based on pyrogenic or precipitated silicas or based on silanized pyrogenic or precipitated silicas can be used. The rheology additive is preferably fumed silicas, modified and unmodified phyllosilicates, precipitated silicas, cellulose ethers, polysaccharides, PU and acrylate thickeners, urea derivatives, castor oil derivatives, polyamides and fatty acid amides and polyolefins, if they are in solid form, pulverized celluloses and / or Suspending agents such as Xanthan gum.

The composition of the invention can be formulated as a two- or multi-component system.

If ingredient A and ingredient B do not react with each other without the use of an accelerator at room temperature, they may be stored together. If a reaction occurs at room temperature, the component A and the component B must be arranged reaction-inhibiting separately. In the presence of an accelerator, it must either be stored separately from ingredients A and B, or the ingredient containing the accelerator must be stored separately from the other ingredient. This ensures that the two components A and B of the binder are mixed together just prior to use and trigger the curing reaction. This makes the system easier to handle.

In a preferred embodiment of the invention, the composition according to the invention is packaged as a two-component system, wherein the component A and the component B are arranged reaction-inhibiting separately. Accordingly contains a first component, the component I, the component A and a second component, the component II, the component B. This ensures that the two components A and B of the binder are mixed together immediately prior to use and trigger the curing reaction , This makes the system easier to handle.

In this case, the multifunctional Michael acceptor is preferably contained in an amount of 2 to 95 wt .-% in the component I. The multifunctional Michael donor is preferably contained in the amount of from 2 to 95% by weight, more preferably in an amount of from 2 to 85% by weight, in the component II.

The component C can be contained as a total mixture or divided into individual components in one or more components. The division of ingredient C is dependent on the compatibility of the compounds contained in the composition, so that neither a reaction of the compounds contained in the composition with each other or a mutual interference can take place. This depends on the connections used. This ensures that the highest possible proportion of fillers can be achieved. This leads to a good cooling, even with low layer thicknesses of the composition.

The composition is applied as a paste with a brush, a roller or by spraying onto the substrate, which may be metallic, plastic in the case of cable trays or soft rock from mineral wool. Preferably, the composition is applied by means of an airless spray process.

The composition according to the invention is characterized by a relatively rapid curing by an addition reaction and thus unnecessary physical drying compared to the solvent and water-based systems. This is particularly important when the coated components have to be loaded or further processed quickly, either by coating with a cover layer or by moving or transporting the components. Also, the coating is thus much less susceptible to external influences on the site, such as exposure to (rain) water or dust and dirt, which in losemittel- or water-based systems can lead to washing out of water-soluble constituents, or in the absorption of dust to a reduced ablative effect. Due to the low viscosity of the composition despite the high solids content, which can be up to 99 wt .-% in the composition without the addition of volatile solvents, the composition remains easy to process, in particular by conventional spraying.

Therefore, the composition according to the invention is particularly suitable as a fire protection coating, in particular sprayable coating for components on a metallic and non-metallic basis. The composition of the invention is mainly used in the construction sector as a coating, in particular fire protection coating for individual cables, cable bundles, cable trays and cable ducts or other lines use and as fire protection coating for steel construction elements, but also for construction elements of other materials, such as concrete or wood.

Another object of the invention is therefore the use of the composition according to the invention as a coating, in particular as a coating for construction elements or components made of steel, concrete, wood and other materials, such as plastics, in particular as fire protection coating for individual cables, cable bundles, cable trays and cable ducts or other Lines or Softschotts.

The present invention also relates to objects obtained when the composition of the invention has cured. The objects have excellent ablative properties.

The following examples serve to further illustrate the invention. EMBODIMENTS

For the preparation of ablative compositions according to the invention, the constituents listed below are used. In each case, the individual components are mixed with the aid of a dissolver and homogenized. For the Application, these mixtures are then mixed or applied either before spraying or during spraying.

To determine the fire protection properties, the cured composition was subjected to an EN ISO 1 1925-2 test. The test is carried out in a draft-free Mitsubishi FR-D700SC Electric Inverter. During the test, a small burner flame is directed onto the surface of the sample at an angle of 45 ° for 30 s, which corresponds to surface flaming. In each case, samples with the dimensions 1 1 cm x 29.5 cm and an application thickness of 2-3 mm are used. These samples cured at room temperature and were aged at 40 ° C for three days.

After aging for three days at 40 ° C, the flammability and height of the affected area are checked.

Cure time and cure history were determined. It was tested with a spatula when the curing of the coating starts. For the following Examples 1 and 2, aluminum trihydrate (HN 434 of J. M. Huber Corporation, Finland) was used as ingredient C and used in an amount of 18.0 g:

example 1

Component A

 Component Quantity [g]

 Glycol di (3-mercaptopropionate) 32.8

Durcal 5 ¹⁾ 36,0

 Calcium carbonate, ground component B

 Component Quantity [g]

 1,1,1-tris (hydroxymethyl) propane triacrylate 27.2

Durcal 5 36.0 Example 2

Component A

Comparative Example 1

As a comparison was based on aqueous dispersion technology (acrylate dispersion) commercial fire protection product (Hilti CFP SP-WB).

Table 1: Results of determination of curing time, ignition and flame height

Comparative Example 1 Example 2 Example 1

 Curing time 24 h <1 h <1 h

Inflammation yes no no

Flame height 150 mm 32 mm 26 mm

Claims

1 . A fire-retardant composition comprising an A component containing a multifunctional Michael acceptor having at least two electron-deficient carbon multiple bonds per molecule as a Michael acceptor functional group with a B constituent containing a multifunctional Michael donor containing at least two thiol Groups per molecule as a Michael-donor functional group, and with a C-component containing at least one ablative fire-retardant additive.

2. The composition of claim 1, wherein the Michael-acceptor functional group has the structure (XX):

Ri, R ₂ and R _{3 are} each independently hydrogen, a linear, branched or cyclic, optionally substituted alkyl group, aryl group, aralkyl group or alkylaryl group, these independently of one another additional ether groups, carboxyl groups, carbonyl groups, thiol-analogous groups, nitrogen-containing groups or Combinations thereof may contain.

The composition of claim 2 wherein each Michael acceptor functional group is attached directly to a backbone, either directly or via a linker.

A composition according to claim 3 wherein the backbone is a monomer, an oligomer or a polymer.

A composition according to claim 4, wherein the skeleton is a polyol compound selected from the group consisting of alkanediols, alkylene glycols, glycerin, 2- (hydroxymethyl) propane-1,3-diol, 1,1,1-tris ( hydroxymethyl) ethane, 1,1,1-trimethylolpropane, di (trimethylolpropane), tricyclodecanedimethylol, 2,2,4-trimethyl- 1, 3-pentanediol, bisphenol A, cyclohexanedimethanol, alkoxylated and / or ethoxylated and / or propoxylated derivatives of neopentyl glycol, tetraethylene glycol cyclohexanedimethanol, hexanediol, 2- (hydroxymethyl) propane-1,3-diol, 1,1,1-tris (hydroxymethyl ) ethane, 1,1,1-trimethylolpropane and castor oil, pentaerythritol, sugars, polyvalent derivatives thereof, or mixtures thereof.

A composition according to any one of the preceding claims, wherein the multifunctional Michael donor has at least three thiol groups per molecule.

A composition according to any one of the preceding claims, wherein the multifunctional Michael donor is selected from the group consisting of glycol bis (2-mercaptoacetate), glycol bis (3-mercaptopropionate), 1,2-propylene glycol bis (2 -mercaptoacetate), 1,2-propylene glycol bis (3-mercaptopropionate), 1,3-propylene glycol bis (2-mercaptoacetate), 1,3-propylene glycol bis (3-mercaptopropionate), tris (hydroxymethyl) methane tris (2-mercaptoacetate), tris (hydroxymethyl) methane tris (3-mercaptopropionate), 1,1,1-tris (hydroxymethyl) ethane tris (2-mercaptoacetate), 1,1,1-tris (hydroxymethyl) ethane tris (3-mercaptopropionate), 1,1,1-trimethylolpropane tris (2-mercaptoacetate), ethoxylated 1,1,1-trimethylolpropane tris (2-mercaptoacetate), propoxylated 1,1,1-trimethylolpropane tris (2 -mercaptoacetate), 1, 1, 1 -

Trimethylolpropane tris (3-mercaptopropionate), ethoxylated 1,1,1-trimethylolpropane tris (3-mercaptopropionate), propoxylated trimethylolpropane tris (3-mercaptopropionate), 1,1,1-trimethylolpropane tris (3-mercaptobutyrate),

Pentaerythritol tris (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptobutyrate), pentaerythritol tetrakis (3 n-butyl) thiodiglykolat -mercaptobutyrat), 2-ethylhexyl, / ^'so-octyl thioglycolate, di (, glycol di-3-mercaptopropionate, 1, 6-hexanedithiol, ethylene glycol bis (2-mercaptoacetate) and tetra (ethylene glycol) dithiol ,

A composition according to any one of the preceding claims, wherein the reactive equivalent ratio is in the range of 0.1: 1 to 10: 1.

9. A composition according to any one of the preceding claims, wherein the component A and / or the component B further contains a catalyst for the Michael addition reaction.

10. The composition according to any one of the preceding claims, wherein the one acting ablative fire retardant additive is selected from the group at least consisting of LiN0 ₃ -3H ₂ 0, Na2C03H20 (thermonatrite), Na ₂ C0 ₃ -7H ₂ 0, Na ₂ CO ₃ - 10H ₂ O (sodium carbonate), Na ₂ Ca (C0 _{3) 2} .2H ₂ 0 (Pirssonit), Na ₂ Ca (C0 _{3) 2} -5H ₂ 0 (Gaylussite), Na (HC0 ₃₎ of Na ₂ C0 ₃ -2H ₂ 0 (trona), Na ₂ S ₂ 0 ₃ -5H ₂ 0, Na ₂ 0 ₃ Si-5H ₂ 0, KF-2H ₂ 0, CaBr ₂ -2H ₂ 0, CaBr ₂ -6H ₂ 0, CaSO ₄ - 2H ₂ 0 (gypsum), Ca (S0 ₄₎ - _^1/2 H ₂ 0 (bassanite), Ba (OH) ₂ -8 H ₂ 0, Ni (N0 _{3) 2} -6H ₂ 0, Ni (N0 _{3) 2} -4H ₂ 0, Ni (NO ₃ ) ₂ -2H ₂ 0, Ζη (Ν0 ₃ ) ₂ · 4Η ₂ 0, Ζη (Ν0 ₃ ) ₂ · 6Η ₂ 0, (ΖηΟ) ₂ (Β ₂ 0 ₃ ) ₂ · 3Η ₂ 0, Mg (N0 _{3) 2} -6H ₂ 0 (US 5985013 A), MgS0 ₄ -7H ₂ 0 (EP1069172A), Mg (OH) _2, AI (OH) _3, ΑΙ (ΟΗ) ₃ · 3Η ₂ 0, AIOOH (boehmite), Al ₂ [S0 ₄ ] ₃ -nH ₂ 0 with n = 14-18 (US 4,462,831 B), optionally mixed with AINH ₄ (S0 ₄ ) ₂ -12H ₂ 0 (US5104917A), KAI (S0 ₄ ) ₂ -12H ₂ O (EP1069172A), CaO-Al ₂ O ₃ -10H ₂ O (Nes quehonit), MgC0 ₃ -3H ₂ 0 (wermlandite), Ca ₂ Mg ₁₄ (Al, Fe) ₄ C0 ₃ (OH) ₄₂ -29H ₂ 0 (Thaumasit), Ca ₃ Si (OH) ₆ (S0 ₄₎ (C0 ₃ ) -12H ₂ 0 (artinite), Mg ₂ (OH) ₂ C0 ₃ -H ₂ O (ettringite), 3CaO-Al ₂ 0 ₃ -3CaS0 ₄ -32H ₂ 0 (hydromagnesite), Mg ₅ (OH) ₂ ( C0 ₃ ) ₄ -4H ₂ 0 (hydrocalumite), Ca ₄ Al ₂ (OH) ₁₄ -6H ₂ 0 (hydrotalcite), Mg ₆ Al ₂ (OH) ₁₆ C0 ₃ -4H ₂ 0 Alumohydrocalcite, CaAl ₂ (OH) ₄ (C0 ₃ ) ₂ -3H ₂ 0 Scarbroite, Al ₁₄ (C0 ₃ ) ₃ (OH) ₃₆ Hydrogranate, 3CaO-Al ₂ 0 ₃ -6H ₂ 0 Dawsonite, NaAl (OH) C0 ₃ , hydrous zeolites, vermiculites, colemanite, Perlites, mica, alkali silicates, borax, modified carbon, graphites, silicic acids and mixtures thereof.

1 1. Composition according to one of the preceding claims, wherein the composition further contains organic and / or inorganic additives and / or other additives.

12. A composition according to any one of the preceding claims, which is formulated as a two- or multi-component system.

13. Use of the composition according to any one of claims 1 to 12 as a coating.

14. Use according to claim 13 for the coating of structural elements.

15. Use according to claim 13 for the coating of non-metallic components.

16. Use according to any one of claims 13 to 15 as fire protection layer, in particular for individual cables, cable bundles, cable routes and cable ducts or other lines or soft bulkheads.

17. Hardened objects obtained by curing the composition according to any one of claims 1 to 12.