Foamable multi-component composition and foamed fire protection profile with temperature-regulating fillers

Description

[0001] The present invention relates to a foamable multi-component composition for the production of foamed fire protection profiles, as well as to fire protection profiles produced from the multi-component composition according to the invention. The foamable multi-component composition and the fire protection profile comprise at least one temperature-regulating filler that improves the fire resistance duration in the event of a fire. Furthermore, the present invention relates to the use of temperature-regulating fillers to improve the fire resistance duration of fire protection profiles, in particular fire protection profiles with a low density. The invention is set forth in the attached set of claims.

[0002] When laying cables, such as pipes, electrical cables, and the like, these are routed through openings in building components, especially structural elements like walls and ceilings. To prevent the passage of fire and smoke in the event of a fire, fire-resistant sealing materials, such as fire-resistant cushions and fire-resistant blocks, are installed between the inner walls of the openings and the cables passing through them. These often consist of polyurethane foams. However, other foams, such as those based on epoxy amines, are also used.

[0003] Patent specification WO2019 / 145175 A1 describes an assembly consisting of several fire-resistant profiles. The fire-resistant profiles used to manufacture the assembly have a reduced density of 100 kg / m³ to 200 kg / m³ in their cured state. This has the particular advantage that the fire-resistant profiles are at least somewhat more compressible, thus eliminating the need for time-consuming cutting when sealing penetrations. However, a reduction in density can negatively affect the fire resistance duration in the event of a fire. WO2019 / 145175 A1 therefore proposes the use of an inorganic fiber material and a film. The fire-resistant profiles are designed in such a way that they fuse together in the event of a fire.

[0004] EP 3 696 206 A1 discloses an expandable graphite as an intumescent additive, as part of a foamable, intumescent multi-component composition based on polyisocyanates and NCO-reactive polyols and / or amino-functional compounds and other additives. EP 3 327 069 A1 also describes an expandable graphite as part of a foamable, intumescent multi-component composition based on silyl-terminated prepolymers, with further flame retardants that cause chemical intumescence. EP 1 400 547 A1 discloses two-component foam systems for construction purposes, which are based on a polyisocyanate component, an aqueous polyacrylate copolymer dispersion, water as an intumescent agent, polyols, and a hydrous phyllosilicate.CN 111 117 211 A discloses a foamable multi-component composition containing polyisocyanate, polyether polyol, expandable graphite as an intumescent fire protection additive, catalyst, foam stabilizer, water as a blowing agent and silica gel as a temperature-regulating filler.

[0005] However, there remains a need to combine the installation advantages of low densities in fire protection profiles with improved fire resistance.

[0006] It is therefore an object of the present invention to provide a solution with which the fire resistance duration of foamed fire protection profiles, in particular of foamed fire protection profiles with a low density, can be reliably improved in the event of a fire.

[0007] The problem underlying the invention was surprisingly solved by using temperature-regulating fillers in a foamable multi-component composition. Temperature-regulating fillers, as defined in the present invention, are those fillers that are capable of producing a cooling effect in the event of a fire. This cooling effect can be achieved through active or passive cooling. Active cooling refers to a controlled reduction in temperature, for example, caused by a chemical reaction. Passive cooling refers to an insulating effect. The use of temperature-regulating fillers in fire protection profiles thus makes it possible, in the event of a fire, to delay or even prevent heat transfer to the side facing away from the fire.

[0008] A second object of the invention is a fire protection profile produced from the foamable multi-component composition according to the invention.

[0009] A third object of the invention is also the use of the inventive foamable multi-component composition in fire protection profiles to improve the fire resistance duration.

[0010] For a better understanding of the invention, the following explanations of the terminology used herein are considered useful. For the purposes of the invention: " Endothermic fillers" These are fillers that undergo an endothermic reaction when heat is applied (such as in a fire). An endothermic reaction is a chemical reaction in which energy is absorbed from the environment. The term " filler " are to be understood as organic and / or inorganic, preferably inorganic, compounds that increase the volume of the multi-component composition;" thermal conductivity Thermal conductivity is a material property and describes a material's ability to transport thermal energy in the form of heat. It is measured in W / mK. Multi-component composition "is a composition comprising several separately stored components, such that a reaction of the individual components only occurs after all components have been mixed. In a preferred embodiment of the invention, the multi-component composition is a Two-component composition, which comprises two separately stored components. The two-component composition includes an isocyanate component (A) and a component (B) that is reactive towards isocyanate groups, so that a reaction of the isocyanate groups contained in the isocyanate component (A) only occurs after the two components are mixed; Isocyanates" are compounds that possess a functional isocyanate group -N=C=O and are characterized by the structural unit RN=C=O (with R as the organic residue); " Polyisocyanates " are compounds that have at least two functional isocyanate groups -N=C=O; diisocyanates, which also fall under the definition of polyisocyanate, are characterized, for example, by the structure O=C=NRN=C=O, where R represents any organic residue; " medium NCO functionality", describes the number of isocyanate groups in the compound; in a mixture of isocyanates, the "average NCO functionality" describes the average number of isocyanate groups in the mixture and is determined according to the formula: average NCO functionality (mixture) = Σ average NCO functionality (isocyanate i) / ni , i.e., the sum of the average NCO functionality of the individual component divided by the number of individual components; Isocyanate component(A)" or A-component describes a component of the multi-component composition, which includes at least one polyisocyanate and, if applicable, at least one filler and / or at least one rheology additive and / or other additives; Amines " are compounds with at least one functional NH group derived from ammonia by replacing one or two hydrogen atoms with hydrocarbon groups and exhibiting the general structures RNH₂ (primary amines) and R₂NH₂ (secondary amines) (see: IUPAC Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"), Compiled by A.D. McNaught and A. Wilkinson, Blackwell Scientific Publications, Oxford (1997)); As " alcohols "Polyols" are organic compounds in which at least one hydroxyl group (-OH) is bonded to a saturated carbon atom. "Polyols" are alcohols that have at least two functional hydroxyl groups (-OH). NH functionality " or " OH functionality" of an amine or an alcohol describes the number of active hydrogen atoms that can react with an isocyanate group; " medium NH functionality" or " medium "OH functionality" describes the number of active hydrogen atoms in an amine or alcohol that can react with an isocyanate group. This results from the number and NH or OH functionality of the amino or hydroxyl groups contained in the compound. Reactive component (B) that is reactive towards isocyanate groups or also " B-component " is a component of the multi-component composition, which comprises at least one amine reactive towards isocyanate groups and / or at least one alcohol reactive towards isocyanate groups. The "B component" may optionally also comprise at least one filler and / or at least one rheology additive and / or other additives; " a ", " one ", " one"The article used before a class of chemical compounds, e.g., before the word "isocyanate," indicates that one or more compounds falling under this class of chemical compounds, e.g., various isocyanates, may be meant. In a preferred embodiment, this article refers only to a single compound; "at least one", "at least one", "at least one" numerically "one or more". In a preferred embodiment, this term is numerically "a", "an", "a" meant; "contain", "comprise" and "include", that, in addition to the aforementioned components, further components may be present. These terms are inclusive and therefore also encompass... "consist of". "consist of" This is meant to be conclusive and means that no further components can be present. In a preferred embodiment, the terms mean "contain", "comprise" and "include" the term "consist of"; Temperature-regulating fillers

[0011] The foamable multi-component composition according to the invention comprises at least one temperature-regulating filler as defined in claim 1. The temperature-regulating filler can be used in the isocyanate component (A) and / or in the B component. In a preferred embodiment of the invention, the temperature-regulating filler is contained at least in the B component. In a further preferred embodiment, the temperature-regulating filler is present only in the B component, and the isocyanate component (A) does not contain a temperature-regulating filler.

[0012] The term "temperature-regulating filler"This term refers to a filler that, when exposed to heat (such as in the event of a fire), has a temperature-inhibiting effect for at least a certain period of time. The temperature-regulating filler is an endothermic filler containing at least one crystalline or semi-crystalline inorganic compound containing water of hydration, selected from the group consisting of ettringites, layered double hydroxides (LDH), or mixtures thereof, or it is a temperature-regulating filler with a thermal conductivity <1 W / m·K and selected from the group consisting of brick dust, aerogels, or mixtures thereof.

[0013] Endothermic fillers are those fillers that undergo an endothermic reaction when exposed to heat (such as in the event of a fire). An endothermic reaction is a chemical reaction in which energy is absorbed from the surroundings.

[0014] Preferably, the endothermic reaction of the endothermic filler used begins in a temperature range of 70 °C to 300 °C (so-called onset temperature determined by thermogravimetric analysis (TGA)), preferably in a temperature range of 70 °C to 200 °C, and particularly in a temperature range of 70 °C to 115 °C. Within the specified temperature ranges, an equilibrium exists between the desired cooling mechanism and the reaction temperature of the intumescent fire protection additive.

[0015] The endothermic filler is preferably used in a weight percentage range of 1 to 70 based on the total weight of the multi-component composition, in particular in a proportion of 10 wt.% to 15 wt.%, in the multi-component composition according to the invention.

[0016] One option for selecting endothermic fillers is the use of crystalline or semi-crystalline inorganic compounds containing water of hydration (H₂O). Water of hydration, also known as water of crystallization, is water that occurs bound within the crystalline or semi-crystalline solid. The release of the water of hydration from the crystalline / semi-crystalline inorganic compound occurs via an endothermic reaction. It is particularly advantageous to use crystalline or semi-crystalline solids with the highest possible water of crystallization content. Preferably, the weight percentage of water of crystallization in the crystalline or semi-crystalline solid used is at least 15 wt%, and preferably at least 20 wt%.

[0017] The temperature-regulating filler according to the present invention is an endothermic filler containing at least one crystalline or semi-crystalline inorganic compound comprising water of hydration, selected from the group consisting of ettringites, layered double hydroxides (LDH) or mixtures thereof.

[0018] The term ettringite, as used in the present invention, refers to calcium aluminum sulfate hydrates. Naturally occurring ettringite minerals have a composition with the structural formula Ca₆Al₂[(OH)₁₂(SO₄)₃]·26H₂O. Ettringite can also be produced synthetically. In a preferred embodiment of the invention, synthetically produced ettringite with the formula 3CaO·Al₂O·3·3CaSO₄·32H₂O is used as an endothermic filler. This is commercially available, for example, under the trade name CASUL Powder H1i. A positive endothermic effect can be observed even with a quantity of at least 1 wt% ettringite based on the total weight of the foamable multi-component composition. In a preferred embodiment, the weight percentage of ettringite based on the total weight of the foamable multi-component composition is 1 wt.% to 50 wt.%, preferably 10 to 25 wt.%.

[0019] The term Layered Double Hydroxides (LDHs) refers to a class of ionic solid compounds exhibiting a layered molecular structure with the molecular structure [M(II) 1-x M(III) x (OH) 2 ] x+< (A n-< x / n )·mH 2 O, where x is a number from 0.22 to 0.33, M is a metal, and A n-< is an n-valent anion. LDHs are typically synthetic materials derived from natural hydrotalcite, Mg 6 Al 2 (OH) 16 [CO 3 ]·4H 2 O. Within the scope of the present invention, LDHs with an MgO:Al 2 O 3 ratio of 70:30 are particularly suitable. This is commercially available, for example, under the trade name PLURAL MG70. In a preferred embodiment, the weight percentage of LDH based on the total weight of the multi-component composition is 7 wt.% to 50 wt.%, preferably 10 wt.% to 30 wt.%.

[0020] Another temperature-regulating filler according to the present invention is a temperature-regulating filler with a thermal conductivity of <1 W / m·K and selected from the group consisting of brick dust, aerogels, or mixtures thereof. Such materials impart a heat-insulating effect to the fire protection profile in the event of a fire.

[0021] The use of brick dust is particularly advantageous in this context. Brick dust has a thermal conductivity of 0.3 to 0.7 W / (m·K).

[0022] Brick dust is obtained by grinding bricks. For the purposes of this invention, the term "brick" refers to all masonry bricks as defined in DIN EN 771-1. Accordingly, masonry bricks are building blocks made of clay or other clay-containing materials, with or without sand or other additives, which are fired at a sufficiently high temperature to achieve a ceramic bond. The term "building block" refers to a pre-formed element for constructing masonry. Ceramic clinker bricks or finely ground ceramics, such as sanitary ceramics, can also be used.

[0023] In principle, brick dust can be used in various particle sizes. Following the grinding process, the brick dust is typically subjected to a sieving process. By selecting the sieve(s) with a defined mesh size, the particle size of the brick dust can be adjusted to a specific range. For example, when using a sieve with a mesh size of 0.3 mm, the brick dust will contain particles with a size of ≤ 0.3 mm (particle size range > 0 to 0.3 mm). However, due to the varying orientation of the brick dust particles during the sieving process, it is also possible that a small proportion of the particles will be larger than the sieve mesh size. This is particularly relevant for asymmetrically shaped particles (e.g., rod-shaped).To account for this, the so-called d90 value is used to specify the particle size within the scope of the present invention. The d90 value is a parameter indicating that 90% of the sample volume has a particle size smaller than the specified value. Within the scope of the present invention, the d90 value is determined by means of static light scattering (device: Beckman Coulter LS 13 320 / Dry Powder System). In a particularly preferred embodiment, the brick dust has a d90 value in the range of 0.5 mm to 0.01 mm, preferably in the range of 0.35 mm to 0.05 mm, and more preferably in the range of 0.30 mm to 0.1 mm.

[0024] Commercially, the advantageous brick dusts are available, for example, from Pilosith GmbH, Peter Stadler GmbH or Kalkladen GmbH.

[0025] In a preferred embodiment, the weight percentage of brick dust based on the total weight of the foamable multi-component composition is 1 wt.% to 70 wt.%, preferably 10 to 40 wt.%, more preferably 15 to 25 wt.%.

[0026] Furthermore, so-called aerogels are suitable for use as fillers with low thermal conductivity within the scope of the present invention. Aerogels are understood to be highly porous solids in which > 90% of the volume consists of pores. Aerogels typically exhibit a thermal conductivity in the range of approximately 0.2 W / mK. Preferably, silicate-based aerogels are used within the scope of the present invention. However, it is also conceivable that aerogels based on plastic and / or carbon could be used. For example, Aerogel Particles P100 from Cabot are commercially available.

[0027] Due to the low weight of the aerogel particles, the quantity is usually specified volumetrically and not gravimetrically. In a preferred embodiment of the invention, 7 to 80 ml, preferably 20 to 70 ml, of aerogel are used per 100 g of the foamable multi-component composition. The use of a higher quantity of aerogel particles results in a porous mass rather than foam when producing the foamed fire protection profile.

[0028] In a particularly preferred embodiment of the invention, the foamable multi-component composition comprises both an endothermic filler and a filler with a thermal conductivity of < 1 W / m·K. In the event of a fire, this initially delays the heat input due to the insulating effect of the filler with the low thermal conductivity. Once the reaction temperature of the endothermic filler is reached, additional "active cooling" occurs through the endothermic reaction. In a particularly preferred embodiment, the endothermic filler and the filler with a thermal conductivity of < 1 W / m·K are used in a weight percentage ratio of 1:1. Isocyanate component (A)

[0029] The multi-component system according to the invention comprises at least one isocyanate component (A) and at least one component (B) that is reactive towards isocyanate groups. The isocyanate component (A) and the component (B) that is reactive towards isocyanate groups are separated from each other prior to application in a reaction-inhibiting manner.

[0030] The isocyanate component (A) comprises at least one polyisocyanate. Any aliphatic and / or aromatic isocyanates known to those skilled in the art, with an average NCO functionality of 2 or greater, can be used as the polyisocyanate, either individually or in any mixture with one another. The NCO functionality indicates how many NCO groups are present in the polyisocyanate. Polyisocyanate means that the compound contains two or more NCO groups.

[0031] Suitable aromatic polyisocyanates are those with aromatically bonded isocyanate groups, such as diisocyanatobenzenes, toulol diisocyanates, diphenyl diisocyanates, diphenylmethane diisocyanates, diisocyanatonaphathalins, triphenylmethane triisocyanates, but also those with isocyanate groups that are bonded to an aromatic via an alkylene group, such as a methylene group, such as bis- and tris-(isocyanatoalkyl)benzenes, -toluenes and -xylenes.

[0032] Preferred examples of aromatic polyisocyanates are: 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,5-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, tetramethyl-1,3-xylylene diisocyanate, tetramethyl-1,4-xylylene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,4-bis(isocyanatomethyl)benzene, ethylphenyl diisocyanate, 2-dodecyl-1,3-phenylene diisocyanate, 2,4,6-triisopropyl-m-phenylene diisocyanate, 2,4,6-trimethyl-1,3-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate. 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, diphenylene methane 2,4'-diisocyanate, diphenylene methane 2,2'-diisocyanate, Diphenylenemethane-4,4'-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, 5-( p-Isocyanatobenzyl)-2-methyl-m-phenylene diisocyanate, 4,4-diisocyanato-3,3,5,5-tetraethyldiphenylmethane, 5,5'-ureylenedi-o-tolyl diisocyanate, 4-[(5-isocyanato-2-methylphenyl)methyl]-m-phenylene diisocyanate, 4-[(3-isocyanato-4-methylphenyl)methyl]-m-phenylene diisocyanate, 2,2'-methylene-bis[6-(o-isocyanatobenzyl)phenyl] diisocyanate.

[0033] Preferably, aliphatic isocyanates are used which have a carbon backbone (without the contained NCO groups) of 3 to 30 carbon atoms, preferably of 4 to 20 carbon atoms.

[0034] Examples of aliphatic polyisocyanates are bis(isocyanatoalkyl) ethers or alkane diisocyanates, such as methane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate (e.g., hexamethylene diisocyanate, HDI), heptane diisocyanate (e.g., 2,2-dimethylpentane-1,5-diisocyanate, octane diisocyanate), nonane diisocyanate (e.g., trimethyl-HDI (TMDI), usually as a mixture of the 2,4,4- and 2,2,4-isomers), 2-methylpentane-1,5-diisocyanate (MPDI), nonane triisocyanate (e.g.,4-Isocyanatomethyl-1,8-octanediisocyanate, 5-methyl nonanediisocyanate), decane diisocyanates, decane triisocyanates, undecane diisocyanates, undecane triisocyanates, dodecane diisocyanates, dodecane triisocyanates, 1,3- and 1,4-bis-(isocyanatomethyl)cyclohexanes (H 6 XDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), bis-(4-isocyanatocyclohexyl)methane (H 12 MDI), bis-(isocyanatomethyl)norbornane (NBDI) or 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI), octagydro-4,7-methano-1 H-indendiemthyl diisocyanate, norbornene diisocyanate, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane, ureylene bis(p-phenylene methylene-p-phenylene) diiscoyanate.

[0035] Particularly preferred isocyanates are hexamethylene diisocyanate (HDI), trimethyl-HDI (TMDI), pentane diisocyanate (PDI), 2-methylpentane-1,5-diisocyanate (MPDI), isophorone diisocyanate (IPDI), 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 3(4)-isocyanatomethyl-1-methyl-cyclohexyl isocyanate (IMCI) and / or 4,4'-bis(isocyanatocyclohexyl)methane (H12MDI) or mixtures of these isocyanates.

[0036] Even more preferably, the polyisocyanates are in the form of prepolymers, biuretes, isocyanurates, iminooxadiazinediones, uretdiones and / or allophanates, which can be produced by oligomerization of difunctional isocyanates or by reacting the isocyanate compounds with polyols or polyamines, individually or as a mixture, and which have a mean NCO functionality of 2 or greater.

[0037] Examples of suitable, commercially available isocyanates are Desmodur® < N 3900, Desmodur® < N 100, Desmodur® < Ultra N 3200, Desmodur® < Ultra N 3300, Desmodur® < Ultra N 3600, Desmodur® < N 3800, Desmodur® < XP 2675, Desmodur® < 2714, Desmodur® < 2731, Desmodur® < N 3400, Desmodur® < XP 2679, Desmodur® < XP 2731, Desmodur® < XP 2489, Desmodur® < E 3370, Desmodur® < XP 2599, Desmodur® < XP 2617, Desmodur® < XP 2406, Desmodur® < XP 2551 , Desmodur®< XP 2838, Desmodur®< XP 2840, Desmodur®< VL, Desmodur®< VL 50, Desmodur®< VL 51, Desmodur®< ultra N 3300, Desmodur®< eco N 7300, Desmodur®< E23, Desmodur®< E XP 2727, Desmodur®< E 30600, Desmodur®< E 2863XPDesmodur®< H, Desmodur®< VKS 20 F, Desmodur®< 44V20I, Desmodur®< 44P01, Desmodur®< 44V70 L, Desmodur®< N3400, Desmodur®< N3500 (each available from Covestro AG), Tolonate™< HDB, Tolonate™< HDB-LV, Tolonate™< HDT, Tolonate™< HDT-LV, Tolonate™< HDT-LV2 (available from Vencorex), Basonat®< HB 100,Basonat® < HI 100, Basonat® < HI 2000 NG (available from BASF), Takenate® < 500, Takenate® < 600, Takenate® < D-132N(NS), Stabio® < D-376N (each available from Mitsui), Duranate® < 24A-100, Duranate® < TPA-100, Duranate® < TPH-100 (each available from Asahi Kasai), Coronate® < HXR, Coronate® < HXLV, Coronate® < HX, Coronate® < HK (each available from Tosoh).

[0038] The weight percentage ratios of the isocyanate compound and the group reactive towards isocyanate groups in the B component are preferably chosen such that the equivalent ratio of isocyanate groups to groups reactive towards the isocyanate group is between 0.3 and 1.7, preferably between 0.5 and 1.5 and more preferably between 0.9 and 1.4. Component (B) that is reactive towards isocyanate groups

[0039] According to the invention, the foamable multi-component composition comprises at least one component (B) reactive towards isocyanate groups. Preferably, the component reactive towards isocyanate groups comprises at least one compound selected from the group consisting of compounds with at least two amino groups, polyols, and combinations thereof.

[0040] Suitable amines include all compounds with at least two amino groups, wherein the amino groups are primary and / or secondary amino groups capable of reacting with isocyanate groups to form a urea group (-NC(O)-N), and these compounds are generally known to the person skilled in the art.

[0041] According to a preferred embodiment, the amine reactive towards isocyanate groups is selected from the group consisting of aliphatic, alicyclic, araliphatic and aromatic amines.

[0042] Amines reactive towards isocyanate groups are generally known to those skilled in the art. Examples of suitable amines reactive towards isocyanate groups are given below, without limiting the scope of the invention. These can be used individually or in any mixture with one another. Examples include: 1,2-diaminoethane(ethylenediamine), 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, 2,2-dimethyl-1,3-propanediamine (neopentanediamine), diethylaminopropylamine (DEAPA), 2-methyl-1,5-diaminopentane, 1,3-diaminopentane, 2,2,4- or 2,4,4-trimethyl-1,6-diaminohexane and mixtures thereof (TMD), 1,3-bis(aminomethyl)cyclohexane, 1,2-bis(aminomethyl)cyclohexane, hexamethylenediamine (HMD), 1,2- and 1,4-diaminocyclohexane (1,2-DACH and 1,4-DACH), bis(4-amino-3-methylcyclohexyl)methane, diethylenetriamine (DETA). 4-azaheptane-1,7-diamine, 1,11-diamino-3,6,9-trioxundecane, 1,8-diamino-3,6-dioxaoctane, 1,5-diamino-methyl-3-azapentane, 1,10-diamino-4,7-dioxadecane,Bis(3-aminopropyl)amin, 1,13-Diamino-4,7,10-trioxatridecan, 4-Aminomethyl-1,8-diaminooctan, 2-Butyl-2-ethyl-1,5-diaminopentan, N,N-Bis-(3-aminopropyl)methylamin, Triethylentetramin (TETA), Tetraethylenpentamin (TEPA), Pentaethylenhexamin (PEHA), 1,3-Benzoldimethanamin (m-Xylylendiamin, mXDA), 1,4-Benzoldimethanamin (p-Xylylendiamin, pXDA), 5-(Aminomethyl)bicyclo[[2.2.1]hept-2-yl]methylamin (NBDA, Norbornandiamin), Dimethyldipropylentriamin, Dimethylaminopropyl-aminopropylamin (DMAPAPA), 2,4-Diamino-3,5-dimethylthiotoluol (Dimethylthio-toluoldiamin, DMTDA), 3-Aminomethyl-3,5,5-trimethylcyclohexylamin (Isophorondiamin (IPDA)), Diaminodicyclohexylmethan (PACM), Diethylmethylbenzoldiamin (DETDA), 3,3'-Diaminodiphenylsulfon (Dapson), gemischte polycyclische Amine (MPCA) (z.B. Ancamine 2168), Dimethyldiaminodicyclohexylmethan (Laromin C260), 2,2-Bis(4-aminocyclohexyl)propan, (3(4),8(9)Bis(aminomethyl)tricyclo[5.2.1.02,6]decan (Isomerengemisch, tricyclischer primärer Amine; TCD-Diamin),Methylcyclohexyldiamine (MCDA), N,N'-diaminopropyl-2-methylcyclohexane-1,3-diamine, N,N'-diaminopropyl-4-methylcyclohexane-1,3-diamine, N-(3-aminopropyl)cyclohexylamine, and 2-(2,2,6,6-tetramethylpiperidin-4-yl)propane-1,3-diamine.,

[0043] Polyether polyamines can also be used as amines. These polyether polyamines, also called alkoxylated polyamines or polyoxyalkene polyamines, comprise compounds with aliphatic amino groups, meaning the amino groups are attached to the ends of a polyether backbone. The polyether backbone is based on pure or mixed polyalkylene oxide units, such as polyethylene glycol (PEG) or polypropylene glycol (PPG). The polyether backbone is obtained by reacting a diol or trialcohol initiator with ethylene oxide (EO) and / or propylene oxide (PO), followed by the conversion of the terminal hydroxyl groups to amino groups. in the R: The remainder of an initiator for oxyalkylation consists of 2 to 12 carbon atoms and 2 to 8 groups with active hydrogen atoms. T: hydrogen or a C1-C4 alkyl group, V and U: independent of each other are hydrogen or T n: a value between 0 and 100, m: is an integer between 2 and 8, where m corresponds to the number of groups with an active hydrogen atom that were originally contained in the initiator for the oxyalkylation.

[0044] In further embodiments, n has a value between 35 and 100, or less than 90, less than 80, less than 70, or less than 60. In another embodiment, R has 2 to 6, or 2 to 4, or 3 groups with active hydrogen atoms, in particular hydroxyl groups. In another embodiment, R is an aliphatic initiator with multiple active hydrogen atoms. In yet another embodiment, T, U, and V are each methyl groups.

[0045] Examples of suitable polyetheramines are the D, ED, EDR and T series polyetheramines marketed by Huntsman Corporation under the brand name JEFFAMINE®, where the D series includes diamines and the T series includes triamines, the E series includes compounds having a framework consisting essentially of polyethylene glycol, and the R series includes highly reactive amines.

[0046] The products of the D series include amino-terminated polypropylene glycols of general formula (II), where x is a number with a mean value between 2 and 70. Commercially available products in this series are JEFFAMINE®< D-230 (n ~ 2.5 / mean 230), JEFFAMINE®< D-400 (n ~ 6.1 / mean = 430), JEFFAMINE®< D-2000 (n ~ 33 / mean 2000) and JEFFAMINE®< D-4000 (n ~ 68 / mean 4000).

[0047] The products of the ED series comprise amino-terminated polyethers based on an essentially polyethylene glycol skeleton with the general formula (III), where y is a number with a mean between 2 and 40 and x+z is a number with a mean between 1 and 6. Commercially available products in this series are: JEFFAMINE®< HK511 (y = 2.0; x + z ~ 1.2 / mean 220), JEFFAMINE®< ED-600 (y ~ 9.0; x + z -3.6 / mean 600), JEFFAMINE®< ED-900 (y ~ 12.5; x + z ~ 6.0 / mean 900), and JEFFAMINE®< ED-2003 (y ~ 39; x + z ~ 6.0 / mean 2000).

[0048] The products of the EDR series include amino-terminated polyethers with the general formula (IV) where x is an integer between 1 and 3. Commercially available products in this series are: JEFFAMINE® DER-148 (x = 2 / Mw 148) and JEFFAMINE® DER-176 (x = 3 / Mw 176).

[0049] The products of the T-series include triamines obtained by reaction of propylene oxide with a triol initiator and subsequent amination of the terminal hydroxyl groups, having the general formula (V) or isomers thereof. where R is hydrogen or a C1-C4 alkyl group, preferably hydrogen or ethyl, n is 0 or 1, and x + y + z corresponds to the number of moles of propylene oxide units, where x + y + z is an integer between about 4 and about 100, particularly between about 5 and about 85. Commercially available products from this series are: JEFFAMINE® < T-403 (R = C2H5; n = 1; x + y + z = 5-6 / Mw 440), JEFFAMINE® < T-3000 (R = H; n = 0; x + y + z = 50 / Mw 3000), and JEFFAMINE® < T-5000 (R = H; n = 0; x + y + z = 85 / Mw 5000).

[0050] Furthermore, the secondary amines of the SD and ST series are suitable, the SD series comprising secondary diamines and the ST series secondary triamines, which are obtained from the above series by reductive alkylation of the amino groups, in which the amino end groups are reacted with a ketone, e.g. acetone, and subsequently reduced, so that sterically hindered secondary amino end groups with the general formula (VI) are obtained:

[0051] Commercially available products from this series are: JEFFAMINE ®< SD-231 (starting product D230 / Mw 315), JEFFAMINE ®< SD-401 (starting product D-400 / Mw 515), JEFFAMINE ®< SD-2001 (starting product D-2000 / Mw 2050) and JEFFAMINE ST-404 (starting product T-403 / Mw 565).

[0052] In one embodiment of the invention, polyaspartic acid esters are used as compounds with at least two amino groups, since their reactivity towards isocyanate groups is significantly reduced compared to the other polyamines described above.

[0053] Suitable polyaspartic acid esters are selected from compounds of the general formula (VII), In this formula, R<1 and R<2 can be the same or different and represent organic residues inert towards isocyanate groups; R<3 and R<4 can be the same or different and represent hydrogen or organic residues inert towards isocyanate groups; X represents an n-valent organic residue inert towards isocyanate groups; and n represents an integer of at least 2, preferably 2 to 6, more preferably 2 to 4, and most preferably 2. R<1 and R<2 preferably represent, independently of each other, a hydrocarbon group, optionally a substituted one, preferably a C1-C9 hydrocarbon group, and more preferably a methyl, ethyl, or butyl group; and R<3 and R<4 preferably each represent hydrogen.

[0054] In one embodiment, X represents an n-valent hydrocarbon group obtained by removing the amino groups from an aliphatic or araliphatic polyamine, preferably by removing the primary amino groups from an aliphatic polyamine, particularly preferably a diamine. In this context, the term polyamine includes compounds with two or more primary and optionally additional secondary amino groups, wherein the primary amino groups are preferably terminal.

[0055] In a preferred embodiment, X represents a residue such as is obtained by removing the primary amino groups from 1,4-diaminobutane, 1,6-diaminohexane, 2,2,4- or 2,4,4-trimethyl-1,6-diaminohexane, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 4,4'-diamino-dicyclohexylmethane or 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, diethylenetriamine and triethylenetetramine, and wherein n in formula (VII) represents the number 2.

[0056] Mixtures of polyaspartic acid esters can also be used.

[0057] Examples of suitable polyaspartic acid esters are marketed by Covestro AG under the brand name DESMOPHEN®. Commercially available products include DESMOPHEN® NH 1220, DESMOPHEN® NH 1420, and DESMOPHEN® NH 1520. The described compounds with at least two amino groups can be used individually or as a mixture, depending on the desired reactivity. In particular, the polyamines can serve as bridging compounds when used in addition to the polyether polyamines or the polyaspartic acid esters.

[0058] When polyols are used as components reactive towards isocyanate compounds, all compounds with two or more hydroxyl groups are suitable. Preferably, the polyol is composed of a backbone of polyester, polyether, polyurethane, and / or alkanes, or mixtures thereof. The backbone can be linear or branched and may contain the functional hydroxyl groups terminally and / or along the chain.

[0059] In a preferred embodiment, the polyol contains one or more polyester polyols. Preferably, the polyester polyols are selected from condensation products of di- and polycarboxylic acids, e.g., aromatic acids such as phthalic acid and isophthalic acid, aliphatic acids such as adipic acid and maleic acid, cycloaliphatic acids such as tetrahydrophthalic acid and hexahydrophthalic acid, and / or their derivatives, such as anhydrides, esters, or chlorides, and an excess of multifunctional alcohols, e.g., aliphatic alcohols such as ethanediol, 1,2-propanediol, 1,6-hexanediol, neopentyl glycol, glycerol, trimethylolpropane, and cycloaliphatic alcohols such as 1,4-cyclohexanedimethanol.

[0060] Furthermore, the polyester polyols are selected from polyacrylate polyols, such as copolymers of esters of acrylic and / or methacrylic acid, e.g., ethyl acrylate, butyl acrylate, methyl methacrylate with additional hydroxyl groups, and styrene, vinyl esters, and maleic acid esters. The hydroxyl groups in these polymers are introduced via functionalized esters of acrylic and methacrylic acid, e.g., hydroxyethyl acrylate, hydroxyethyl methacrylate, and / or hydroxypropyl methacrylate.

[0061] Furthermore, the polyester polyols are selected from polycarbonate polyols. Suitable polycarbonate polyols are polycarbonates containing hydroxyl groups, such as polycarbonate diols. These are obtained by reacting carbonic acid or carbonic acid derivatives with polyols or by copolymerizing alkylene oxides, such as propylene oxide, with CO₂. Additionally or alternatively, the polycarbonates used are composed of linear aliphatic chains. Suitable carbonic acid derivatives include carbonic acid diesters, such as diphenyl carbonate, dimethyl carbonate, or phosgene.

[0062] Polyether polycarbonate diols can also be used instead of or in addition to pure polycarbonate diols.

[0063] Furthermore, the polyester polyols are selected from polycaprolactone polyols produced by ring-opening polymerization of ε-caprolactone with multifunctional alcohols such as ethylene glycol, 1,2-propanediol, glycerol and trimethylolpropane.

[0064] Polyether polyols selected from addition products of, for example, ethylene and / or propylene oxide and multifunctional alcohols such as, for example, ethylene glycol, 1,2-propanediol, glycerol and / or trimethylolpropane are also particularly preferred.

[0065] Polyurethane polyols produced by polyaddition of diisocyanates with excess amounts of di- and / or polyols are also particularly preferred.

[0066] Di- or multifunctional alcohols selected from C 2 -C 10 -alcohols with the hydroxyl groups at the ends and / or along the chain are also particularly preferred.

[0067] The most preferred materials are the above-mentioned polyester polyols, polyether polyols and C 2 -C 10 -alcohols that are di- and / or trifunctional and / or tetrafunctional.

[0068] Examples of suitable polyester polyols include DESMOPHEN® < 1100, DESMOPHEN® < 1652, DESMOPHEN® < 1700, DESMOPHEN® < 1800, DESMOPHEN® < 670, DESMOPHEN® < 800, DESMOPHEN® < 850, DESMOPHEN® < VP LS 2089, DESMOPHEN® < VP LS 2249 / 1, DESMOPHEN® < VP LS 2328, DESMOPHEN® < VP LS 2388, DESMOPHEN® < XP 2488 (Covestro AG), K-FLEX XM-360, K-FLEX 188, K-FLEX XM-359, K-FLEX A308 and K-FLEX XM-332 (King Industries).

[0069] Examples of suitable commercially available polyether polyols include: ACCLAIM® POLYOL 12200 N, ACCLAIM® POLYOL 18200 N, ACCLAIM® POLYOL 4200, ACCLAIM® POLYOL 6300, ACCLAIM® POLYOL 8200 N, ARCOL® POLYOL 1070, ARCOL® POLYOL 1105 S, DESMOPHEN® 1110 BD, DESMOPHEN® 1111 BD, DESMOPHEN® 1262 BD, DESMOPHEN® 1380 BT, DESMOPHEN® 1381 BT, DESMOPHEN® 1400 BT, DESMOPHEN® 2060 BD, DESMOPHEN® 2061 BD, DESMOPHEN® < 2062 BD, DESMOPHEN® < 3061 BT, DESMOPHEN® < 4011 T, DESMOPHEN® < 4028 BD, DESMOPHEN® < 4050 E, DESMOPHEN® < 5031 BT, DESMOPHEN® < 5034 BT, DESMOPHEN® < 10WF15, DESMOPHEN® < 10WF16, DESMOPHEN® < 10WF18, DESMOPHEN® < 5168T and DESMOPHEN® < 5035 BT (Bayer; Covestro); Lupranol 2043, Lupranol 2048, Lupranol 2090, Lupranol 2092, Lupranol 2095, Pluriol E600 (BASF); Voranol CP 755, Voranol RA 800, Voranol CP 6001, Voranol EP 1900 (Dow) or mixtures of polyesters and polyether polyols such as WorleePol 230 (Worlee).

[0070] Examples of suitable alcohols include ethanediol, propanediol, propanetriol, butanediol, butanetriol, pentanediol, pentanetriol, hexanediol, hexanetriol, heptanediol; heptanetriol, octanediol, octanetriol, nonanediol, nonanetriol, decanediol and decanetriol.

[0071] In a preferred embodiment, the component (B) reactive towards isocyanate groups comprises a mixture of one or more compounds with two amino groups and one or more polyols. A mixture of one or more polyols with one or more polyaspartic acid esters is particularly preferred, with a mixture of one or more polyaspartic acid esters with triols and / or tetraols being especially preferred.

[0072] Preferably, a catalyst is used for the reaction of the isocyanate compound with the component reactive towards isocyanate groups. The catalyst is preferably selected from among amines, tin-containing compounds, bismuth-containing compounds, zirconium-containing compounds, aluminum-containing compounds, or zinc-containing compounds. These are preferably tin octoate, tin oxalate, tin chloride, dioctyltin di-(2-ethylhexanoate), dioctyltin dilaurate, dioctyltin dithioglycolate, dibutyltin dilaurate, monobutyltin tris-(2-ethylhexanoate), dioctyltin dineodecanoate, dibutyltin dineodecanoate, Dibutyltin diacetate, dibutyltin oxide, monobutyltin dihydroxychloride, organotin oxide, monobutyltin oxide, dioctyltin dicarboxylate, dioctyltin stannoxane, bismuth carboxylate, bismuth oxide, bismuth neodecanoate, zinc neodecanoate, zinc octoate, zinc acetylacetonate, zinc oxalate, zinc acetate, zinc carboxylate, aluminum chelate complex, Zirconium chelate complex, dimethylaminopropylamine, N, N -Dimethylcyclohexylamin, N,N- Dimethylethanolamin, N-( 3- Dimethylaminopropyl)- N , N-diisopropanolamine, N- Ethylmorpholine, / V-Methylmorpholine, Pentamethyldiethylentriamine and / or Triethylenediamine. Examples of common catalysts are Bolt ®< Cat 24, Bolt ®< Cat 320, Bolt ®< Cat 15 (Borchers), TIB KAT 129, TIB KAT P129, TIB KAT 160, TIB KAT 162, TIB KAT 214, TIB KAT 162, TIB KAT 1216 TIB KAT 220, TIB KAT 232, TIB KAT 248, TI B KAT 248 LC, TI B KAT 250, TIB KAT 250, TIB KAT 256, TIB KAT 318, TIB Si 2000, TIB KAT 716, TIB KAT 187, TIB KAT 2007, TIB KAT 200 616, TIB KAT 620, TIB KAT 634, TIB KAT 635, (TIB Chemicals), K-KAT ®< XC-B221 , K-KAT ®< 348, K-KAT ®< 4205, K- KAT ®< 5218, K-KAT ®< K-KAT ®< 35 XK-639, K-KAT ®< XK-604, K-KAT ®< XK-618 (King Industries), JEFFCAT ®< DMAPA, JEFFCAT ®< DMCHA, JEFFCAT ®< DMEA, JEFFCAT ®< DPA, JEFFCAT ®< NEM, JEFFCAT ®< DPA, JEFFCAT ®< NEM, JEFFCAT ®< DPA, JEFFCAT ®< NEM, JEFFCAT®, JEFFCAT ®< TAMM,< JEFFCAT ®< TD-100 (Huntsman) und DABCO 33LV (Sigma Aldrich). In particular, the Multicomponent Composition preferably includes at least one meaningful compound as a Catalyst.

[0073] According to the invention, the composition contains an intumescent additive, wherein the additive can comprise either a single compound or a mixture of several compounds.

[0074] Advantageously, the additives used as intumescent layer-forming agents are those that form an intumescent, expanded, insulating layer of flame-retardant material under the influence of heat. This layer protects the substrate from overheating and thereby prevents or at least delays changes in the mechanical and static properties of load-bearing components caused by heat. The formation of a voluminous, insulating layer, namely an ash layer, can be achieved through the chemical reaction of a mixture of appropriately matched compounds that react with each other upon exposure to heat. Such systems are known to those skilled in the art under the term chemical intumescence and can be used according to the invention. Alternatively, the voluminous, insulating layer can be formed by physical intumescence. Both systems can be used individually or together as a combination according to the invention.

[0075] The formation of an intumescent layer through chemical intumescence generally requires at least three components: a carbon source, a dehydrogenation catalyst, and a gas-forming agent, which are often contained within a binder. Upon exposure to heat, the binder softens, releasing the fire-retardant additives. In the case of chemical intumescence, these additives can react with each other, while in the case of physical intumescence, they can expand. Thermal decomposition of the dehydrogenation catalyst produces an acid that acts as a catalyst for the carbonization of the carbon source. Simultaneously, the gas-forming agent decomposes thermally, producing inert gases that cause the carbonized (charred) material and, if present, the softened binder to expand, forming a voluminous, insulating foam.

[0076] In an embodiment of the invention in which the insulating layer is formed by chemical intumescence, the intumescent layer-forming additive comprises at least one carbon framework former (if the binder cannot be used as such), at least one acid former, at least one gas former, and at least one inorganic framework former. The components of the additive are selected, in particular, to develop synergism, with some of the compounds being able to fulfill multiple functions.

[0077] Suitable carbon sources include compounds commonly used in intumescent flame retardants and known to those skilled in the art, such as starch-like compounds, e.g., starch and modified starch, and / or polyhydric alcohols (polyols), such as saccharides and polysaccharides, and / or a thermoplastic or thermosetting polymeric resin binder, such as a phenolic resin, a urea resin, a polyurethane, polyvinyl chloride, poly(meth)acrylate, polyvinyl acetate, polyvinyl alcohol, a silicone resin, and / or a rubber. Suitable polyols are those from the sugar group, pentaerythritol, dipentaerythritol, tripentaerythritol, polyvinyl acetate, polyvinyl alcohol, sorbitol, and EO-PO polyols. Pentaerythritol, dipentaerythritol, or polyvinyl acetate are preferred.

[0078] It should be mentioned that the polymer, which serves as a binder, can itself also function as a carbon supplier in the event of a fire, so that the addition of an additional carbon supplier is not always necessary.

[0079] Suitable dehydrogenation catalysts or acid-forming agents include compounds commonly used in intumescent fire protection formulations and known to those skilled in the art, such as a salt or ester of an inorganic, non-volatile acid, selected from sulfuric acid, phosphoric acid, or boric acid. Essentially, phosphorus-containing compounds are used, the range of which is very broad, as they encompass several oxidation states of phosphorus, such as phosphines, phosphine oxides, phosphonium compounds, phosphates, elemental red phosphorus, phosphites, and phosphates. Examples of phosphoric acid compounds include: monoammonium phosphate, diammonium phosphate, ammonium phosphate, ammonium polyphosphate, melamine phosphate, melamine resin phosphates, potassium phosphate, and polyol phosphates such as pentaerythritol phosphate, glycerol phosphate, sorbitol phosphate, mannitol phosphate, dulcite phosphate, neopentyl glycol phosphate, and ethylene glycol phosphate.

[0080] Dipentaerythritol phosphate and the like. Preferably, a polyphosphate or an ammonium polyphosphate is used as the phosphoric acid compound. Melamine resin phosphates are understood to be compounds such as reaction products of Lamelite C (melamine-formaldehyde resin) with phosphoric acid. Examples of sulfuric acid compounds include: ammonium sulfate, ammonium sulfamate, nitroaniline bisulfate, 4-nitroaniline-2-sulfonic acid, and 4,4-dinitrosulfanilamide, and the like. Melamine borate can be mentioned as an example of a boric acid compound.

[0081] Suitable gas-forming agents include compounds commonly used in flame retardants and known to those skilled in the art, such as cyanuric acid or isocyanic acid and their derivatives, melamine and its derivatives. These include cyanamide, dicyanamide, dicyandiamide, guanidine and its salts, biguanide, melamine cyanurate, cyanic acid salts, cyanic acid esters and amides, hexamethoxymethylmelamine, dimelamine pyrophosphate, melamine polyphosphate, and melamine phosphate. Hexamethoxymethylmelamine or melamine (cyanuramide) is preferred.

[0082] Also suitable are components whose mode of action is not limited to a single function, such as melamine polyphosphate, which acts as both an acid former and a gas former. Further examples are described in GB 2 007 689 A1, EP 139 401 A1 and US-3 969 291 A1.

[0083] In an embodiment of the invention in which the insulating layer is formed by physical intumescence, the intumescent additive comprises at least one thermally expandable compound, such as a graphite intercalation compound, also known as expandable graphite. These may also be contained in the binder, in particular in a homogeneous form.

[0084] Suitable examples of expandable graphite include known intercalation compounds of sulfuric acid, nitric acid, acetic acid, Lewis acids, and / or other strong acids in graphite. These are also known as graphite salts. Expandable graphites that release SO₂, SO₃, CO₂, H₂O, NO, and / or NO₂ upon expansion at temperatures of, for example, 120 to 350°C are preferred. The expandable graphite can be present, for example, in the form of platelets with a maximum diameter in the range of 0.1 to 5 mm. Preferably, this diameter is in the range of 0.5 to 3 mm. Suitable expandable graphites for the present invention are commercially available. In general, the expandable graphite particles are uniformly distributed in the fire protection elements according to the invention.

[0085] In a further embodiment of the invention, the insulating layer is formed by both chemical and physical intumescence, so that the intumescent layer-forming additive comprises a carbon supplier, a dehydrogenation catalyst and a gas former as well as thermally expandable compounds.

[0086] In principle, the intumescent additive can be present in the multi-component composition in a wide weight percentage range, preferably in an amount of 10 to 70 wt.% based on the total weight of the multi-component composition. If the insulating layer is formed by physical intumescence, the intumescent additive is preferably present in an amount of 10 to 40 wt.% based on the total weight of the multi-component composition. To achieve the highest possible intumescence rate, the proportion of the intumescent additive in the overall formulation is set as high as possible, while ensuring that the viscosity of the composition does not become too high so that it remains easy to process. Preferably, the proportion is 12 to 35 wt.% and particularly preferably 15 to 30 wt.% based on the total weight of the multi-component composition.

[0087] Since the ash crust formed in a fire is generally too unstable and, depending on its density and structure, can be blown away by air currents, negatively impacting the insulating effect of the coating, at least one ash crust stabilizer is preferably added to the components listed above. The basic principle is that the inherently very soft carbon layers that form are mechanically hardened by inorganic compounds. The addition of such an ash crust stabilizer contributes significantly to stabilizing the intumescent crust in the event of a fire, as these additives increase the mechanical strength of the intumescent layer and / or prevent it from dripping. Examples of ash crust stabilizers include...Suitable scaffolding agents include compounds commonly used in fire protection formulations and known to those skilled in the art, such as expandable graphite and particulate metals like aluminum, magnesium, iron, and zinc. The particulate metal can be in the form of a powder, platelets, flakes, fibers, threads, and / or whiskers, with a particle size of <50 µm, preferably 0.5 to 10 µm. When using the particulate metal in the form of fibers, threads, and / or whiskers, a thickness of 0.5 to 10 µm and a length of 10 to 50 µm are preferred.As an alternative or additional ash crust stabilizer, an oxide or compound of a metal from the group comprising aluminum, magnesium, iron, or zinc can be used, in particular iron oxide, preferably iron trioxide, titanium dioxide, a borate such as zinc borate, and / or a glass frit made of low-melting glasses with a melting point preferably at or above 400°C, phosphate or sulfate glasses, melamine polyzinc sulfates, ferroglasses, or calcium borosilicates. The addition of such an ash crust stabilizer contributes significantly to the stabilization of the ash crust in the event of a fire, as these additives increase the mechanical strength of the intumescent layer and / or prevent its dripping. Examples of such additives can also be found in US 4,442,157 A, US 3,562,197 A, GB 755,551 A, and EP 138,546 A1.

[0088] In addition, ash crust stabilizers such as melamine phosphate or melamine borate may be present.

[0089] Optionally, one or more flame retardants, such as phosphate esters, halogen-containing compounds such as tri(2-chloroisopropyl) phosphate (TOPP), tris(2-ethylhexyl) phosphate, dimethylpropanephosphonate, triethyl phosphate, and the like, can be added to the composition according to the invention. Some such compounds are described, for example, in S. V. Levchik, E. D. Weil, Polym. Int. 2004, 53, 1901-1929. The flame retardants may preferably be present in an amount of 3 to 6% by weight, based on the total composition.

[0090] According to the invention, the composition contains a blowing agent comprising one or more compounds capable of releasing carbon dioxide (CO₂) through reaction. All common chemical blowing agents that release carbon dioxide through a chemical reaction between two components are suitable as blowing agents. According to the invention, the individual components of the blowing agent are separated from one another by inhibiting their reaction before the composition is used.

[0091] In the simplest embodiment of the invention, the propellant comprises or consists of water, which, upon mixing with the isocyanate of the isocyanate component (A), releases carbon dioxide. The weight percentage of water is preferably 0.1 to 10 wt.%, more preferably 0.2 to 8 wt.%, and further preferably 0.2 to 6 wt.% based on the total weight of the multi-component composition.

[0092] In a preferred embodiment of the invention, the multi-component composition comprises a foaming catalyst that catalyzes the reaction of the isocyanate with water to form carbon dioxide. Preferably, N,N,N'-trimethyl-N'-hydroxyethylbisaminoethyl ether (Jeffcat ZF-10), bis-(2-dimethylaminoethyl) ether (Jeffcat ZF-20), 70% bis-(2-dimethylaminoethyl) ether in dipropylene glycol (Jeffcat ZF-22), and N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine (Dabco NE300) are used.

[0093] In another embodiment, the propellant comprises an acid and a compound that can react with acids to form carbon dioxide.

[0094] Suitable compounds that can react with acids to form carbon dioxide include carbonate- and hydrocarbonate-containing compounds, particularly metal or (especially quaternary) ammonium carbonates, such as carbonates of alkali or alkaline earth metals, for example CaCO3, NaHCO3, Na2CO3, K2CO3, (NH4)O3, and the like, with chalk (CaCO3) being preferred. Various types of chalk with different grain sizes and surface properties, such as coated or uncoated chalk, or mixtures of two or more of these, can be used. Coated chalk types are preferred because they react more slowly with the acid, thus ensuring controlled foaming and / or a tailored foaming and curing time.

[0095] Any acidic compound capable of reacting with carbonate- or hydrocarbonate-containing compounds to release carbon dioxide can be used as the acid, such as phosphoric acid, hydrochloric acid, sulfuric acid, ascorbic acid, polyacrylic acid, benzoic acid, toluenesulfonic acid, tartaric acid, glycolic acid, lactic acid; organic mono-, di-, or polycarboxylic acids, such as acetic acid, chloroacetic acid, trifluoroacetic acid, fumaric acid, maleic acid, citric acid, or the like; aluminum dihydrogen phosphate, sodium hydrogen sulfate, potassium hydrogen sulfate, aluminum chloride, urea phosphate, and other acid-releasing chemicals or mixtures of two or more of these. The acid produces the gas as the actual propellant.

[0096] An aqueous solution of an inorganic and / or organic acid can be used as the acid component. Buffered solutions of citric, tartaric, acetic, phosphoric acid, and the like can also be used.

[0097] To give the formed foam greater stability, the cells must remain stable until the binder has cured, preventing the collapse of the polymeric foam structure. Stabilization becomes increasingly necessary the lower the desired density of the foam, i.e., the greater the volume expansion. Stabilization is usually achieved using foam stabilizers.

[0098] If necessary, the composition according to the invention can therefore further contain a foam stabilizer. Alkyl polyglycosides are suitable as foam stabilizers, for example. These can be obtained by methods known to those skilled in the art by reacting longer-chain monoalcohols with mono-, di-, or polysaccharides. The longer-chain monoalcohols, which may optionally also be branched, preferably have 4 to 22 carbon atoms, more preferably 8 to 18 carbon atoms, and particularly preferably 10 to 12 carbon atoms in an alkyl group. Specifically, the following are listed as longer-chain monoalcohols: 1-butanol, 1-propanol, 1-hexanol, 1-octanol, 2-ethylhexanol, 1-decanol, 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tetradecanol (myristyl alcohol), and 1-octadecanol (stearyl alcohol). Mixtures of the aforementioned longer-chain monoalcohols can also be used.Other foam stabilizers include known anionic, cationic, amphoteric, and nonionic surfactants, as well as mixtures thereof. Alkyl polyglycosides, EO / PO block copolymers, alkyl or aryl alkoxylates, siloxane alkoxylates, esters of sulfosuccinic acid, and / or alkali or alkaline earth metal alkanoates are preferred. EO / PO block copolymers are particularly preferred.

[0099] The foam stabilizers can be included in any of the components of the multi-component composition according to the invention, as long as they do not react with each other.

[0100] In one embodiment, the composition according to the invention further comprises at least one additional component, selected from plasticizers, crosslinking agents, biocides, organic and / or inorganic additives and / or other additives.

[0101] The plasticizer's function is to soften the cured polymer network. Furthermore, the plasticizer introduces an additional liquid component, ensuring complete wetting of the fillers and adjusting the viscosity to make the coating processable. The plasticizer can be present in the composition in such a quantity that it adequately fulfills the functions described above.

[0102] Suitable plasticizers are selected from derivatives of benzoic acid, phthalic acid, e.g. phthalates such as dibutyl, dioctyl, dicyclohexyl, diisooctyl, diisodecyl, dibenzyl or butylbenzyl phthalate, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, caprylic acid and citric acid, alkyl phosphate esters and derivatives of polyesters and polyethers, epoxidized oils, C 10 -C 20 -alkyl sulfonic acid esters of phenol and alkyl esters. The plasticizer is preferably an ester derivative of terephthalic acid, a triol ester of caprylic acid, a glycol diester, a diol ester of aliphatic dicarboxylic acids, an ester derivative of citric acid, a secondary alkylsulfonic acid ester, ester derivatives of glycerol with epoxide groups, and ester derivatives of phosphates. The plasticizer bis(2-ethylhexyl) terephthalate or trihydroxymethylpropyl caprylate is more preferred.

[0103] Triethylene glycol bis(2-ethylhexanoate), 1,2-cyclohexanedicarboxylic acid diisononyl ester, a mixture of 75-85% secondary alkylsulfonic acid esters, 15-25% secondary alkanedisulfonic acid diphenyl esters, and 2-3% non-sulfonated alkanes, triethyl citrate, epoxidized soybean oil, tri-2-ethylhexyl phosphate, or a mixture of n-octyl and n-decyl succinate. A phosphate ester is most preferred as the plasticizer, since these can act as both plasticizers and flame retardants.

[0104] The plasticizer may preferably be present in the composition in an amount of up to 30 wt.%, more preferably up to 20 wt.% and more preferably up to 8 wt.%, based on the total composition.

[0105] In addition to the additives already described, the composition may contain common auxiliary agents such as wetting agents, for example based on polyacrylates and / or polyphosphates, dyes, fungicides, or various fillers such as vermiculite, inorganic fibers, quartz sand, micro glass beads, mica, silicon dioxide, mineral wool, and the like.

[0106] Additional additives, such as thickeners and / or rheology additives, as well as fillers, can be added to the composition. Rheology additives, such as anti-settling agents, anti-flow agents, and thixotropic agents, preferably include polyhydroxycarboxylic acid amides, 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, as well as aqueous or organic solutions or mixtures of these compounds. Rheology additives based on pyrogenic or precipitated silicas or on silanized pyrogenic or precipitated silicas can also be used.The rheology additive preferably consists of pyrogenic silicas, modified and unmodified layered silicates, precipitated silicas, cellulose ethers, polysaccharides, PU and acrylate thickeners, urea derivatives, castor oil derivatives, polyamides and fatty acid amides and polyolefins, provided they are in solid form, powdered celluloses and / or suspension agents such as xanthan gum.

[0107] The composition according to the invention can be formulated as a two- or multi-component system, the term multi-component system also including two-component systems. The composition is preferably formulated as a two-component system in which the individual components of the blowing agent are separated from one another in a reaction-inhibiting manner prior to use of the composition, and the isocyanate compounds are separated from component B, which is reactive towards isocyanate groups, in a reaction-inhibiting manner prior to use of the composition according to the invention.

[0108] The other components of the composition are distributed according to their compatibility with each other and with the compounds contained in the composition, and may be present in one or both components. Furthermore, the distribution of the other components, particularly the solid components, may depend on the desired quantities of these components in the composition. This distribution may result in a higher proportion of each component relative to the total composition. The intumescent fire protection additive may be present as a complete mixture or as individual components in one or more components. The distribution depends on the compatibility of the compounds contained in the composition, ensuring that no reaction occurs between the compounds themselves or with the other components.Neither mutual interference nor a reaction of these compounds with the compounds of the other components can occur. This depends on the compounds used.

[0109] Another object of the present invention is a fire protection profile produced from the multi-component composition according to the invention. The fire protection profiles according to the invention are produced by mixing the components of the multi-component composition according to the invention. As a result of the reaction of the components, foaming occurs.

[0110] Preferably, the fire protection profiles according to the invention are manufactured in a continuous production process, in which the fire protection profiles are separated to the desired length at the end. To give the fire protection profile the desired shape, support elements that adhere to all sides can be used during the foaming process.

[0111] The fire protection profile preferably has a rectangular cross-section. This makes it particularly easy to install the fire protection profiles seamlessly in a wall or ceiling opening.

[0112] The fire-resistant profile sections can be cut to lengths of, for example, 80 cm to facilitate easy handling during packaging and transport. Before installation, the profile sections can be cut to shorter lengths by the user if necessary.

[0113] A further aspect of the present invention is the use of the inert foamable multi-component composition in fire protection profiles, particularly in low-density fire protection profiles, to improve fire resistance. In the cured state, the fire protection profiles preferably have a density between 100 kg / m³ and 200 kg / m³. Preferably, the fire protection profile comprises polyurethane and / or polyurea as a binder. Where applicable, all the above descriptions apply in these cases.

[0114] The invention is explained in more detail below with reference to a series of examples. All examples and illustrations support the scope of the claims. However, the invention is not limited to the specific embodiments shown in the examples and illustrations. EXAMPLES OF EXECUTION

[0115] All components of the compositions listed here are - unless otherwise stated - commercially available and were used in commercially standard quality.

[0116] All percentages given in the examples refer to the total weight of the described composition as a basis for calculation, unless otherwise stated. List of components used in the examples and references (explanation of abbreviations) as well as their trade names and sources:

[0117] Table 1: List of components used in the examples Description Desmophen 5168 T Polypropylene ether polyol (Covestro) Water H₂O (tap water) Dabco 33 LV Oxydipropanol 67% + 1,4-diazabicyclooctane 33% (Evonik) Jeffcat ZF 10 2-(2- / 2-Dimethylaminoethoxy)-ethylmethylamino)-ethanol (Huntsman) Kropfmühl ES 700 FS pH Expanded graphite (Kropfmühl company) Desmodur 44V20L Methylene diphenyl isocyanates (Covestro) Casul H1i Ettringite with the structural formula 3 Ca•Al 2 O 3 •3 CaSO 4 •32 H 2 O (Ettringite) (Remondis Production GmbH); Crystal water content 45% Pural MG 70 Aluminum-magnesium hydroxycarbonate with a 70:30 ratio of MgO:Al2O3 (Sasol company) Special brick flour 0 - 3 mm Brick dust with a grain size of ≤ 3 mm (Peter Stadler GmbH) Aerogel Particles P100 Silicate-based aerogel (Cabot) Preparation of component B, which is reactive towards isocyanate groups

[0118] First, the polyol is placed in a beaker, followed by the addition of water and the catalysts. The mixture is stirred with a spatula for 20 seconds until a homogeneous liquid is obtained. Next, the expanding graphite is added, and the mixture is stirred until a homogeneous mass is formed. Finally, the endothermic fillers and / or the fillers with low heat capacity are added, and the mixture is stirred again until homogeneous. Preparation of a cup foam

[0119] To produce a beaker foam, 100g of foam formulation is prepared in a 580ml beaker. Isocyanate component A is added to component B and stirred in rapidly for 5 seconds. Then, the mixture is allowed to set until the foam has reached its full height and solidified. The reaction is complete when the foam is no longer sticky, typically after 40 seconds. Barrel oven test

[0120] To perform a so-called barrel oven test, a block of aerated concrete measuring 300 x 300 x 70 mm (W x L x H) is prepared. Four holes, each with a diameter of 8 cm, are drilled into the block using a hole saw, resulting in a volume of 140.7 ml. The block is placed on a flat surface so that the cylindrical holes are contained at the bottom. Component B and the isocyanate component A are mixed in a beaker according to Table 2, stirred for approximately 5 seconds, and poured directly into one of the holes. The hole is then sealed from above with a weight of at least 1 kg to prevent the foam from expanding beyond the cylindrical shape. After approximately 40 seconds, the weight can be removed. The resulting foam should completely fill the cylinder and have a density of 130 g / L. Once all openings are filled, the block is placed in the designated opening of a Rhode G80 gas top-loading pot burner.This allows the heat transfer to the non-fire side to be measured. Thermocouples are attached to the center of the foam cylinders on the outside. A predefined temperature program is then run. The required gas flame is started, and the furnace heats up from room temperature to 650 °C within the first 10 minutes. Over the next 50 minutes, the temperature continues to rise continuously until it reaches approximately 950 °C after one hour. For evaluation, the temperature readings from the thermocouples after 60 minutes are used and compared to a reference temperature. The results are shown in the following table (compositions as per Table 2): Table 3: Results of the barrel furnace test Formulation Temperature after 60 min [°C] [%] Temperature relative to the reference reference 294,3 100 Example 1 (1 wt.% Casul H1i) 197,8 67 Example 2 (7 wt.% Pural MG 70) 199,8 68 Example 3 (1 wt.% brick dust) 241,7 82 Example 4 (7 ml aerogel) 160,3 54 Thermogravimetric analysis (TGA) of the fillers

[0121] For thermogravimetric analysis, approximately 50 mg of the filler material to be measured is weighed into a sample crucible using a spatula. The sample is then placed in a Mettler Toledo TGA / DSC3+ instrument. The sample is heated in an air atmosphere at a heating rate of 10 K / min within a temperature range of 30 °C to 1100 °C. The weight loss of the sample is recorded during the heating process.

[0122] The onset temperatures of the temperature-regulating fillers shown in the following table were determined using thermogravimetric analysis (TGA): Table 4: Determination of the onset temperature using TGA analysis Temperature-regulating filler Onset temperature (TGA) Casul H1i 96 °C Plural MG 70 181 °C

Claims

1. Foamable multi-component composition comprising i) at least one isocyanate component A containing at least one polyisocyanate, ii) at least one component B which is stored separately from the isocyanate component A in a reaction-inhibiting manner and is reactive with respect to isocyanate groups, containing at least one compound selected from the group consisting of compounds having at least two amino groups, polyols and combinations thereof, iii) at least one fire protection additive that forms an insulation layer, and iv) a blowing agent comprising one or more compounds capable of releasing CO2 through reaction, the individual components of the blowing agent being separated from each other in a reaction-inhibiting manner prior to the use of the multi-component composition, characterized in that the isocyanate component A and / or the component B which is reactive with respect to isocyanate groups comprises at least one temperature-regulating filler, the temperature-regulating filler being an endothermic filler containing at least one crystalline or semi-crystalline inorganic compound which comprises water of hydration and is selected from the group consisting of ettringites, layered double hydroxides (LDH) or mixtures thereof, or being a temperature-regulating filler which has a thermal conductivity < 1 W m-1 K-1 and being selected from the group consisting of brick dust, aerogels or mixtures thereof.

2. Foamable multi-component composition according to claim 1, characterized in that the endothermic reaction of the endothermic filler begins in a temperature range from 70°C to 300°C.

3. Foamable multi-component composition according to claim 1 or claim 2, characterized in that the weight percentage fraction of the temperature-regulating filler is in a range from 1 to 70 wt.%, based on the total weight of the foamable multi-component composition.

4. Foamable multi-component composition according to any of the preceding claims, characterized in that the multi-component composition comprises both an endothermic filler and a filler having a thermal conductivity < 1 W m-1 K-1.

5. Foamable multi-component composition according to claim 4, characterized in that the endothermic filler and the filler having a thermal conductivity < 1 W m-1 K-1 are used in a weight percentage ratio of 1:1.

6. Foamable multi-component composition according to any of the preceding claims, characterized in that the blowing agent comprises water.

7. Foamable multi-component composition according to any of the preceding claims, characterized in that the fire protection additive that forms an insulation layer is selected from graphite intercalation compounds, expandable silicate material or combinations thereof.

8. Fire-protection profile produced from a foamable multi-component composition according to any of the preceding claims.

9. Fire protection profile according to claim 8, characterized in that the fire protection profile has a density between 100 kg / m3 and 200 kg / m3 in the cured state.

10. Use of the foamable multi-component composition according to any of claims 1 to 7 in fire protection profiles, in particular in fire protection profiles having a low density, for improving the fire resistance duration in the event of a fire.

11. Use according to claim 10, characterized in that the fire protection profile comprises a polyurethane foam and / or a polyurea foam.