Sustainable-polyol-based base composition, foam composition produced therefrom, and moulded body produced therefrom for fire-protection purposes

Abstract

The present invention relates to a polyol-based base composition comprising at least one sustainable polyol and a sustainable filler, and to a foam composition for producing a foamed moulded body for fire-protection purposes. The present invention also relates to a moulded body produced from the foam composition and to a method for producing the moulded body. The compositions according to the invention and the moulded body produced therefrom for fire-protection purposes comprise at least one sustainable polyol and at least one sustainable filler, as a result of which the CO2 balance of the moulded body and the ash deposit hardness in the event of a fire are improved.

Description

[0001] Sustainable polyol-based base composition, foam composition made therefrom and molded article made therefrom for fire protection purposes

[0002] The present invention relates to a polyol-based base composition comprising at least one sustainable polyol and one sustainable filler, as well as to a foam composition for producing a foamed molded article for fire protection purposes. Furthermore, the present invention relates to a molded article produced from the foam composition and a process for producing the molded article. The compositions according to the invention and the molded article for fire protection purposes produced therefrom comprise at least one sustainable polyol and at least one sustainable filler, thereby improving the carbon dioxide balance of the molded article and the ash crust hardness in the event of a fire.

[0003] background

[0004] When laying cables, such as pipelines, electrical cables, and the like, they are routed through openings in structural elements, particularly building components such as walls and ceilings. To prevent the passage of fire and smoke in the event of a fire, fire barrier materials, such as fire cushions and fire blocks, are inserted between the interior walls of the openings and the cables passing through them. These are so-called molded bodies, which are produced within a defined manufacturing process. These molded bodies are often based on polyurethane foam. In addition, fire protection materials based on polyurethane foam for joint applications already exist.

[0005] Also known are so-called in-situ foams. In-situ foam is a foam that is sprayed or poured directly onto the site of use and then expanded.

[0006] A distinction is made between single-component and multi-component foams. Many in-situ foams are made of polyurethane (PU).

[0007] Over the past few years, improving the carbon dioxide (CO2) footprint in the manufacture of fire protection products has become increasingly important for climate protection. The European Union's climate targets aim to reduce greenhouse gases by 55% by 2030 compared to 1990 levels, and to achieve climate neutrality by 2050. To produce foamed molded bodies for fire protection applications, such as fire protection cushions and fire protection blocks, raw materials are extracted from nature and disposed of as waste after use. During the processing of the raw materials into the final product, carbon dioxide is constantly released, which is harmful to the climate.

[0008] For each product, a carbon footprint (CFP) can be determined, which describes its carbon footprint. A product's CFP is typically determined as part of a life cycle assessment according to ISO 14040 / 14044. The use of recycled materials generally improves a product's carbon footprint.

[0009] It is generally known that sustainable raw materials, such as natural oil-based polyols or bio-based polyols, can be used to reduce the carbon footprint of polyurethane-based foam compositions. Natural oil-based polyols based on castor oil are often used for this purpose.

[0010] However, natural oil-based PU fire protection foams often suffer from performance issues in the event of a fire, such as an excessively soft ash crust. It has been shown that these performance disadvantages are due to the use of the natural oil-based polyol, so natural oil-based polyols cannot be used in any desired amount, typically < 15 wt.%.

[0011] In view of the above, there is therefore a need to be able to provide foamed molded bodies for fire protection applications based on polyurethane, which are characterized by an improved CC>2 balance and have at least comparable fire protection properties with regard to ash crust stability.

[0012] The object of the invention is therefore to provide foamed molded bodies for fire protection applications based on polyurethanes that exhibit an improved carbon dioxide balance compared to known molded bodies for fire protection applications. The foamed molded bodies should exhibit at least comparable, preferably improved, fire protection properties to those of foamed molded bodies based on natural oil-based polyurethanes already known from the prior art.

[0013] The object underlying the invention could surprisingly be achieved by using a polyol-based base composition comprising at least one sustainable polyol and at least one sustainable filler according to claim 1.

[0014] A second subject matter of the invention is further a foam composition comprising the polyol-based base composition and at least one polyisocyanate.

[0015] A third object of the invention is a molded article made from the foam composition for fire protection applications.

[0016] A fourth aspect of the invention is also a process for producing the shaped body from the polyol-based base composition.

[0017] A fifth aspect is also the use of at least one sustainable polyol and at least one sustainable filler to improve the CO2 balance of a foamed molded article based on polyurethane.

[0018] For a better understanding of the invention, the following explanations of the terminology used herein are considered useful. For the purposes of the invention, the following definitions apply: - "Polyol-based base composition" is a composition comprising at least one sustainable polyol, at least one intumescent additive, at least one sustainable filler, and a blowing agent. The polyol-based base composition is designed so that a reaction of the components only occurs after mixing with at least one polyisocyanate.

[0019] - “Foam composition” means a homogenized, partially homogenized or non-homogenized composition comprising the polyol-based base composition and at least one polyisocyanate.

[0020] - “Shaped body” means the foamed reaction product of the polyol-based base composition with at least one polyisocyanate, which is brought into a predefined shape by a molding process.

[0021] - "Sustainable polyol" is a collective term for all polyols based on natural or recyclable raw materials and not a direct product of exclusively petrochemical production (so-called synthetic polyols). In particular, the term "sustainable polyol" includes natural oil-based polyols and bio-based polyols, but also polyols that are recycled to such an extent that they can be used as polyol products.

[0022] - "Sustainable filler" is a collective term for all fillers whose use can reduce the carbon footprint of a composition or product / manufactured article. Sustainable fillers are generally of natural origin or result from low-energy-intensive processes, recycling, treatment, or reuse processes, or arise as waste products in industrial processes. Sustainable fillers within the meaning of the present invention include, in particular, lignin (a biopolymer incorporated into the plant cell wall), modified lignin such as kraft lignin, and / or all forms of starch (polysaccharide with the formula (CeHioO5)n). "Isocyanates" are compounds that have a functional isocyanate group -N=C=O and are characterized by the structural unit RN=C=O (with R as the organic radical);

[0023] - 'Polyisocyanates' are compounds containing at least two functional isocyanate groups -N=C=O; diisocyanates, which also fall within the definition of polyisocyanate, are characterised, for example, by the structure O=C=NRN=C=O, where R represents any organic radical;

[0024] - "average NCO functionality" describes the number of isocyanate groups in the compound; in the case of 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) = Z average NCO functionality (isocyanate i) / ni, i.e. the sum of the average NCO functionality of the individual components divided by the weight percentage of the individual components;

[0025] - "Alcohols" are organic compounds in which at least one -OH hydroxyl group is bonded to a carbon atom. "Polyols" are alcohols that have at least two -OH hydroxyl functional groups.

[0026] - “OH functionality” of an alcohol describes the number of active hydrogen atoms per polyol that can react with an isocyanate group;

[0027] - "a", "an", "another" as an article before a chemical compound class, e.g., before the word "isocyanate," means one or more compounds falling within this chemical compound class, e.g., different isocyanates. In a preferred embodiment, this article refers to only a single compound;

[0028] - "at least one", "at least one", "at least one" numerically "one or more". In a preferred embodiment, this term means "one", "an", "another" numerically; - "contain", "comprise", and "include" indicate that, in addition to the components mentioned, further components may be present. These terms are meant inclusively and therefore also include "consist of". "Consist of" is meant conclusively and means that no further components may be present. In a preferred embodiment, the terms "contain", "comprise", and "include" mean the term "consist of"

[0029] According to the invention, the polyol-based base composition comprises at least one sustainable polyol a1).

[0030] In a preferred embodiment, the sustainable polyol is a polyol based on one or more natural oils. The term "natural oil" in the context of the present invention is defined as a starting material that is not derived from petroleum. This includes, in particular, oils derived from a plant, including its fruits, shells, nuts, and / or seeds. However, animal fats and / or oils or any other non-petroleum-derived oil can also be used. These naturally occurring materials are environmentally friendly and are also referred to as bio-based starting materials. Polyols produced from these various non-petroleum sources are often also referred to as "renewable polyols," "bio-based polyols," and / or "sustainable polyols."

[0031] While some natural oils contain hydroxyl groups, most natural oils must be converted into hydroxyl-containing polyols by chemical processes such as hydroxylation, epoxidation, ozonolysis, hydroformylation / hydrogenation, or other suitable processes.

[0032] Examples of such natural oils as starting materials for sustainable polyols that do not contain hydroxyl groups in their naturally occurring form include soybean oil, canola oil, sunflower oil, corn oil, linseed oil, poppyseed oil, cottonseed oil, tung oil, palm oil, peanut oil, fish oil, olive oil, safflower oil, rapeseed oil, and coconut oil. To produce sustainable polyols based on one or more natural oils, the natural oils are hydroxylated or alkoxylated, for example, using a suitable process. In this context, reference is made to patent EP2202256 A1, which describes suitable processes for the hydroxylation or alkoxylation of natural oils.

[0033] Cashew shell oil (cashew shell liquid, cashew shell oil) is particularly preferred as a starting material for the production of sustainable polyols. Cashew shell oil-based polyether polyols and cashew shell oil-based polyester polyols are particularly preferred.

[0034] Cashew nut shell oil-based polyols are commercially available, for example, from Elmira Industrial Supplies under the trade name ExaPhen or from Cardolite Corp.

[0035] In a further embodiment of the invention, castor oil can also be used as sustainable polyol a1).

[0036] It is also possible to use a recycled polyol as sustainable polyol a1), either alone or in combination with the aforementioned natural oil-based polyols. The term "recycled polyol" in the context of the present invention refers to a polyol produced by recycling polyurethane-based consumer goods, such as polyurethane mattresses.

[0037] Recycled polyols based on polyurethane-based mattresses are commercially available from RAMPF under the brand Recypol® or from Dow under the brand Renuva®.

[0038] In addition, bio-based polyester polyols from the Rokrapol Group (Robert Kraemer GmbH & Co. KG, Germany) can also be used. Usable polyesters from the Rokrapol Group are obtained by condensation of polyalcohols with polycarboxylic acids or their anhydrides. Polyesters from the Rokrapol Group are available in hydroxy- and / or carboxy-functional and linear or branched versions. These polyester polyols are made from up to 100% renewable raw materials. Examples include Rokrapol RK 7480, Rokrapol RK 7481, Rokrapol RK 7486 and Rokrapol RK 7774. Particularly preferred is the bio-based polyester polyol from the Rokrapol Group, Rokrapol RK 7481, with a

[0039] Molecular weight of 1100 g / mol.

[0040] In a preferred embodiment, the polyol-based

[0041] In addition to the at least one sustainable polyol a1), the base composition contains at least one further polyol a2) that does not fall under the definition of a sustainable polyol a1) within the meaning of the present invention. In other words, this means that the polyol a2) is a so-called synthetic polyol derived from petroleum or petroleum derivatives.

[0042] The polyol-based base composition thus preferably comprises a polyol mixture of at least two polyols, wherein the ratio of the sustainable polyol a1) and the further polyol a2) is preferably 10:1 to 1:100, more preferably 5:1 to 1:10, more preferably 4:1 to 1:5. Particularly preferably, the ratio of the sustainable polyol a1) and the further polyol a2) is not greater than 2:1, particularly preferably not greater than 1.5:1.

[0043] The at least one further polyol a2) is preferably selected from the group of polyether polyols, polyester polyols or mixtures thereof.

[0044] Polyether polyols are composed of a polyether backbone. The backbone can be linear or branched and contain the functional hydroxyl groups terminally and / or along the chain.

[0045] The polyether polyols are preferably prepared by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin with themselves or by adding these epoxides, optionally in admixture or successively, to starting components containing reactive hydrogen atoms such as water, alcohols, ammonia, or amines. Particularly preferred epoxides are ethylene oxide and propylene oxide.

[0046] 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 1 105 S, DESMOPHEN® 1 1 10 BD, DESMOPHEN® 1 11 1 BD, DESMOPHEN® 1262 BD, DESMOPHEN® 1380 BT, DESMOPHEN® 1381 BT,

[0047] DESMOPHEN® 1400 BT, DESMOPHEN® 2060 BD, DESMOPHEN® 2061 BD,

[0048] DESMOPHEN® 2062 BD, DESMOPHEN® 3061 BT, DESMOPHEN® 401 1 T,

[0049] DESMOPHEN® 4028 BD, DESMOPHEN® 4050 E, DESMOPHEN® 5031 BT,

[0050] 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 blends of polyester and polyether polyols such as WorleePol 230 (Worlee).

[0051] In a preferred embodiment, polyol a2) contains one or more polyester polyols. The polyester polyols are preferably 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 amount of polyfunctional 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.

[0052] Furthermore, the polyester polyols are selected from polyacrylate polyols, such as copolymers of esters of acrylic and / or methacrylic acid, such as 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. Furthermore, the polyester polyols are selected from polycarbonate polyols. Usable polycarbonate polyols are polycarbonates containing hydroxyl groups, such as polycarbonatediols. These are obtainable 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.

[0053] The weight percentage of all polyols in the polyol-based base composition is preferably 20 wt.% to 95 wt.%. Based on the total weight of the foam composition, the weight percentage is preferably >10 wt.% to 95 wt.%, more preferably 20 wt.% to 92 wt.%, even more preferably 25 wt.% to 80 wt.%.

[0054] Sustainable filler

[0055] The polyol-based base composition according to the invention and the foam composition according to the invention comprise at least one sustainable filler.

[0056] The term "sustainable filler" in the sense of the present invention describes a filler selected from the group consisting of (modified) lignin, starch and mixtures thereof.

[0057] It has surprisingly been found that the inventive use of a sustainable filler makes it possible to use sustainable polyols in the polyol-based base composition without compromising the fire protection performance of molded articles produced from the polyol-based base composition in the event of a fire. In particular, molded articles produced from a polyol-based base composition according to the invention are characterized by improved ash crust hardness. The term lignin in the sense of the present invention refers to a biopolymer that is synthesized in the cells of trees, shrubs, bamboo, rattan, cereals, and other grasses and incorporated into the cell wall. To obtain lignin, it is separated from cellulose. Lignin is a by-product of paper and pulp production.The term “lignin” in the sense of the present invention also includes chemically modified variants, such as the so-called kraft lignin.

[0058] The term starch in the sense of the present invention refers to a polysaccharide with the formula (CeH OsJn), which consists of aD-glucose units. Starch is one of the most important components of plant cells and is obtained from plants by known methods.

[0059] Within the scope of the present invention, all naturally occurring starches known to the person skilled in the art can be used. These include, in particular, tuber starches and cereal starches. Potato starch, sweet potato starch, cassava starch, or mixtures thereof can be used as tuber starch. Barley starch, wheat starch, rye starch, rice starch, or corn starch can be used as cereal starch. Horse chestnut starch or pea starch can also be used. The use of corn starch is preferred.

[0060] The water content of the starch used is preferably below 10%, more preferably below 6%. This is preferably achieved by drying the starch before it is added to the polyol-based base composition.

[0061] The sustainable filler is preferably used in a weight percentage range of 1 to 70 wt.% based on the total weight of the polyol-based base composition, in particular in a proportion of 2 wt.% to 50 wt.%, more preferably in a proportion of 3 wt.% to 40 wt.% in the polyol-based base composition according to the invention. With regard to the foam composition, it preferably contains the sustainable filler in a weight percentage range of 1 to 40 wt.%, preferably in a proportion of 2 wt.% to 30 wt.%, more preferably in a proportion of 3 wt.% to 20 wt.%, based on the total weight of the foam composition.

[0062] Insulating additive

[0063] According to the invention, the polyol-based base composition contains an intumescent additive, wherein the additive may comprise either a single compound or a mixture of several compounds.

[0064] Advantageously, insulating layer-forming additives are those that expand under the influence of heat and form an insulating layer of flame-resistant material. The formation of a voluminous, insulating layer, namely an ash layer, can be achieved through the chemical reaction of a mixture of correspondingly 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 in combination according to the invention.

[0065] The formation of an intumescent layer through chemical intumescence generally requires at least three components: a carbon source, a dehydrogenation catalyst, and a gas generator, which are often contained in a binder. When exposed to heat, the binder softens and the fire-retardant additives are released, allowing them to react with each other in the case of chemical intumescence or expand in the case of physical intumescence. Thermal decomposition of the dehydrogenation catalyst converts the acid into the carbonizing catalyst. At the same time, the gas generator thermally decomposes to form inert gases, causing the carbonized (charred) material and, if necessary, the softened binder to expand, forming a voluminous, insulating foam.In one embodiment of the invention in which the insulating layer is formed by chemical intumescence, the insulating layer-forming additive comprises at least one carbon framework former (if the binder cannot be used as such), at least one acid generator, at least one gas generator, and at least one inorganic framework former. The components of the additive are selected in particular so that they can develop synergism, with some of the compounds being able to fulfill multiple functions.

[0066] Suitable carbon sources include the compounds commonly used in intumescent flame retardants and known to those skilled in the art, such as 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 polyols from the group consisting of sugar, pentaerythritol, dipentaerythritol, tripentaerythritol, polyvinyl acetate, polyvinyl alcohol, sorbitol, EO polyols, PO polyols, and EO-PO polyols. Pentaerythritol, dipentaerythritol, or polyvinyl acetate are preferred.

[0067] It should be noted that the polymer which serves as a binder can 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.

[0068] Suitable dehydrogenation catalysts or acid generators are the compounds commonly used in intumescent fire protection formulations and known to the person skilled in the art, such as a salt or an 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 extend across several oxidation states of phosphorus, such as phosphines, phosphine oxides, phosphonium compounds, phosphates, elemental red phosphorus, phosphites, and phosphates. Examples of phosphoric acid compounds that can be mentioned are: monoammonium phosphate, diammonium phosphate, ammonium phosphate, ammonium polyphosphate, melamine phosphate,

[0069] Melamine resin phosphates, potassium phosphate, polyol phosphates such as pentaerythritol phosphate, glycerol phosphate, sorbitol phosphate, mannitol phosphate, dulcitol phosphate, neopentyl glycol phosphate, ethylene glycol phosphate,

[0070] Dipentaerythritol phosphate, and the like. A polyphosphate or an ammonium polyphosphate is preferably used as the phosphoric acid compound. Melamine resin phosphates are understood to mean 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, among others. Melamine borate is an example of a boric acid compound.

[0071] Suitable gas generators are compounds commonly used in flame retardants and known to those skilled in the art, such as cyanuric acid or isocyanic acid and their derivatives, and melamine and their 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 (cyanuric acid amide) is preferred.

[0072] Also suitable are components whose mode of action is not limited to a single function, such as melamine polyphosphate, which acts both as an acid generator and a gas generator. Further examples are described in GB 2 007 689 A1, EP 139 401 A1, and US Pat. No. 3 969 291 A1.

[0073] In one embodiment of the invention in which the insulating layer is formed by physical intumescence, the insulating layer-forming additive comprises at least one thermally expandable compound, such as a graphite intercalation compound, also known as expandable graphite. These can also be contained in the binder, especially homogeneously.

[0074] Examples of suitable 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 referred to 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, for example, be in the form of platelets with a maximum diameter in the range of 0.1 to 5 mm. This diameter is preferably in the range of 0.5 to 3 mm. Expandable graphites suitable for the present invention are commercially available.

[0075] In a further embodiment of the invention, the insulating layer is formed by both chemical and physical intumescence, so that the insulating layer-forming additive comprises a carbon supplier, a dehydrogenation catalyst and a gas generator as well as thermally expandable compounds.

[0076] In principle, the intumescent additive can be present in the polyol-based base composition in a wide range of weight percentages, namely preferably in an amount of 5 to 80 wt.% based on the total weight of the polyol-based base composition. If the insulating layer is formed by physical intumescence, the intumescent additive is preferably present in an amount of 5 to 80 wt.% based on the total weight of the polyol-based base 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 the composition can still be processed easily. The proportion is preferably 5 to 80 wt.% and particularly preferably 10 to 70 wt.%, based on the total weight of the polyol-based base composition.

[0077] Since the ash crust formed in the event of a fire is generally too unstable and, depending on its density and structure, can be blown away by air currents, which negatively impacts the insulating effect, at least one ash crust stabilizer is preferably added to the components listed above. The basic principle is that the resulting carbon layers, which are very soft in themselves, are mechanically strengthened by inorganic compounds. The addition of such an ash crust stabilizer contributes to a significant stabilization of 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 off. Ash crust stabilizers orSuitable framework formers include the compounds commonly used in fire protection formulations and known to the person skilled in the art, for example expandable graphite and particulate metals such as aluminum, magnesium, iron, and zinc. The particulate metal may be in the form of a powder, platelets, flakes, fibers, filaments, and / or whiskers, with the particulate metal in the form of powder, platelets, or flakes having a particle size of <50 μm, preferably from 0.5 to 10 μm. When using the particulate metal in the form of fibers, filaments, and / or whiskers, a thickness of 0.5 to 10 μm and a length of 10 to 50 μm is preferred.Alternatively or additionally, an oxide or a compound of a metal from the group comprising aluminum, magnesium, iron, or zinc can be used as an ash crust stabilizer, 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 temperature of 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 to a significant stabilization of the ash crust in the event of a fire, since these additives increase the mechanical strength of the intumescent layer and / or prevent it from dripping off. 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.

[0078] Ash crust stabilizers such as melamine phosphate or melamine borate may also be included.

[0079] Optionally, one or more flame retardants can be added to the composition according to the invention, such as phosphate esters, halogen-containing compounds such as tri-(2-chloroisopropyl) phosphate (TOPP), tris(2-ethylhexyl) phosphate, dimethylpropanephosphonate, triethyl phosphate, and the like. Some such compounds are described, for example, in S. V. Levchik, E. D. Weil, Polym. Int. 2004, 53, 1901-1929. The flame retardants can preferably be present in an amount of 3 to 6 wt.%, based on the total composition.

[0080] Propellant

[0081] According to the invention, the polyol-based base composition contains a blowing agent. In principle, all chemical and physical blowing agents known to those skilled in the art are suitable as blowing agents. These include, in particular, those capable of releasing CO2 or H2.

[0082] The polyol-based base composition preferably contains a blowing agent comprising one or more compounds capable of releasing carbon dioxide (CO2) through reaction. Suitable blowing agents include all common chemical blowing agents that release carbon dioxide through a chemical reaction between two components.

[0083] According to the invention, the blowing agent is designed so that a reaction only occurs after activation. Activation also includes mixing with another component, such as the polyisocyanate described later.

[0084] In the simplest embodiment of the invention, the blowing agent comprises water or consists of water, which releases carbon dioxide upon mixing with the polyisocyanate. The term "water" in this context also includes water-releasing complexes, adducts, and inclusion compounds. 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 foam composition.

[0085] Further examples of propellants are alkanes such as n-pentane, isopentane, mixtures of iso- and n-pentane, cyclopentane, cyclohexane, mixtures of butane isomers and the alkanes mentioned, halogenated olefins or halogenated compounds such as dichloromethane, dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, 1,1,1,2-tetrafluoroethane, tetrafluoroethane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,3,3-pentafluoropropane, chlorodifluoroethane, 1,1-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane, heptafluoropropane and sulfur hexafluoride and carbon dioxide. Carbon dioxide, cyclopentane, n-pentane and iso-pentane are preferably used individually or as a mixture, optionally in admixture with water. Other suitable blowing agents are carboxylic acids such as formic acid, acetic acid, oxalic acid and chemical blowing agents which release gases during the foaming process, such as azo compounds.These propellants are preferably used in combination with water.

[0086] In another embodiment, the propellant comprises an acid and a compound that can react with acids to form carbon dioxide.

[0087] As compounds which can react with acids to form carbon dioxide, carbonate- and hydrocarbonate-containing compounds, in particular metal or (in particular quaternary) ammonium carbonates, such as carbonates of alkali or alkaline earth metals, for example CaCOs, NaHCOs, NaaCOs, KaCO3, (NH4)2CO3 and the like, with CaCOs being preferred.

[0088] Any acidic compound capable of reacting with carbonate- or bicarbonate-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,

[0089] Potassium hydrogen sulfate, aluminum chloride, urea phosphate, and other acid-releasing chemicals, or mixtures of two or more of these. The acid generates the gas that serves as the actual propellant.

[0090] An aqueous solution of an inorganic and / or organic acid can be used as the acid component. Buffered solutions of citric, tartaric, acetic, phosphoric, and the like can also be used. To impart greater stability to the foam being formed, the formed cells must remain stable until the binder cures to prevent the polymeric foam structure from collapsing. Stabilization becomes more necessary the lower the density of the foam, i.e., the greater the volume expansion. Stabilization is usually achieved using foam stabilizers or regulators, also known as cell openers.

[0091] If necessary, the polyol-based base composition according to the invention can therefore further contain a foam stabilizer / regulator. Suitable examples include alkyl polyglycosides. These are obtainable 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 C atoms, preferably 8 to 18 C atoms, and particularly preferably 10 to 12 C atoms in an alkyl radical. Specific examples of longer-chain monoalcohols include 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 above-mentioned longer-chain monoalcohols can also be used.Other foam stabilizers include known anionic, cationic, amphoteric, and nonionic surfactants, as well as mixtures thereof. Preference is given to using alkyl polyglycosides, EO / PO block copolymers, alkyl or aryl alkoxylates, siloxane alkoxylates, polyether polysiloxanes, esters of sulfosuccinic acid, and / or alkali or alkaline earth metal alkanoates. EO / PO block copolymers are particularly preferred.

[0092] Foam composition according to the invention

[0093] A second aspect of the present invention is also a foam composition comprising the previously described polyol-based base composition and at least one polyisocyanate. To produce the foam composition, the components of the polyol-based base composition are mixed with the polyisocyanate and homogenized. The polyisocyanate used may be any aliphatic, cycloaliphatic, and / or aromatic isocyanates known to those skilled in the art with an average NCO functionality of 2 or higher, individually or in any desired mixtures. The NCO functionality indicates how many NCO groups are present in the polyisocyanate. Polyisocyanate means that the compound contains two or more NCO groups.

[0094] Suitable aromatic polyisocyanates are those with aromatically bound isocyanate groups, such as diisocyanatobenzenes, toluene diisocyanates, diphenyl diisocyanates, diphenylmethane diisocyanates, diisocyanatonaphthalenes, triphenylmethane triisocyanates, but also those with isocyanate groups which are bound to an aromatic via an alkylene group, such as a methylene group, such as bis- and tris-(isocyanatoalkyl)-benzenes, -toluenes and -xylenes.

[0095] Preferred examples of aromatic polyisocyanates are: 2,2'-, 2,4'- and 4,4'- diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- tolylene diisocyanate, 2,5-tolylene diisocyanate, 2,6-tolylene 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, diphenylene-methane-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-b / s[6-(o-isocyanatobenzyl)phenyl] diisocyanate. Polymeric polyisocyanates, especially polymeric diphenylmethane diisocyanate, can also be used. Examples of aliphatic polyisocyanates are bis-(isocyanatoalkyl) ethers or alkane diisocyanates, such as methane diisocyanate, propane diisocyanates, butane diisocyanates, pentane diisocyanates, hexane diisocyanates (e.g. hexamethylene diisocyanate, HDI), heptane diisocyanates (e.g. 2,2-dimethylpentane-1,5-diisocyanate, octane diisocyanates, nonane diisocyanates (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 triisocyanates (e.g. 4-isocyanatomethyl-1,8-octane diisocyanate, 5-methylnonane diisocyanate),

[0096] Decane diisocyanates, decane triisocyanates, undecane diisocyanates, undecane triisocyanates, dodecane diisocyanates, dodecane triisocyanates, 1,3- and 1,4-bis-(isocyanatomethyl)cyclohexane (HßXDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), bis-(4-isocyanatocyclohexyl)methane (H12MDI), bis-(isocyanatomethyl)norbornane (NBDI) or 3(4)-isocyanatomethyl-1-methyl-cyclohexyl isocyanate (IMCI), octagydro-4,7-methano-1 H-indenedimethyl diisocyanate, norbornene diisocyanate, 5-isocyanato-1-

[0097] (isocyanatomethyl)-1,3,3-trimethylcyclohexane, ureylenebis(p-phenylene methylene-p-phenylene) diiscoyanate.

[0098] Preferably, the polyisocyanates may also be present as prepolymers, biurets, isocyanurates, iminooxadiazinediones, uretdiones and / or allophanates, which can be prepared by oligomerization of difunctional isocyanates or by reaction of the isocyanate compounds with polyols or polyamines, individually or as a mixture, and which have an average NCO functionality of 2 or greater.

[0099] Examples of suitable, commercially available polyisocyanates 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® 44V20L, 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® Hl 100, Basonat® Hl 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), Voranate T-80 (Type I and II), Isonate 181, Isonate 240, Isonate 125M, Isonate 125 MDR, Isonate 143L, Isonate 50 O,P', PAPI 20, PAPI 27, PAPI 94, PAPI 95, PAPI 901, PAPI 580N (each from DOW).

[0100] The weight percentage of the polyisocyanate based on the total weight of the foam composition is preferably > 0 wt% to 50 wt%, more preferably 1 wt% to 40 wt%, even more preferably 5 wt% to 35 wt%.

[0101] The weight percentage ratios of the polyisocyanate and the polyol are preferably chosen so that the equivalent ratio of isocyanate groups to -OH groups is between 0.1 and 1.7, preferably between 0.2 and 1.2 and more preferably between 0.4 and 1.1.

[0102] Preferably, a catalyst is used both for the reaction of the polyisocyanate with the polyol and for the reaction of the isocyanate with the blowing agent. In a preferred embodiment of the invention, the foam composition comprises a foam and gel catalyst. 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), N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine (Dabco NE300), or 1,4-diazabicyclo[2.2.2]octane in dipropylene glycol (DABCO 33LV) are used.

[0103] Examples of other compounds that can be used as catalysts are 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-dimethylcyclohexylamine, N,N- Dimethylethanolamine, N-(3-dimethylaminopropyl)-N,N-diisopropanolamine, N-ethylmorpholine, / V-methylmorpholine, pentamethyldiethylenetriamine and / or triethylenediamine.

[0104] In one embodiment, the composition according to the invention further contains at least one further component selected from plasticizers, crosslinking agents, biocides, organic and / or inorganic additives and / or other additives.

[0105] The plasticizer's function is to soften the cured polymer network. Furthermore, the plasticizer's function is to introduce an additional liquid component so that the fillers are completely wetted and the viscosity is adjusted to make the coating processable. The plasticizer can be included in the composition in such an amount that it can adequately fulfill the functions just described.

[0106] 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, Cw-C2i-alkylsulfonic acid esters of phenol and alkyl esters. Preferably, the plasticizer is an ester derivative of terephthalic acid, a triol ester of caprylic acid, a glycol diester, diol esters of aliphatic dicarboxylic acids, ester derivative of citric acid, secondary alkylsulfonic acid esters, ester derivatives of glycerol with epoxy groups and ester derivatives of phosphates.More preferably, the plasticizer is bis(2-ethylhexyl) terephthalate, trihydroxymethylpropyl caprylate, 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 ester, 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. Most preferably, the plasticizer is a phosphate ester, as these can act as both plasticizers and flame retardants.

[0107] The plasticizer may preferably be present in the composition in an amount of up to 30% by weight, more preferably up to 20% by weight and more preferably up to 8% by weight, based on the total composition.

[0108] In addition to the additives already described, the composition may optionally contain conventional auxiliaries such as wetting agents, for example based on polyacrylates and / or polyphosphates, dyes, fungicides, or various fillers such as vermiculite, inorganic fibers, quartz sand, glass microspheres, mica, silicon dioxide, mineral wool, and the like.

[0109] 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-sagging agents, and thixotropic agents are preferably 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 the compounds. Rheology additives based on pyrogenic or precipitated silicas, or based on silanized pyrogenic or precipitated silicas, can also be used.The rheology additive preferably comprises pyrogenic 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, provided they are in solid form, powdered celluloses and / or suspending agents such as xanthan gum.

[0110] The present invention also further provides a foamed molded article for fire protection applications produced from the foam composition according to the invention. For this purpose, the components of the polyol-based base composition are mixed with the polyisocyanate and homogenized. Mixing and homogenization preferably take place via a mixing head. The homogenized foam composition is introduced into a molding element with a predefined geometry. As a result of the reaction of the polyisocyanate with the polyol and the blowing agent, foaming occurs in the molding element. Following complete curing, the molding element can be removed, and the foamed molded article can be removed.

[0111] The foamed molded body preferably has a rectangular cross-section. This allows for particularly easy and seamless installation of fire protection profiles in a wall or ceiling opening.

[0112] A fifth subject matter is also the use of at least one sustainable filler selected from the group consisting of (kraft) lignin, starch and mixtures thereof in a polyol-based base composition comprising at least one sustainable polyol for improving the ash crust hardness under the action of heat of a shaped body produced from the polyol-based base composition.

[0113] The invention is explained in more detail below using 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.

[0114] EXAMPLES OF IMPLEMENTATION

[0115] Unless otherwise stated, all components of the compositions listed here are commercially available and were used in commercially usual quality.

[0116] All percentages given in the examples refer to the total weight of the described composition as a calculation basis, unless otherwise stated.

[0117] Table 1: Composition of Reference Examples 1 to 4 and Examples 1 to 2 according to the invention [in wt.%] and results of the determination of the ash crust hardness

[0118] Table 2: Composition of Reference Examples 5 to 76 and of Examples 3 and 4 according to the invention [in wt.%] and results of the determination of the ash crust hardness

[0119] Production of a foamed molded body (foam block)

[0120] The individual components of the examples in Tables 2 and 3 were stirred into a homogeneous mixture in a suitable container (e.g., a paper cup) using a wooden spatula. The mixture was then poured into a plastic mold (20 cm x 13.5 cm x 5 cm) in a sealable metal casing, and the casing was sealed. After approximately 5 minutes, the foamed mold was removed from the mold.

[0121] Marko-TMA and determination of ash crust hardness

[0122] A cylindrical sample with a diameter of 45 mm and a height of 20 mm was punched out of the produced mold. This sample was placed in a metal cylinder, loaded with a 100 g weight, and introduced into the Macro TMA from ASG Analytik-Service Gesellschaft. The sample was ashed using the following temperature program: The metal cylinder was heated to 650 °C at a heating rate of 15 °C / min. After holding this temperature for 10 minutes, the test setup was allowed to cool to room temperature. Using a texture analyzer

[0123] The ash crust hardness of the resulting ash was determined using a CT3 4500 from Brookfield (FOCS7 attachment).

Claims

PATENT CLAIMS 1. Polyol-based base composition for producing a foamed molded article for fire protection applications comprising - at least one sustainable polyol a1) - at least one intumescent fire protection additive, and - a blowing agent, characterized in that the polyol-based base composition comprises at least one sustainable filler selected from the group consisting of starch, lignin or mixtures thereof.

2. Polyol-based base composition according to claim 1, characterized in that the sustainable polyol a1) is based on one or more natural oils.

3. Polyol-based base composition according to claim 2, characterized in that the natural oil is selected from the group consisting of soybean oil, canola oil, cashew nut shell oil, sunflower oil, corn oil, linseed oil, poppy seed oil, cottonseed oil, tung oil, palm oil, peanut oil, fish oil, olive oil, safflower oil, rapeseed oil and coconut oil.

4. Polyol-based base composition according to claim 2 or 3, characterized in that the sustainable polyol a1) is a cashew nut shell oil-based polyol.

5. Polyol-based base composition according to claim 4, characterized in that the sustainable polyol a1) is a cashew nutshell oil-based polyether polyol or a cashew nutshell oil-based polyester polyol or a mixture thereof.

6. Polyol-based base composition according to claim 1, characterized in that the sustainable polyol a1) is a recycled polyol produced from polyurethane-based mattresses.

7. Polyol-based base composition according to one of the preceding claims, characterized in that the polyol-based base composition further comprises a further polyol a2), wherein the further polyol a2) is not a sustainable polyol a1).

8. Polyol-based base composition according to one of the preceding claims, characterized in that the blowing agent comprises one or more compounds capable of releasing CO2 after activation by reaction.

9. A foam composition comprising a polyol-based base composition according to any one of the preceding claims and at least one polyisocyanate.

10. A process for producing a foamed molded article comprising: a. mixing the components of the foam composition according to claim 9; b. introducing the foam composition into a molding element; c. after the components of the foam composition have reacted, removing the molded foamed article from the molding element.

11. A foamed molded article made from a foam composition according to claim 9.

12. Use of at least one sustainable filler selected from the group consisting of lignin, starch and mixtures thereof in a polyol-based base composition comprising at least one sustainable polyol a1) to improve the CO2 balance of the foamed molded body 13. Use according to claim 12, characterized in that the foamed molded body has an improved ash crust hardness according to exposed to heat.

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