Manufacture of Flame-Retardant Polyurethane Foam

Abstract

A composition for producing a PU foam, preferably a rigid PU foam, the composition comprising: - at least one halogen-free polyester polyol and at least one halogenated polyol, - at least one physical blowing agent, - at least one flame retardant selected from the group consisting of: (a) phosphate esters, preferably TCPP, TEP and / or TCEP, especially those from the group of TCPP and / or TEP and / or (b) phosphonates, preferably those from the group of DMMP and / or DMPP, - red phosphorus, and at least one polyisocyanate component, wherein the composition has an index of at least 200.

Description

Technical Field

[0001] The present invention relates to the field of polyurethanes, preferably polyurethane foams, particularly rigid polyurethane foams. In particular, the present invention relates to the production of flame-retardant polyurethane foams, preferably rigid flame-retardant polyurethane foams, using a combination of synergistically acting components, and to compositions for producing such foams, and further to the use of such foams.

[0002] For the purposes of the present invention, polyurethane (PU) is understood in particular to be a product that can be obtained by reacting a polyisocyanate component with a polyol component or a compound having isocyanate-reactive groups. Here, in addition to polyurethanes, further functional groups such as, for example, uretdione, carbodiimide, isocyanurate, allophanate, biuret, urea and / or uretonimine may also occur. Thus, in addition to polyurethanes, polyisocyanurates, polyureas, and polyisocyanate reaction products containing uretdione groups, carbodiimide groups, allophanate groups, biuret groups and uretonimine groups are also understood to be PUs within the meaning of the present invention. A polyurethane foam (PU foam) is understood in the context of the present invention to be a foam obtained as a reaction product of a polyisocyanate component with a polyol component or a compound having isocyanate-reactive groups. Here, in addition to what is referred to as polyurethane, further functional groups such as, for example, allophanate, biuret, urea, carbodiimide, uretdione, isocyanurate or uretonimine may also occur.

[0003] PU rigid foam is an established technical term. The known fundamental difference between flexible and rigid foams is that flexible foams exhibit elastic behavior and thus the deformation is reversible. In contrast, rigid foams are permanently deformed. The terms foam and foam material are used synonymously in the context of the present invention. This also applies to terms based thereon, such as, for example, PU foam or PU foam material.

[0004] In relation to the provision of PU foams, especially rigid PU foams, a particularly important concern is to produce PU foams with excellent flame retardancy. For this purpose, flame retardants are used. Flame retardants themselves are known substances and are used to suppress, delay or prevent the spread of fire. In known prior art, for example, in "Plastics Flammability Handbook", Carl Hanser Verlag, 3rd edition 2004, corresponding flame retardants having flame retardancy and suitable for use in PU foams are described.

[0005] Due to the frequent occurrence of fire accidents, in recent years, the global requirements for the flame retardancy of building materials, especially thermal insulation materials, in the construction field have been increasing very rapidly. For this reason, in countries with particularly high requirements, such as Japan and South Korea, conventional rigid polyurethane foams can no longer be used. This is because conventional rigid polyurethane foams do not meet the new application standards. For example, in South Korea, in accordance with KS F ISO 5660-1:2015-03, the total heat release in a cone calorimeter is 8 MJ / m 2 The heat release rate is specified to be 200 kW / m or less as follows, and as a result, the requirements of that country for rigid polyurethane foams are the strictest in the world. 2

[0006] ​To improve the flame retardancy of polyurethane foams, especially rigid polyurethane foams, it is common to increase the amount of flame retardant used. However, the effects achievable thereby and the maximum amounts that can be used are limited by the fact that the flame retardant adversely affects the overall properties of the foam, such as the mechanical strength of the foam, and / or the processing and manufacture of the polyurethane foam. For example, the use of triethyl phosphate (TEP), tris(2-chloroethyl) phosphate (TCEP) or tris(1-chloro-2-propyl) phosphate (TCPP) usually exhibits a strong plasticizing effect, resulting in a decrease in mechanical durability and thereby limiting the amount used. Other flame retardants, especially those used as solids, are associated with considerable problems regarding dispersion in liquid raw materials, leading to an increase in viscosity, which makes processing extremely difficult or even impossible. Many flame retardants also have ecological and toxicological drawbacks, so it is required to meet all requirements while minimizing their use.

[0007] Against this background, a specific object of the present invention was to provide a PU foam, especially a rigid PU foam, which advantageously meets the increased requirements regarding flame retardancy in accordance with KS F ISO 5660-1:2015-03, i.e., advantageously, the total heat release at a heating rate of 50 kW / m 2 is 8 MJ / m 2 or less and the heat release rate is 200 kW / m 2 or less, while having no or only a very slight impact on the processing and foaming properties.

[0008] In this context, it has surprisingly been found that, within the scope of the present invention, a specific combination of the compounds according to claim 1 can be used in a composition for the production of a PU foam, advantageously a rigid PU foam, especially a rigid PU foam with an index exceeding 200, to solve the above problems. In this case, there is no or only a very slight impact on the processing and foaming properties.

[0009] The above problems are solved by the subject matter of the present invention. The subject matter of the present invention is a composition for the production of PU foams, preferably for the production of rigid PU foams, the composition comprising the following: · at least one halogen-free polyester polyol and at least one halogenated polyol, · at least one physical blowing agent, · at least one flame retardant, comprising the following: (a) a phosphate ester, preferably tris(1-chloro-2-propyl) phosphate (TCPP), triethyl phosphate (TEP) and / or tris(2-chloroethyl) phosphate (TCEP), in particular the group of TCPP and / or TEP and / or (b) a phosphonate, preferably the group of dimethylmethanephosphonate (DMMP) and / or dimethylpropanephosphonate (DMPP) selected from, · red phosphorus, and comprising at least one polyisocyanate component, wherein the composition has an index of at least 200. The upper limit of the index can preferably be, for example, 1000, preferably 500.

[0010] The subject matter of the present invention is associated with a variety of advantages. For example, the subject matter of the present invention enables the provision of PU foams, preferably rigid PU foams, which meet particularly high requirements regarding flame retardancy, such as those specified in KS F ISO 5660-1:2015-03. Advantageously, this can be achieved without impairing other properties of the foam, especially its mechanical properties. With regard to the provision of PU foams, preferably rigid PU foams, it is furthermore possible to obtain a foam structure with a particularly uniform and defect-free fine cell structure. This enables the provision of corresponding PU foams with particularly excellent use properties. Overall, the present invention enables easy processing from the perspective of foam production.

[0011] When the red phosphorus (CAS No 7723-14-0) used according to the present invention is microencapsulated, it is a particularly preferred embodiment of the present invention. The microencapsulation of red phosphorus is well known from the prior art. Possible variants are described, for example, in European Patent Application Publication No. 1262453.

[0012] When the composition according to the present invention further comprises at least one smoke suppressant, it is a particularly preferred embodiment of the present invention, wherein the smoke suppressant is preferably selected from the group consisting of antimony trioxide, zinc stannate, zinc hydroxystannate, zinc borate, calcium borate, zinc pyrophosphate, aluminum orthophosphate and aluminum phosphinate, wherein antimony trioxide and / or zinc borate are most preferred.

[0013] When one or at least one component, for example a compound, is selected from the group consisting of a plurality of components, for example a plurality of compounds, in the sense of the present invention, this means that in the sense of the present invention, the individual components mentioned in this group may be selected or a mixture of this group may be selected. Taking the aforementioned smoke suppressant as an example, this means that, for example, zinc stannate or, for example, antimony trioxide etc. may be selected, or, for example, a mixture of antimony trioxide and zinc hydroxystannate or, for example, other mixtures may be selected.

[0014] The solid flame retardant such as red phosphorus used, or the smoke suppressant, can be introduced into the reaction mixture, for example, via one of the two reactive components (i.e., via the polyol component or via the polyisocyanate component). In this case, introduction via the polyol component is preferred.

[0015] In the composition according to the present invention, at least one halogenated polyol is as follows: (i) Brominated and / or chlorinated aliphatic or aromatic polyether diols and / or polyether triols, preferably brominated aliphatic or aromatic polyether diols and / or polyether triols and (ii) A polyester polyol based on tetrabromophthalate, preferably compound 1 [Chemical formula] selected from the group consisting of, where when compound 1 is the most preferred, this is a particularly preferred embodiment of the present invention.

[0016] When the composition according to the present invention further contains compound 1 and TCPP and / or TEP and antimony trioxide and / or zinc borate, this is a further particularly preferred embodiment of the present invention.

[0017] Furthermore, it is more preferable that the composition according to the present invention contains at least one catalyst, preferably at least one trimerization catalyst, particularly a catalyst selected from the group consisting of ammonium salts and metal salts of 2-ethylhexanoic acid, formic acid, acetic acid, propionic acid, neodecanoic acid and pivalic acid. This also corresponds to a further particularly preferred embodiment of the present invention.

[0018] It is similarly preferred that at least one physical blowing agent is selected from the group consisting of dimethoxymethane, methyl formate, HFC-245fa, 1233zd, 1336mzz, cyclopentane, isopentane and n-pentane, particularly preferably selected from the group consisting of HFC-245fa, 1233zd, cyclopentane, isopentane and n-pentane. This also corresponds to a further particularly preferred embodiment of the present invention.

[0019] Based on 100 parts by weight of the fully halogen-free polyol component · 1 to 80 parts by weight, preferably 1.5 to 50 parts by weight, particularly preferably 2 to 40 parts by weight of the total amount of halogenated polyol · A total of 2 to 60 parts by weight, preferably 5 to 50 parts by weight, particularly preferably 5 to 40 parts by weight of a flame retardant, which is selected from the group consisting of (a) phosphate esters, preferably TCPP, TEP and / or TCEP, and / or (b) phosphonates, preferably selected from the group consisting of DMMP and / or DMPP · A total of 1 to 45 parts by weight, preferably 2 to 35 parts by weight, particularly preferably 5 to 30 parts by weight of red phosphorus · Optionally, a total of 0 to 40 parts by weight, preferably 1 to 35 parts by weight, particularly preferably 1.5 to 25 parts by weight of a smoke suppressant, preferably selected from the group consisting of antimony trioxide, zinc stannate, zinc hydroxystannate, zinc borate, calcium borate, zinc pyrophosphate, aluminum orthophosphate and aluminum phosphinate When it is a feature of the composition according to the present invention that it is included, this also corresponds to a particularly preferred embodiment of the present invention

[0020] Based on 100 parts by weight of the all-halogen-free polyol component · A total of 1 to 80 parts by weight, preferably 1.5 to 50 parts by weight, particularly preferably 2 to 40 parts by weight of Compound 1 · A total of 2 to 60 parts by weight, preferably 5 to 50 parts by weight, particularly preferably 5 to 40 parts by weight of TCPP and / or TEP · A total of 1 to 45 parts by weight, preferably 2 to 35 parts by weight, particularly preferably 5 to 30 parts by weight of red phosphorus · A total of 1 to 40 parts by weight, preferably 1.5 to 35 parts by weight, particularly preferably 1.5 to 25 parts by weight of antimony trioxide and / or zinc borate When it is a feature of the composition according to the present invention that it is included, it is a further particularly preferred embodiment of the present invention

[0021] Furthermore, it is particularly preferred that the composition according to the invention further comprises at least one foam stabilizer, preferably based on polyether siloxane, in particular in an amount of 0.1 to 4 parts per 100 parts of the total polyol component. This corresponds to a particularly preferred embodiment of the invention. Foam stabilizers used in connection with the production of PU foams, preferably based on polyether siloxane, are known per se. Suitable foam stabilizers are also described below.

[0022] When the composition according to the invention contains water and / or formic acid, this is a further particularly preferred embodiment of the invention.

[0023] Of course, the composition according to the invention can, if desired, contain any further optional additives which are known from the prior art and commonly used in connection with the production of polyurethanes, in particular PU foams.

[0024] A further subject of the invention is a method for producing a PU foam, preferably a rigid PU foam, using a foaming reaction mixture comprising the composition according to the invention as defined in any one of claims 1 to 10 or described in the above-mentioned particularly preferred embodiments. The foaming reaction mixture can preferably also consist of the above-mentioned composition according to the invention.

[0025] Particularly preferred PU foam formulations, in particular rigid PU foam formulations, according to the invention have the composition shown in Table 1:

Table 1

[0026] Another further subject of the invention is a PU foam, preferably a rigid PU foam, produced by the method according to the invention using the composition according to the invention.

[0027] The PU foam according to the invention, in particular the rigid PU foam, has a density of 5 to 900 kg / m 3 , preferably 5 to 350 kg / m3 , particularly when it has a unit volume weight of 10 to 200 kg / m 3 , is a preferred embodiment of the present invention.

[0028] A further subject of the present invention relates to the use of the above-described PU foam according to the present invention, in particular a rigid PU foam, as a heat insulating material and / or building material, particularly in building applications, particularly as a sprayed foam, or in the low temperature field or as a pipe jacket for pipes.

[0029] Therefore, the present invention has already been described in detail, and those skilled in the art are proficient in the production of PU, particularly PU foam, using at least one polyol component and at least one polyisocyanate component.

[0030] According to a particularly preferred embodiment of the present invention, the composition according to the present invention particularly comprises the following components: a) A polyol component comprising at least one halogen-free polyester polyol and at least one halogenated polyol b) A polyisocyanate component (at least one polyisocyanate and / or polyisocyanate prepolymer) c) A catalyst that catalyzes the reaction of isocyanate groups with OH groups, NH groups or other isocyanate-reactive groups and / or the reaction of isocyanate groups with each other d) Optionally a foam stabilizer e) A blowing agent f) A flame retardant g) Optionally further additives .

[0031] As the polyol component (a), one or more organic compounds having OH groups, SH groups, NH groups and / or NH 2 groups and having a functionality of 1.8 to 8 can be used. Here, the polyol component comprises at least one organic compound having at least two isocyanate-reactive groups selected from OH groups, SH groups, NH groups and / or NH 2 groups, particularly OH groups.

[0032] A functionality that is not an integer, for example a functionality of 1.8, can result from mixing at least one compound having a relatively high functionality of, for example, 2 or more with at least one compound having a functionality of, for example, 1. This can occur in particular when a polyisocyanate component (b) having a functionality exceeding 2 or an additional crosslinking agent as any additive (g) is used.

[0033] Suitable compounds commonly used in PU production are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3. Auflage 1993, Kapitel 3.1. Usually, compounds having an OH number in the range of 10 to 1200 mg KOH / g are used.

[0034] Particularly preferred compounds are all polyether polyols and polyester polyols commonly used in the production of polyurethane systems, in particular polyurethane foams.

[0035] Polyether polyols can be produced by known methods, for example by polymerization of alkylene oxides, preferably ethylene oxide, 1,3 - propylene oxide, 1,2 - or 2,3 - butylene oxide and / or tetrahydrofuran.

[0036] Preferred polyester polyols are preferably based on esters of aliphatic or aromatic polycarboxylic acids having 2 to 12 carbon atoms. Examples of aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid and fumaric acid. Examples of aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and isomeric naphthalenedicarboxylic acids. Preferred polyester polyols can in particular be obtained by condensation of these polycarboxylic acids with polyhydric alcohols, advantageously diols or triols having 2 to 12 carbon atoms, particularly preferably 2 to 6 carbon atoms, preferably trimethylolpropane, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and / or glycerol.

[0037] Furthermore, polyether polycarbonate polyols, polyols based on natural oils (natural oil-based polyols, NOPs; WO 2005 / 033167, US 2006 / 0293400 A1, WO 2006 / 094227, WO 2004 / 096882, US 2002 / 0103091 A1, WO 2006 / 116456, EP 1678232 B1), filled polyols, prepolymer-based polyols and / or recycled polyols can be used.

[0038] Recycled polyols are polyols obtained from polyurethanes by chemical recycling processes such as solvolysis, for example glycolysis, hydrolysis, acidolysis or aminolysis. The use of recycled polyols is a particularly preferred embodiment of the invention.

[0039] Within the scope of the present invention, the polyol component must always contain at least one halogen-free polyester polyol and at least one halogenated polyol as already described above.

[0040] As the polyisocyanate component (b), generally one or more polyisocyanates having two or more isocyanate groups can be used. The polyisocyanates suitable for the purpose of the present invention are all organic isocyanates having two or more isocyanate groups, particularly aliphatic, alicyclic, araliphatic and preferably aromatic polyisocyanates known per se.

[0041] Examples that can be cited here include alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene-1,4-diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene diisocyanate (PDI) and preferably hexamethylene-1,6-diisocyanate (HMDI), alicyclic diisocyanates, such as cyclohexane 1,3- and 1,4-diisocyanate, and corresponding isomer mixtures, 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 2,4- and 2,6-methylcyclohexyl diisocyanate, and corresponding isomer mixtures, and preferably aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate (TDI), and corresponding isomer mixtures, naphthalene diisocyanate, diethyltoluene diisocyanate, 4,4'- or 2,2'- or 2,4'-diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PMDI, "polymeric MDI"). The organic polyisocyanates can be used alone or in the form of their mixtures. Similarly, it is also possible to use corresponding "oligomers" of diisocyanates, such as IPDI trimers based on isocyanurate, biuret or uretdione. Furthermore, it is also possible to use prepolymers based on the above-mentioned isocyanates. Particularly suitable are mixtures of MDI with higher condensation analogues having an average functionality of 2 to 4, known as "polymeric MDI" (also called "crude MDI" or "raw MDI"), and various isomers of TDI in pure form or as isomer mixtures. It is also possible to use so-called modified isocyanates, which are isocyanates modified by incorporating groups such as urethane, uretdione, isocyanurate, allophanate, etc.Examples of particularly suitable isocyanates are also described, for example, in European Patent No. 1712578, European Patent No. 1161474, International Publication No. 00 / 58383, US Patent Application Publication No. 2007 / 0072951, European Patent No. 1678232 and International Publication No. 2005 / 085310, and these documents are incorporated herein by reference in their entirety.

[0042] The preferred ratio of the total polyisocyanate component to the total polyol component is expressed as an index of the formulation, i.e., the value obtained by multiplying the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g., OH groups, NH groups) by 100, which ranges from 200 to 1000, preferably from 200 to 500. The index 100 represents a molar ratio of reactive groups of 1:1. According to the present invention, the composition described in the claims has an index of at least 200.

[0043] Suitable catalysts (c) that can be used in the production of polyurethanes, particularly PU foams, are known to those skilled in the art from the prior art. In the context of the present invention, all compounds that can catalyze the reaction of isocyanate groups with OH groups, NH groups or other isocyanate-reactive groups and / or the reaction of isocyanate groups with each other can be used. Compounds that catalyze the reaction of isocyanate groups with each other, particularly the trimerization reaction, are known to those skilled in the art as trimerization catalysts and are described, for example, in European Patent Application Publication No. 1745847.

[0044] Here, conventional catalysts known from the prior art can be used, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers having one or more amino groups), ammonium compounds, organometallic compounds and / or metal salts, preferably compounds of tin, iron, bismuth, potassium and / or zinc. In particular, mixtures of such multiple compounds can be used as catalysts.

[0045] The use of the foam stabilizer (d) and its use in the production of PU foams are known to those skilled in the art. The use of the foam stabilizer is optional, and advantageously one or more foam stabilizers are used. As the foam stabilizer, in particular, surface-active compounds (surfactants) can be used. Preferably, the foam stabilizer is used during the production of the PU foam. The foam stabilizer can be used to optimize the desired cell structure and the foaming process. In particular, within the scope of the present invention, one or more known Si-containing compounds that assist in foaming (stabilization, cell adjustment, cell opening, etc.) can be used. These compounds are well known from the prior art. Particularly preferably, at least one foam stabilizer based on polyether siloxane can be used. The corresponding siloxane structures that can be used in the spirit of the present invention are described, for example, in the following patent documents, which only describe the use in conventional PU foams (such as molded foams, mattresses, thermal insulation materials, building foams, etc.): Chinese Patent Specification No. 103665385, Chinese Patent Specification No. 103657518, Chinese Patent Specification No. 103055759, Chinese Patent Specification No. 103044687, US Patent Application Publication No. 2008 / 0125503, US Patent Application Publication No. 2015 / 0057384, European Patent Application Publication No. 1520870, European Patent No. 1211279, European Patent No. 0867464, European Patent No. 0867465, European Patent No. 0275563. In addition to the surface-active Si-containing compounds, Si-free surfactants can also be used. For example, European Patent Application Publication No. 2295485 describes the use of lecithin as a foam stabilizer for the production of rigid PU foams, and US Patent No. 3746663 describes the use of a vinyl pyrrolidone-based structure as a foam stabilizer for the production of rigid PU foams. Further Si-free foam stabilizers are described, for example, in European Patent No. 2511328, German Patent Application Publication No. 1020011007479, German Patent Invention No. 3724716, European Patent No. 0734404, European Patent No. 1985642, German Patent No. 2244350, and US Patent No. 5236961.

[0046] The blowing agent (e) and its use in the production of PU foams are known to those skilled in the art. The use of one blowing agent (e) or a combination of two or more blowing agents (e) generally depends on the type of foaming method used, the type of system, and the use of the resulting PU foam. According to the present invention, at least one physical blowing agent is used. Chemical blowing agents can also be used additionally. Depending on the amount of blowing agent used, high-density or low-density foams are produced. For example, foams with a density of 5 kg / m 3 ~900 kg / m 3 , preferably 5~350, particularly preferably 8~200 kg / m 3 , especially 8~150 kg / m 3 can be produced.

[0047] As the physical blowing agent, one or more suitable compounds having an appropriate boiling point and their mixtures can be used. The preferably usable physical blowing agents have already been mentioned.

[0048] As the chemical blowing agent, for example, one or more compounds that react with NCO groups to release gas, such as water or formic acid, or one or more compounds that release gas during the reaction as a result of a temperature increase, such as sodium bicarbonate, can be used. When the composition according to the present invention contains water and / or formic acid as a chemical blowing agent in addition to the physical blowing agent, this corresponds to a particularly preferred embodiment of the present invention.

[0049] As the flame retardant (f), preferably, as already described, phosphate esters, preferably at least one compound from the group of TCPP, TEP and / or TCEP, and / or phosphonates, preferably at least one compound from the group of DMMP and / or DMPP, and furthermore red phosphorus, preferably microencapsulated red phosphorus, are used.

[0050] As any additive (g), those known in the prior art and one or more substances used in the production of polyurethanes, especially PU foams, can be used. For example, crosslinking agents, chain extenders, stabilizers against oxidative degradation (so-called antioxidants), biocides, cell fining additives, nucleating agents, cell openers, solid fillers, antistatic additives, thickeners, dyes, pigments, color pastes, fragrances and / or emulsifiers, etc. can be used.

[0051] Furthermore, the composition according to the invention optionally contains a so-called smoke suppressant. Preferred smoke suppressants that can be used have already been mentioned. Advantageously, the smoke suppressant has no direct effect on flame retardancy when used alone, but rather significantly enhances the effect of other flame retardants in part and / or reduces the generation of smoke. Smoke suppressants are known to those skilled in the art and include, for example, antimony trioxide, zinc hydroxystannate, zinc stannate, zinc borate, calcium borate or antimony pentoxide. These are also described, for example, in Weil, Edward D., Levchik, Sergei V. (2016) Flame Retardants for Plastics and Textiles - Practical Applications (2nd Edition); Carl Hanser Verlag, Chapter 4, or International Publication No. WO 2009 / 109318, or Su et al., Polymer degradation and stability, 2012;97(11):2128 - 2135, or Horrocks et al., Journal of Fire Sciences, 2010;28(3):217 - 248.

[0052] Unless otherwise apparent from the description herein, all preferred or particularly preferred embodiments of the invention can be combined with one or more other preferred or particularly preferred embodiments of the invention.

[0053] The method for manufacturing a PU foam according to the present invention can be carried out by all known methods, for example, by the hand mixing method or preferably using a foaming machine. When carrying out the method using a foaming machine, high-pressure or low-pressure equipment can be used. The method according to the present invention can be carried out batchwise or continuously, and for example, 1K, 1.5K or 2K systems as described in European Patent Application Publication No. 3717538, US Patent No. 7776934, European Patent No. 1400547 or European Patent No. 2780384 can be used.

[0054] The subject matter according to the present invention will be exemplarily described below, but the scope of application of the present invention is clear from the entire specification and the scope of the claims, and the present invention is not limited to these exemplary embodiments.

[0055] When ranges, general formulas or compound classes are indicated, these shall include not only the corresponding ranges or groups of compounds explicitly mentioned, but also all partial ranges and subgroups of compounds that can be obtained by extracting individual values (ranges) or compounds. When a document is cited within the scope of this specification, its content, especially the content regarding the situation in the context in which the document is cited, shall completely constitute a part of the disclosure content of the present invention. Unless otherwise specified, percent data are data in weight percent units. When an average value is indicated, unless otherwise specified, this is the number average. When parameters determined by measurement are indicated, unless otherwise specified, the measurement was carried out at a temperature of 23 °C and standard pressure.

Examples

[0056] Using the formulations shown in Tables 2 and 3, performance comparisons were made. Comparative foaming was carried out by the hand mixing method. For this purpose, the polyol component, catalyst, water, foam stabilizer, flame retardant, physical blowing agent and optionally further additives were weighed into a beaker and mixed with a disk-type stirrer (6 cm in diameter) at 1000 rpm for 30 seconds (batch size 500 g). By weighing again, the amount of blowing agent evaporated during the mixing process was determined and replenished to bring it back to the original amount. Here, pMDI (“polymeric MDI”) was added, and the mixture was stirred with the aforementioned stirrer at 3000 rpm for 5 seconds and immediately poured into an aluminum mold with dimensions of 25 cm × 50 cm × 7 cm, thermostatically controlled at 60 °C and lined with a polyethylene film. The foam was demolded after 10 minutes. The day after foaming, the foam was analyzed. The surfaces of the upper and lower surfaces, as well as internal defects, were subjectively evaluated on a scale of 1 to 10, where 10 represents a (perfect) defect-free foam and 1 represents a very defective foam.

[0057] The combustion behavior was measured using a cone calorimeter in accordance with KS F ISO 5660-1:2015-03. For this purpose, three test specimens of 10 × 10 × 5 cm were cut out from each foam, and the total heat release (“Total Heat Release”-THR (unit: MJ / m 2 )) within 600 seconds, the peak heat release rate (“Peak Heat Release Rate”-PHRR (unit: kW / m 2 )) within 600 seconds, the mass loss during combustion (unit: %), and the combustion time (unit: seconds), more precisely the time from ignition to extinction of the flame, were measured. The heating rate was 50 kW / m 2 . The arithmetic mean value was obtained from the values of the three test specimens. When THR < 8 MJ / m 2 and PHRR < 200 kW / m 2 were achieved, the test was considered a pass. The results are shown in Tables 4 and 5.

[0058]

Table 2

[0059]

Table 3-1

Table 3-2

[0060]

Table 4

[0061]

Table 5

[0062] From these results, it can be seen that the foam based on the composition according to the present invention meets the flame retardancy requirements in contrast to the selected controls not according to the present invention, and the influence on the related foaming properties by the use of the composition according to the present invention is either none or very small. The fact that not only the mass loss of the composition according to the present invention was significantly reduced but also the combustion time was shortened indicates that the amount of the material transferred to the gas phase is small, which is also an indicator of a significant reduction in smoke generation.

[0063] In Samples 20 and 21, very coarse and unusable foams were obtained, and as a result, the combustion test could not be carried out.

Claims

1. A composition for manufacturing PU foam, wherein the composition is as follows: - At least one halogen-free polyester polyol and at least one halogenated polyol, - At least one physical blowing agent, - At least one flame retardant, which is: (a) Group of phosphate esters and / or (b) Group of phosphonates The ones to be selected from, - Akarin, The composition also comprises at least one polyisocyanate component, wherein the composition has an index of at least 200.

2. The composition according to claim 1, characterized in that the composition further comprises at least one smoke suppressant.

3. The at least one halogenated polyol is as follows: (i) Brominated and / or chlorinated aliphatic or aromatic polyetherdiols and / or polyethertriols Furthermore (ii) Tetrabromophthalate-based polyester polyol The composition according to claim 1 or 2, characterized by being selected from the group consisting of the following.

4. The composition is compound 1 【Chemistry 1】 The composition according to claim 1 or 2, characterized by comprising tris(1-chloro-2-propyl) phosphate and / or triethyl phosphate, and further antimony trioxide and / or zinc borate.

5. The composition according to claim 1 or 2, characterized in that the composition comprises at least one catalyst.

6. The composition according to claim 1 or 2, characterized in that the at least one physical blowing agent is selected from the group consisting of dimethoxymethane, methyl formate, HFC-245fa, 1233zd, 1336mzz, cyclopentane, isopentane, and n-pentane.

7. Per 100 parts by weight of the total halogen-free polyol component - 1 to 80 parts by weight of halogenated polyols - A total amount of 2 to 60 parts by weight of a flame retardant, which is selected from the group of (a) phosphate esters and / or selected from the group of (b) phosphonates. - Total amount of red phosphorus: 1 to 45 parts by weight - Optionally, 0 to 40 parts by weight of smoke suppressant in total. The composition according to claim 1 or 2, characterized in that it contains

8. Per 100 parts by weight of the total halogen-free polyol component - Compound 1 in a total amount of 1 to 80 parts by weight - 2 to 60 parts by weight of tris(1-chloro-2-propyl) phosphate and / or triethyl phosphate in total - Total amount of red phosphorus: 1 to 45 parts by weight - 1 to 40 parts by weight of antimony trioxide and / or zinc borate The composition according to claim 4, characterized in that it contains

9. The composition according to claim 1 or 2, characterized in that it contains at least one foam stabilizer.

10. The composition according to claim 1 or 2, characterized in that it comprises water and / or formic acid.

11. A method for producing a PU foam using a foaming reaction mixture comprising the composition defined in claim 1 or 2.

12. A PU foam manufactured by the method described in claim 11.

13. Use of the PU foam according to claim 12 as an insulating material and / or building material, or in low-temperature fields, or as a pipe jacket for pipes.

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