Foam stabilizer for phenol foam

Abstract

To provide a phenol resin foam material having good performance characteristics.SOLUTION: A composition for producing a phenol resin foam material contains at least one kind of phenol resin, at least one kind of foaming agent, at least one kind of catalyst, and at least one kind of polyether siloxane by formula 1: MaMb1DcDd1, wherein maximum 50 mol% of a residue R1 in polyether siloxane by formula 1 is each independently the same or different alkyl residue having 6 to 18 carbon atoms, and 0.1 to 20 pts.wt. of the total amount of at least the one kind of polyether siloxane by formula 1 is contained based on 100 pts.wt. of the whole phenol resin to be used.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to the field of phenolic foams. In particular, the present invention relates to a composition for producing a phenolic foam, a method for producing a phenolic foam, the phenolic foam produced by the present invention, and the use of a polyether siloxane to improve the insulating capacity of a phenolic foam. Within the scope of the present invention, phenolic foams are understood to mean foams obtained by reacting a phenolic resin with an acid as a catalyst, with the addition of a blowing agent and a foam stabilizer. Phenolic foams are known per se to those skilled in the art and are described, for example, in EP 3830174, DE 602004006376, EP 2898005, EP 1922357, WO 2022043561, EP 4073155, A2 2021238847, or WO 2006114777. Phenolic foam materials may also be referred to as phenolic foam or phenolic foam, and these terms are used interchangeably. This also applies to the present invention.

[0002] In the production of phenolic foam materials, cell-stabilizing or foam-stabilizing additives can generally be used, which must be considered to result in a fine-celled, uniform, and defect-free foam structure, and thus significantly favorably influence the performance properties, particularly the insulating capacity of the foam. For this purpose, foam stabilizers, such as ethoxylated vegetable oil-based foam stabilizers, such as castor oil, as described in EP-A-3830174, can usually be used. The use of polyether-modified siloxanes, also known as polyether siloxanes (PES), as described in, for example, WO 2022043561, U.S. Pat. No. 3,298,973, GB 1,088,056, GB 1,087,056, DE 2,833,002, U.S. Pat. No. 4,067,829, DE 2,254,305, or WO 2009 / 048717, has been found to be particularly effective in further improving performance properties. In particular, the combination of ethoxylated vegetable oil and polyether-modified siloxane results in good performance properties. Therefore, this combination is generally a preferred type of foam stabilizer for the production of phenolic foam materials.

[0003] U.S. Pat. No. 4,067,829, GB 1,087,056, GB 1,088,056, U.S. Pat. No. 3,298,973, DE 2,254,305, WO 2009,048,717, and DE 2,833,002 describe the general use of polyether-modified siloxanes in phenolic foams for foam stabilization.

[0004] WO 2004 / 056911 describes the general use of polyether-modified siloxanes as foam stabilizers for producing closed-cell phenolic foams, which have a polysiloxane content of 25-35 wt. %, a polyethylene oxide content of 50-55 wt. %, and a polypropylene oxide content of 15-20 wt. %.

[0005] WO 2022 / 043561 describes the use of polyether-modified siloxanes in combination with ethoxylated castor oil to produce closed-cell phenolic foams having a polyethylene oxide content of less than 50% by weight, preferably polyether-modified siloxanes having a molar mass of 9,500 to 25,000 g / mol.

[0006] The cited prior art documents do not contain any teaching as to the extent to which foam properties, in particular thermal conductivity and its change over time, can be improved by properly shaping the structure of the polyether-modified siloxane, for example by selecting the chain length of the polysiloxane, its degree of modification, or the composition of the polyether residues.

[0007] Against this background, the object of the present invention was to make it possible to provide phenolic foams that have better performance properties, in particular better thermal conductivity, than phenolic foams produced using conventional foam stabilizers.

[0008] This problem is solved by the subject matter of the present invention, which is a composition for producing a phenolic foam material, comprising at least one phenolic resin, at least one blowing agent, at least one catalyst and a compound of formula 1: M a M 1 b D c D 1 d (Formula 1) and at least one polyether siloxane according to During the ceremony, [ka] a=0~2, b=0 to 2, c=1 to 100, preferably 6 to 80, particularly preferably 6 to 60; d=0 to 40, preferably 1 to 35, particularly preferably 1 to 30; where: a+b=2, a+b+c+d=5 to 140, preferably 9 to 100, particularly preferably 14 to 50, (a+b+c+d) / (b+d)=5 to 8.5, preferably 5 to 8.0, particularly preferably 5 to 7.5, R=each independently the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, H, or -OR 2 , preferably methyl, ethyl, phenyl or H, in particular methyl, R 2 = each independently of the other, the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, or H, R 1 = each independently of the other, the same or different alkyl residues having 6 to 18 carbon atoms, or of formula 2: [ka] are the same or different polyether residues according to R 3 = each independently of one another, the same or different divalent alkyl residues having 2 to 15 carbon atoms, preferably the same or different divalent alkyl residues having 3 to 6 carbon atoms, particularly preferably -(CH2)3-, R 4= each independently of the other, the same or different alkyl residues having 1 to 18 carbon atoms, optionally having an ether function, or the same or different aryl residues having 6 to 18 carbon atoms, optionally having an ether function, or H, preferably H, methyl, ethyl or phenyl, Here, [CR 4 2CR 4 2O] in which four residues R 4 Not all of them are H, and [CR 4 2CR 4 2O], one residue R 4 is methyl and the remaining three residues R 4 But not H, R 5 = R, each independently of the other 2 and C(O)R 2 are identical or different residues selected from the group consisting of: preferably methyl, butyl, H or C(O)Me, particularly preferably H, methyl or C(O)Me, e=0 to 100, preferably 0 to 80, particularly 0 to 60; f=0 to 100, preferably 0 to 80, particularly 0 to 60; g=0 to 100, preferably 0 to 80, particularly 0 to 60; h=0 to 100, preferably 0 to 60, particularly preferably 0; Here, e+f+g+h=5 to 100, preferably 10 to 90, particularly preferably 10 to 80; where the residue R in the polyethersiloxane according to formula 1 1 are, independently of one another, the same or different alkyl residues having 6 to 18 carbon atoms, and The at least one polyethersiloxane according to formula 1 is contained in a total amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total phenolic resin used. It is a composition.

[0009] The subject matter of the present invention has various advantages. It thus makes it possible to provide a phenolic foam that meets known requirements. In particular, the phenolic foam has very good insulating properties, excellent long-term behavior, and high surface quality. Advantageously, this is possible without compromising other properties of the material. Furthermore, a particularly fine-celled, uniform, and defect-free foam structure is possible.

[0010] The subject matter of the present invention makes it possible to provide phenolic foams that have better performance characteristics, particularly better thermal conductivity, than phenolic foams made with conventional foam stabilizers.

[0011] The invention preferably likewise makes it possible to use them in combination with Si-free surfactants known from the prior art, in particular alkoxylated vegetable oils and ethoxylated sorbitan fatty acid esters.

[0012] The composition according to the invention comprises at least one polyether siloxane according to formula 1. Polyether siloxanes which can be preferably used within the meaning of the invention are described in the following preferred embodiments of the invention.

[0013] At least one polyether siloxane according to formula 1 is 1 are preferably characterized in that less than 100 mol %, preferably less than 70 mol %, particularly preferably less than 50 mol % of the polyether siloxanes according to the general formula 2, where f+g+h=0, contain polyether residues R 1 However, it is characterized in that it does not contain a polyether residue of general formula 2 where f+g+h=0.

[0014] Furthermore, the at least one polyether siloxane according to formula 1 is 1 At least 25 mol %, preferably at least 50 mol %, particularly preferably at least 75 mol % of 5It is preferred that the polyether compound is characterized by containing a polyether residue of general formula 2 where R =H. Particularly preferred is that all residues R 1 80mol% to 100mol% of 5 ═H and containing a polyether residue of general formula 2.

[0015] Similarly, the at least one polyethersiloxane according to formula 1 may be a polyethersiloxane in which all residues R 1 at least 30 mol %, preferably at least 40 mol %, particularly preferably at least 50 mol % of which are polyether residues of the general formula 2, e+f+g=17 to 60, preferably 19 to 40; (f+g) / (e+f+g) is greater than 0 and is 0.6, preferably 0.1 to 0.5, and particularly preferably 0.15 to 0.4; and h=0 It is preferably characterized by containing a polyether residue of general formula 2.

[0016] Preferably, the at least one polyethersiloxane according to formula 1 comprises at least two different residues R 1 Includes.

[0017] The at least one polyethersiloxane according to formula 1 is selected from the group consisting of at least two different residues R 1 wherein at least one residue R 1 is a polyether residue according to formula 2 and at least one residue R 1 is an alkyl residue having 6 to 18 carbon atoms, and all residues R 1 Preferably, at most 50 mol %, preferably at most 25 mol %, of the alkyl residues have 6 to 18 carbon atoms.

[0018] The composition according to the invention preferably comprises hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane and / or n-pentane; and halogenated hydrocarbons having 3, 4 or 5 carbon atoms, preferably isopropyl chloride, hydrofluoroolefins or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) and / or 1336mzz The composition comprises at least one blowing agent selected from the group consisting of:

[0019] Furthermore, the composition according to the present invention preferably further contains at least one silicon-free surfactant, preferably selected from the group consisting of alkoxylated vegetable oils and ethoxylated sorbitan fatty acid esters, preferably in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total phenolic resin used.

[0020] Preferably, the alkoxylated vegetable oil is an ethoxylated vegetable oil, preferably an ethoxylated castor oil, and preferably the alkoxylated vegetable oil is contained in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total phenolic resin used.

[0021] The alkoxylated vegetable oil preferably contains 15 to 50 mol of alkylene oxide, and more preferably 20 to 45 mol of alkylene oxide, based on 1 mol of vegetable oil.

[0022] Preferably, the ethoxylated sorbitan fatty acid ester is polysorbate 20, polysorbate 40, and / or polysorbate 80, and the ethoxylated sorbitan fatty acid ester is preferably contained in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total phenolic resin used.

[0023] The composition according to the present invention comprises at least one catalyst, preferably selected from the group consisting of organic acids and inorganic acids, and more preferably selected from the group consisting of sulfuric acid, phosphoric acid, benzenesulfonic acid, xylenesulfonic acid, paratoluenesulfonic acid, ethylbenzenesulfonic acid, naphtholsulfonic acid, cumenesulfonic acid, and phenolsulfonic acid.

[0024] The at least one catalyst is preferably contained in a total amount of 1 to 30 parts by weight, more preferably 1 to 25 parts by weight, and particularly preferably 3 to 20 parts by weight, based on 100 parts by weight of the total phenolic resin used.

[0025] The composition according to the invention comprises at least one phenolic resin, preferably having a water content of 1 to 25% by weight, preferably 4 to 19% by weight, based on the total phenolic resin used.

[0026] Particularly preferred phenolic foam formulations in the sense of the present invention have a density of 5 to 900 kg / m 3 and preferably has the composition listed in Table 1, which corresponds to a preferred embodiment of the present invention: [Table 1]

[0027] A further subject of the present invention is a process for producing a phenolic foam, which is carried out using a reaction mixture containing a composition according to the invention as defined above, in particular as defined in any one of claims 1 to 14.

[0028] Furthermore, for further preferred embodiments and configurations of the method according to the invention, reference is made to the statements already made above in connection with the composition according to the invention.

[0029] A further subject of the present invention is a phenolic foam material, preferably produced by the method according to the invention using a composition according to the invention, in particular as defined in any one of claims 1 to 14.

[0030] The phenolic resin foam material has a viscosity of 5 to 500 kg / m 3 , preferably 10 to 200 kg / m 3 , particularly preferably 12 to 100 kg / m 3 Preferably, the PET film has a density according to ASTM D1622-2020.

[0031] A further object of the invention is the use of the phenolic foam material according to the invention for thermal insulation.

[0032] A further subject of the present invention is the use of at least one polyether siloxane according to formula 1 in the production of phenolic foams, preferably using the compositions according to the invention, in particular as defined in any one of claims 1 to 14.

[0033] A further object of the present invention is the use of at least one polyether siloxane according to formula 1 in the production of a phenolic foam to improve the insulating capacity of the phenolic foam, preferably a phenolic foam according to claim 16, preferably a phenolic foam produced using a composition according to any one of claims 1 to 14.

[0034] Particularly preferred compositions according to the invention are described in more detail below.

[0035] Particularly preferred compositions according to the invention comprise the following components: - at least one phenolic resin, at least one blowing agent, - at least one catalyst, at least one polyether siloxane according to formula 1, - optionally further additives etc. Contains:

[0036] The production of phenolic foams (also synonymously referred to as phenolic foams) is known to those skilled in the art. To produce phenolic foams, one or more phenolic resins, preferably one or more so-called resole resins, are used. Correspondingly usable phenolic resins, preferably resole resins, are known per se. In particular, they can be produced by known methods of condensing phenol or phenolic compounds, such as cresol, xylenol, para-alkylphenols, para-phenylphenols, resorcinol, and the like, with aldehydes, such as formaldehyde, furfural, and acetaldehyde, preferably under basic conditions, for example, by using catalytic amounts of alkali hydroxides, such as sodium hydroxide, potassium hydroxide, or calcium hydroxide, or aliphatic amines, such as trimethylamine or triethylamine, preferably together with an excess amount of aldehyde. This represents a general route for producing phenolic resins, preferably resole resins, and the present invention is not limited to the chemicals listed immediately above.

[0037] The molar ratio of phenolic groups to aldehyde groups is not limited here. Preferably, this ratio is in the range of 1:1 to 1:3, particularly preferably in the range of 1:1.5 to 1:2.5. Preferably, the phenolic resin has a free aldehyde content of 0.1% to 0.5% by weight, but is not limited thereto. This can be determined by potentiometric titration with hydroxylamine hydrochloride in accordance with ISO 11402:2004.

[0038] Preferred phenolic resins that can be used in foam production are liquid at 25°C and standard pressure, i.e., preferably have a water concentration of about 1 to 25% by weight, preferably 5 to 20% by weight, and preferably have methylol groups as reactive substituents, as described, for example, in EP 0170357. If desired, the viscosity of the phenolic resin can be adjusted, in particular, by adjusting the water content. For example, a higher water content typically results in a lower viscosity, which can facilitate both the handling and mixing of the resin during foam production.

[0039] Standard pressure is understood to be a pressure of 101325 Pa.

[0040] The viscosity of the preferred phenolic resins at 25°C and standard pressure is preferably in the range of 1000 to 28000 mPa·s and can be determined by conventional methods known to those skilled in the art, for example, using a Brookfield viscometer. General information about the production and composition of phenolic resins is available from the prior art and is described, for example, in EP-A-3830174, EP-A-2898005, WO-A-2022043561, or EP-A-4073155.

[0041] Blowing agents and their use in the production of phenolic foams are known to those skilled in the art. Their selection may depend, for example, on the type of system and the intended use of the resulting phenolic foam. Depending on the amount of blowing agent used, for example, foams with high or low density can be produced. Thus, for example, a blowing agent of 5 kg / m is preferred according to ASTM D1622-20. 3 ~900kg / m 3 , preferably 5 to 500 kg / m 3 , particularly preferably 10 to 200 kg / m 3 , especially 12 to 100 kg / m 3 Foams having densities of 1000 to 15000 can be produced.

[0042] Particularly preferably usable blowing agent has already been mentioned above.Can be used as possible blowing agent, for example, one or more of the corresponding compounds with suitable boiling point, for example, hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane or n-pentane, halogenated hydrocarbons, for example, chlorinated hydrocarbons, for example, dichloroethane, 1,2-dichloroethene, n-propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, 1,1-dichloroethene, trichloroethene or chloroethene, or fluorocarbons (HFC), for example, HFC245fa, HFC134a or HFC365mfc, hydrofluoroolefins (HFO), or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz, and their mixtures.

[0043] Particularly suitable catalysts have already been mentioned above. Catalysts suitable for producing phenolic foams are known to those skilled in the art, for example, from the prior art and are described, for example, in EP-A-0170357 or DE-A-602004006376. In this case, preferred are conventional organic and inorganic acids known from the prior art. Preferably, one or more acids are used. Sulfuric acid, phosphoric acid, benzenesulfonic acid, xylenesulfonic acid, paratoluenesulfonic acid, ethylbenzenesulfonic acid, naphtholsulfonic acid, cumenesulfonic acid, and / or phenolsulfonic acid are particularly suitable. In particular, mixtures of several of these compounds can be used as catalysts. The preferred amount of catalyst used to ensure complete reaction can be influenced, in particular, by the water content of the phenolic resin and / or, if the catalyst is present as an aqueous solution, by its water content. For example, a higher water content may require a higher acid concentration.

[0044] Phenolic resin foams can be formed by known methods, i.e., by reacting a mixture containing, inter alia, a phenolic resin, a blowing agent, a foam stabilizer, and a catalyst. When a catalyst is added to the mixture of the phenolic resin, the blowing agent, and the foam stabilizer, an exothermic reaction occurs between the methylol groups and the phenol, resulting in the formation and cross-linking of methylene bridges. Water is released by condensation. For example, the type and amount of acid used, the properties of the blowing agent, and the structure of the foam stabilizer can affect the exothermicity of the reaction and foam formation.

[0045] Foam stabilizers and their use in the production of phenolic foam materials are generally known to those skilled in the art, as described above. According to the present invention, at least one polyethersiloxane according to Formula 1 is used. The at least one polyethersiloxane according to Formula 1 functions as a foam stabilizer. In addition, additional foam stabilizers that assist in foam production can also be used. These compounds are well known in the prior art. For example, EP 3830174 A1 describes the use of ethoxylated castor oil.

[0046] The optional additives may be one or more of the substances known in the art that are commonly used in the production of phenolic foam materials, such as viscosity reducers, plasticizers, hardeners, flame retardants, cell-refining additives, fillers, dyes, pigments, and / or fragrances. Suitable optional additives are described, for example, in EP-A-3830174, U.S. Pat. No. 4,444,912, and EP-A-1,922,357.

[0047] Optional solid fillers include metal hydroxides such as aluminum hydroxide or magnesium hydroxide, metal carbonates such as calcium carbonate, magnesium carbonate, barium carbonate, or zinc carbonate, metal oxides such as aluminum oxide or zinc oxide, or metal powders such as zinc. Monoethylene glycol or polyester polyols can be optionally used to reduce the viscosity of the phenolic resin. Optional hardeners include compounds with amino groups such as urea or dicyandiamide. Urea is preferred. These can be used, for example, during foaming or during the production of the phenolic resin.

[0048] The process according to the invention for producing phenolic foam materials can be carried out by any known method, which is known to those skilled in the art and is described in the patent literature, including, for example, EP 3830174 A1.

[0049] Unless otherwise apparent from this specification, any preferred or particularly preferred embodiment of the present invention may be combined with one or more of the other preferred or particularly preferred embodiments of the present invention.

[0050] When ranges, general formulas, or classes of compounds are described, they include not only the corresponding ranges or compound groups explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by extracting the individual values ​​(ranges) or compounds. When documents are cited within this specification, their contents, especially those relating to the matter in the context in which this document is cited, are fully incorporated into the disclosure of the present invention. When average values ​​are mentioned, they are number averages unless otherwise specified. When parameters determined by measurement are described, these measurements were carried out at a temperature of 23°C and preferably at a pressure of 101325 Pa, unless otherwise specified.

[0051] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto. [Example]

[0052] Polyether siloxanes were prepared and tested in application technology as described below.

[0053] The catalyst used for hydrosilylation was a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution in xylene (w(Pt)=2%). The CAS number of this complex is 68478-92-2. The catalyst was purchased from Sigma-Aldrich and used as received.

[0054] The SiH-functional siloxane used was prepared as described in Example 1 of DE 10 2008 042 181 A1.

[0055] The basic preparation of allyl polyethers is well known to those skilled in the art and is described, for example, in Example 1 of EP-A-4314111. Allyl alcohol was used as the starting alcohol as well.

[0056] All reactions were carried out by the Schlenk technique using nitrogen as the protective gas.

[0057] Example 1: Production of PES1 To synthesize the polyethersiloxane PES1, a 500 mL four-neck flask equipped with a precision glass stirrer (KPG-Rührer), a thermometer, a reflux condenser, and a nitrogen inlet was heated with 100 mL of methyl methyl siloxane (MeSiO(SiMeO)). 38 (SiMeHO) 10 64 g of SiH-functional siloxane of SiMe3 was dissolved in 36 g of polyether of formula CH2=CHCHO(CH2CH2O)9(CH2CH(CH3)O)1H, 11 (CH2CH(CH3)O) 10106 g of polyether of formula CH2=CHCH2O(CH2CH2O) 23 94 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0058] Example 2: Production of PES2 To synthesize polyether siloxane PES2, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 40 84 g of a SiH-functional siloxane of formula (SiMeHO)SiMeH was mixed with 38 g of a polyether of formula CH=CHCHO(CHCHO)(CHCH(CH)O)H and 38 g of a polyether of formula CH=CHCHO(CHCHO) 12 178 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0059] Example 3: Production of PES3 To synthesize polyethersiloxane PES3, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 14 58 g of a SiH-functional siloxane of the formula (SiMeHO)SiMe was added to a solution of 100 g of a siloxane having the formula CH=CHCH0(CHCH0) 23112 g of polyether of formula (CH2CH(CH3)O)4H and CH2=CHCH2O(CH2CH2O) 12 130 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0060] Example 4: Production of PES4 To synthesize polyethersiloxane PES4, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 14 61 g of a SiH-functional siloxane of the formula (SiMeHO)SiMe was added to a solution of 100 g of a siloxane having the formula CH=CHCH0(CHCH0) 11 (CH2CH(CH3)O) 10 101g of polyether of formula CH2=CHCH2O(CH2CH2O) 12 138 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0061] Example 5: Production of PES5 To synthesize the polyether siloxane PES5, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 38 (SiMeHO) 1051 g of SiMe3 SiH functional siloxane was added to a solution of 100 ml of a siloxane having the formula CH2=CHCH2O(CH2CH2O) 22 (CH2CH(CH3)O) 11 132 g of polyether of formula CH2=CHCH2O(CH2CH2O) 12 116 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0062] Example 6: Preparation of PES6 To synthesize the polyethersiloxane PES6, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 14 52 g of a SiH-functional siloxane of the formula (SiMeHO)SiMe was added to a solution of 100 g of a siloxane having the formula CH=CHCH0(CHCH0) 22 (CH2CH(CH3)O) 11 132 g of polyether of formula CH2=CHCH2O(CH2CH2O) 12 116 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0063] Example 7: Production of PES7 To synthesize the polyether siloxane PES7, a solution of 1,2-dimethyl-3,4-dimethyl-2 ...55 75 g of SiH-functional siloxane of the formula CH2=CHCH2O(CH2CH2O) 23 225 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0064] Example 8: Production of PES8 To synthesize the polyethersiloxane PES8, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 38 (SiMeHO) 10 57 g of SiMe3 SiH functional siloxane was added to a solution of 100 ml of a siloxane having the formula CH2=CHCH2O(CH2CH2O) 23 113 g of polyether of formula (CH2CH(CH3)O)4H and CH2=CHCH2O(CH2CH2O) 12 130 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0065] Example 9: Production of PES9 To synthesize the polyethersiloxane PES9, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 123 (SiMeHO) 2566 g of SiMe3 SiH functional siloxane was added to a solution of 100 ml of a siloxane having the formula CH2=CHCH2O(CH2CH2O) 23 108 g of polyether of formula (CHCH(CH)O)H and CH=CHCHO(CHCHO) 12 125 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0066] Example 10: Preparation of PES10 To synthesize the polyether siloxane PES10, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 37.1 (SiMeHO) 2.9 131 g of SiH-functional siloxane of the formula CH2=CHCH2O(CH2CH2O) 12 168 g of polyether (CH2CH(CH3)O)7CH3 was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0067] Example 11: Preparation of PES11 To synthesize polyether siloxane PES11, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 51 110 g of SiH-functional siloxane of the formula CH2=CHCH2O(CH2CH2O)13 190 g of polyether (CHCH(CH)O)H was mixed with the resulting mixture. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0068] Example 12: Preparation of PES12 To synthesize polyethersiloxane PES12, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 65 148 g of a SiH-functional siloxane of the formula CH2=CHCH2O(CH2CH2O) 10 The mixture was mixed with 151 g of a polyether of 1,3-dimethyl-1,1,3,3-tetramethyldisiloxane. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0069] Example 13: Preparation of PES13 To synthesize polyethersiloxane PES13, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 108 (SiMeHO) 10 126 g of SiMe3 SiH functional siloxane was dissolved in water in a 1000 ml solution of the formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O) 11The mixture was mixed with 174 g of a polyether of 1,3-dimethyl-1,1,3,3-tetramethyldisiloxane. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0070] Example 14: Preparation of PES14 To synthesize polyethersiloxane PES14, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 21 121 g of a SiH-functional siloxane of formula CH=CHCH0(CHCH0) 12 89 g of polyether of formula (CHCH(CH)O)H and CH=CHCHO(CHCHO) 12 89 g of polyether (CH2CH(CH3)O)7Me was mixed with each other. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then started. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0071] Example 15: Preparation of PES15 To synthesize the polyether siloxane PES15, a solution of 1,2-dimethyl-3,4-dimethyl-2 ... 28 (SiMeHO) 10 89 g of SiMe3 SiH functional siloxane was dissolved in water with the formula CH2=CHCH2O(CH2CH2O) 10211 g of polyether of H was mixed with each other. The mixture was heated to 90°C. 0.15 g of a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was then added. An exothermic reaction then began. The reaction mixture was then stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetric analysis. The degree of conversion was 100%. A clear product was obtained.

[0072] [Table 2]

[0073] Manufacture of phenolic foam materials For application technology comparison, the formulations shown in Table 3 were used. Comparative foaming runs were performed using the manual mixing method. To do so, the phenolic resin (batch amount 180 ± 5 g) and foam stabilizer were weighed into a beaker and mixed with a disk stirrer (6 cm diameter) at 20 °C and 1000 rpm for 15 seconds. The blowing agent was then added and mixed at 1500 rpm for 30 seconds. Subsequently, the acid was added, and the mixture was stirred at 2500 rpm for 30 seconds and transferred to a thermostatically controlled aluminum mold (25 cm × 25 cm × 7 cm) lined with polyethylene film and heated to 60 °C. After 30 minutes, the foam was demolded and cured in an oven heated to 60 °C for 42 hours.

[0074] The open cell ratio is 100 cm 3 The initial thermal conductivity (λ value in mW / m K) was determined on a 2.5 cm thick disc using a LaserComp FOX200 type device at an average temperature of 23 °C, in accordance with the specifications of the EN12667:2001 standard, immediately after curing in the oven and cooling to room temperature. To determine the aging values, the specimens were stored in the oven at 70 °C for 7 days, after which the thermal conductivity was determined again as described above.

[0075] [Table 3]

[0076] The polyether siloxane foam stabilizer according to the invention was investigated both alone and in combination with Si-free surfactants, using TAGAT® CH40 as an ethoxylated castor oil and Polysorbate 80 from Evonik Operations GmbH. The results are shown in Table 4.

[0077] [Table 4]

[0078] These results show that a higher foam quality and thermal conductivity can be achieved with the foam stabilizer according to the invention than with foam stabilizers not according to the invention. In particular, the λ value after aging, which is crucial for the application, shows a significant improvement. All other foam properties relevant for use are not affected or only slightly affected by the foam stabilizer according to the invention.

[0079] A preferred embodiment of the present invention is as follows. 1. A composition for producing a phenolic foam material, comprising: at least one phenolic resin, at least one blowing agent, at least one catalyst, and a compound represented by Formula 1: M a M 1 b D c D 1 d (Formula 1) and at least one polyether siloxane according to During the ceremony, [ka] a=0~2, b=0 to 2, c=1 to 100, preferably 6 to 80, particularly preferably 6 to 60; d=0 to 40, preferably 1 to 35, particularly preferably 1 to 30; where: a+b=2, a+b+c+d=5 to 140, preferably 9 to 100, particularly preferably 14 to 50, (a+b+c+d) / (b+d)=5 to 8.5, preferably 5 to 8.0, particularly preferably 5 to 7.5, R=each independently the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, H, or -OR 2 , preferably methyl, ethyl, phenyl or H, in particular methyl, R 2 = each independently of the other, the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, or H, R 1 = each independently of the other, the same or different alkyl residues having 6 to 18 carbon atoms, or of formula 2: [ka] are the same or different polyether residues according to R 3 = each independently of one another, the same or different divalent alkyl residues having 2 to 15 carbon atoms, preferably the same or different divalent alkyl residues having 3 to 6 carbon atoms, particularly preferably -(CH2)3-, R 4 = each independently of the other, the same or different alkyl residues having 1 to 18 carbon atoms, optionally having an ether function, or the same or different aryl residues having 6 to 18 carbon atoms, optionally having an ether function, or H, preferably H, methyl, ethyl or phenyl, Here, [CR 4 2CR4 2O] in which four residues R 4 Not all of them are H, and [CR 4 2CR 4 2O], one residue R 4 is methyl and the remaining three residues R 4 But not H, R 5 = R, each independently of the other 2 and C(O)R 2 are identical or different residues selected from the group consisting of: preferably methyl, butyl, H or C(O)Me, particularly preferably H, methyl or C(O)Me, e=0 to 100, preferably 0 to 80, particularly 0 to 60; f=0 to 100, preferably 0 to 80, particularly 0 to 60; g=0 to 100, preferably 0 to 80, particularly 0 to 60; h=0 to 100, preferably 0 to 60, particularly preferably 0; Here, e+f+g+h=5 to 100, preferably 10 to 90, particularly preferably 10 to 80; where the residue R in the polyethersiloxane according to formula 1 1 are, independently of one another, the same or different alkyl residues having 6 to 18 carbon atoms, and The at least one polyethersiloxane of formula 1 is contained in a total amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total phenolic resin used; composition. 2. The at least one polyether siloxane according to formula 1 is 1 are characterized in that less than 100 mol %, preferably less than 70 mol %, particularly preferably less than 50 mol % of the polyether siloxanes according to the general formula 2, where f+g+h=0, contain polyether residues R 1The composition according to 1 above, characterized in that it does not contain a polyether residue of general formula 2 where f+g+h=0. 3. The at least one polyether siloxane according to formula 1 is 1 At least 25 mol %, preferably at least 50 mol %, particularly preferably at least 75 mol % of 5 3. The composition according to 1 or 2 above, characterized in that it contains a polyether residue of general formula 2, where =H. 4. The at least one polyether siloxane according to formula 1 is 1 at least 30 mol %, preferably at least 40 mol %, particularly preferably at least 50 mol % of which are polyether residues of the general formula 2, e+f+g=17 to 60, preferably 19 to 40; (f+g) / (e+f+g) is greater than 0 and is 0.6, preferably 0.1 to 0.5, and particularly preferably 0.15 to 0.4; and h=0 4. The composition according to any one of 1 to 3 above, characterized in that it contains a polyether residue of general formula 2. 5. The at least one polyethersiloxane according to formula 1 comprises at least two different residues R 1 5. The composition according to any one of 1 to 4 above, characterized in that it comprises: 6. The at least one polyethersiloxane according to formula 1 comprises at least two different residues R 1 wherein at least one residue R 1 is a polyether residue according to formula 2, and at least one residue R 1 is an alkyl residue having 6 to 18 carbon atoms, where all residues R 1 6. The composition according to any one of 1 to 5 above, characterized in that up to 50 mol %, preferably up to 25 mol % of the above are alkyl residues having 6 to 18 carbon atoms. 7. The at least one blowing agent is hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane or n-pentane; and halogenated hydrocarbons having 3, 4 or 5 carbon atoms, preferably isopropyl chloride, hydrofluoroolefins or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz; 7. The composition according to any one of 1 to 6 above, characterized in that it is selected from the group consisting of: 8. The composition according to any one of items 1 to 7, further comprising at least one silicon-free surfactant, preferably selected from the group consisting of alkoxylated vegetable oils and ethoxylated sorbitan fatty acid esters, preferably in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total phenolic resin used. 9. The composition according to item 8, wherein the alkoxylated vegetable oil is an ethoxylated vegetable oil, preferably an ethoxylated castor oil, and the alkoxylated vegetable oil is preferably contained in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total phenolic resin used. 10. The composition described in 8 or 9 above, characterized in that the alkoxylated vegetable oil contains 15 to 50 mol of alkylene oxide, preferably 20 to 45 mol of alkylene oxide, based on 1 mol of vegetable oil. 11. The composition according to any one of items 8 to 10, wherein the ethoxylated sorbitan fatty acid ester is polysorbate 20, polysorbate 40, and / or polysorbate 80, and the ethoxylated sorbitan fatty acid ester is preferably contained in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total phenolic resin used. 12. The composition according to any one of 1 to 11, wherein the at least one catalyst is selected from the group consisting of organic acids and inorganic acids, preferably the at least one catalyst is selected from the group consisting of sulfuric acid, phosphoric acid, benzenesulfonic acid, xylenesulfonic acid, paratoluenesulfonic acid, ethylbenzenesulfonic acid, naphtholsulfonic acid, cumenesulfonic acid, and phenolsulfonic acid. 13. The composition according to any one of items 1 to 12, characterized in that the at least one catalyst is contained in a total amount of 1 to 30 parts by weight, preferably 1 to 25 parts by weight, and particularly preferably 3 to 20 parts by weight, based on 100 parts by weight of the total phenolic resin used. 14. The composition according to any one of 1 to 13, characterized in that the at least one phenolic resin has a water content of 1 to 25% by weight, preferably 4 to 19% by weight, based on the total weight of the phenolic resins used. 15. A method for producing a phenolic foam material, characterized in that it is carried out using a reaction mixture containing a composition as defined in any one of 1 to 14 above. 16. Preferably, 5 to 500 kg / m 3 , preferably 10 to 200 kg / m 3 , particularly preferably 12 to 100 kg / m 3 16. A phenolic foam material produced by the method of claim 15, characterized in that it has a density according to ASTM D1622-20 of 1000 MPa.

Claims

1. 1. A composition for producing a phenolic foam material, comprising: At least one phenolic resin, at least one blowing agent, at least one catalyst, and a compound represented by Formula 1: M ａ M １ ｂ D ｃ D １ ｄ (Equation 1) and at least one polyether siloxane according to During the ceremony, 【Chemistry 1】 a=0 to 2; b=0 to 2; c=1 to 100, preferably 6 to 80, particularly preferably 6 to 60; d=0 to 40, preferably 1 to 35, particularly preferably 1 to 30; where: a+b=2, a+b+c+d=5 to 140, preferably 9 to 100, particularly preferably 14 to 50; (a+b+c+d) / (b+d)=5 to 8.5, preferably 5 to 8.0, particularly preferably 5 to 7.5; R=each independently of the other, the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, H, or —O—R ２ , preferably methyl, ethyl, phenyl or H, in particular methyl, R ２ = each independently of the others, the same or different alkyl residues having 1 to 16 carbon atoms, the same or different aryl residues having 6 to 16 carbon atoms, or H, R １ = each independently of the other, the same or different alkyl residues having 6 to 18 carbon atoms, or of formula 2: 【Chemistry 2】 are the same or different polyether residues according to R ３ = each independently of the other, the same or different divalent alkyl residues having 2 to 15 carbon atoms, preferably the same or different divalent alkyl residues having 3 to 6 carbon atoms, particularly preferably -(CH ２ ) ３ - and R ４ = each independently of the other, the same or different alkyl residues having 1 to 18 carbon atoms, optionally having an ether function, or the same or different aryl residues having 6 to 18 carbon atoms, optionally having an ether function, or H, preferably H, methyl, ethyl or phenyl, Here, [CR ４ ２ CR ４ ２ O], and four residues R ４ Not all of them are H, and [CR ４ ２ CR ４ ２ O], one residue R ４ is methyl and the remaining three residues R ４ But not H, R ５ = each independently of the other, R ２ and C(O)R ２ are identical or different residues selected from the group consisting of: preferably methyl, butyl, H or C(O)Me, particularly preferably H, methyl or C(O)Me, e=0 to 100, preferably 0 to 80, in particular 0 to 60; f=0 to 100, preferably 0 to 80, in particular 0 to 60; g=0 to 100, preferably 0 to 80, in particular 0 to 60; h=0 to 100, preferably 0 to 60, particularly preferably 0; where e+f+g+h=5 to 100, preferably 10 to 90, particularly preferably 10 to 80; where the residue R in the polyethersiloxane according to formula 1 １ are, independently of one another, the same or different alkyl residues having 6 to 18 carbon atoms, and the at least one polyethersiloxane according to formula 1 is contained in a total amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total phenolic resin used; composition.

2. The at least one polyether siloxane according to formula 1 is １ are characterized in that less than 100 mol %, preferably less than 70 mol %, particularly preferably less than 50 mol % of the polyether siloxanes according to the general formula 2, where f + g + h = 0, and particularly preferably the at least one polyether siloxane according to formula 1 contains the residue R １ The composition of claim 1, characterized in that it does not contain a polyether residue of general formula 2 where f+g+h=0.

3. The at least one polyether siloxane according to formula 1 is １ At least 25 mol %, preferably at least 50 mol %, particularly preferably at least 75 mol % of ５ 3. The composition according to claim 1, characterized in that it contains a polyether residue of general formula 2, where =H.

4. The at least one polyether siloxane according to formula 1 is １ at least 30 mol %, preferably at least 40 mol %, particularly preferably at least 50 mol % are polyether residues of the general formula 2, e+f+g=17 to 60, preferably 19 to 40; (f+g) / (e+f+g) is greater than 0 and less than 0.6, preferably from 0.1 to 0.5, particularly preferably from 0.15 to 0.4; and h=0 4. The composition according to claim 1, characterized in that it contains a polyether residue of general formula 2.

5. The at least one polyether siloxane according to formula 1 comprises at least two different residues R １ 5. The composition according to claim 1, characterized in that it comprises:

6. The at least one polyether siloxane according to formula 1 comprises at least two different residues R １ wherein at least one residue R １ is a polyether residue according to formula 2, and at least one residue R １ is an alkyl residue having 6 to 18 carbon atoms, where all residues R １ 6. The composition according to claim 1, wherein at most 50 mol %, preferably at most 25 mol %, of the alkyl residues have 6 to 18 carbon atoms.

7. The at least one blowing agent is hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane or n-pentane; and halogenated hydrocarbons having 3, 4 or 5 carbon atoms, preferably isopropyl chloride, hydrofluoroolefins or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz 7. The composition according to claim 1, wherein the composition is selected from the group consisting of:

8. 8. The composition according to claim 1, further comprising at least one silicon-free surfactant, preferably selected from the group consisting of alkoxylated vegetable oils and ethoxylated sorbitan fatty acid esters, preferably in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total phenolic resin used.

9. 9. The composition according to claim 8, wherein the alkoxylated vegetable oil is an ethoxylated vegetable oil, preferably an ethoxylated castor oil, and the alkoxylated vegetable oil is preferably contained in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total phenolic resin used.

10. 10. The composition according to claim 8 or 9, characterized in that the alkoxylated vegetable oil contains from 15 to 50 mol of alkylene oxide, preferably from 20 to 45 mol of alkylene oxide, based on 1 mol of vegetable oil.

11. The composition according to any one of claims 8 to 10, characterized in that the ethoxylated sorbitan fatty acid ester is polysorbate 20, polysorbate 40, and / or polysorbate 80, and the ethoxylated sorbitan fatty acid ester is preferably contained in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total phenolic resin used.

12. 12. The composition of any one of claims 1 to 11, characterized in that the at least one catalyst is selected from the group consisting of organic acids and inorganic acids, preferably the at least one catalyst is selected from the group consisting of sulfuric acid, phosphoric acid, benzenesulfonic acid, xylenesulfonic acid, paratoluenesulfonic acid, ethylbenzenesulfonic acid, naphtholsulfonic acid, cumenesulfonic acid, and phenolsulfonic acid.

13. 13. The composition according to claim 1, wherein the at least one catalyst is contained in a total amount of 1 to 30 parts by weight, preferably 1 to 25 parts by weight, particularly preferably 3 to 20 parts by weight, based on 100 parts by weight of the phenolic resin used.

14. 14. The composition according to claim 1, wherein the at least one phenolic resin has a water content of 1 to 25% by weight, preferably 4 to 19% by weight, based on the total phenolic resin used.

15. 15. A process for producing a phenolic foam material, characterized in that it is carried out using a reaction mixture containing a composition as defined in any one of claims 1 to 14.

16. Preferably, 5 to 500 kg / m ３ , preferably 10 to 200 kg / m ３ , particularly preferably 12 to 100 kg / m ３ 16. A phenolic foam material produced by the method of claim 15, characterized in that it has a density according to ASTM D1622-20 of 1000 psi.

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