Foam stabilizers for phenolic foams

Abstract

The present invention relates to a composition for producing phenolic foams, comprising at least one phenolic resin, at least one blowing agent, at least one catalyst and at least one polyethersiloxane of formula 1 MaMb1DcDd1, to a process for producing phenolic foams, and to phenolic foams produced by the process.

Description

TECHNICAL FIELD

[0001] The present invention belongs to the field of phenolic foams. In particular, the present invention relates to a composition for preparing a phenolic foam, to a method for preparing a phenolic foam, to a phenolic foam prepared according to the present invention, and to the use of a polyether modified siloxane for improving the insulating capacity of a phenolic foam. In the context of the present invention, phenolic foam is understood to mean in particular a foam obtainable by reacting a phenolic resin with an acid as catalyst while adding a blowing agent and a foam stabilizer. Phenolic foams are known per se to the person skilled in the art and are described, for example, in EP 3830174 A1, DE 602004006376 T2, EP 2898005 A1, EP 1922357 A1, WO 2022043561 A1, EP 4073155 A1, AU 2021238847 A1 or WO 2006114777 A1. Phenolic foams can also be referred to as phenol resin foams or phenol foams. These terms are treated synonymously. This also applies to the present invention. BACKGROUND

[0002] In phenolic foam preparation, it is generally possible to use cell stabilizing additives or foam stabilizing additives which ensure fine cells with a low defect level, a uniform foam structure and thus a substantially positive influence on the performance characteristics of the foam, in particular, for example, the thermal insulation capacity. For this purpose, it is generally possible to use foam stabilizers, for example based on ethoxylated vegetable oils such as castor oil, as described, for example, in EP 3830174 A1. It has been found that a particularly effective means of further improving the performance characteristics is the use of polyether-modified siloxanes, also referred to as polyether siloxanes (PES), as described, for example, in WO 2022043561 A1, US 3298973 A, GB 1088056 A, GB 1087056 A, DE 2833002 A1, US 4067829 A, DE 2254305 A1 or WO 2009 / 048717 A1. In particular, the combination of ethoxylated vegetable oils with polyether-modified siloxanes leads to good performance characteristics. This combination thus constitutes a class of foam stabilizers which is generally preferred in the preparation of phenolic foams.

[0003] US 4067829 A, GB 1087056, GB 1088056, US 3298973 A, DE 2254305 A1, WO 2009 048717 A1 and DE 2833002 A1 describe the general use of polyether-modified siloxanes for foam stabilization in phenolic foams.

[0004] WO 2004 / 056911 A2 describes the general use of polyether-modified siloxanes as foam stabilizers for the preparation of closed-cell phenolic foams, these having a polysiloxane content of 25 to 35% by weight, a polyethylene oxide content of 50 to 55% by weight and a polypropylene oxide content of 15 to 20% by weight.

[0005] WO 2022 / 043561 A1 describes the use of polyether-modified siloxanes in combination with ethoxylated castor oil for the preparation of closed-cell phenolic foams, these having a polyethylene oxide content of < 50% by weight. Therein the use of polyether-modified siloxanes having a molar mass of 9500 to 25000 g / mol is preferred.

[0006] The prior art documents mentioned do not contain a teaching about the extent to which the structure of the polyether-modified siloxane can improve the foam properties, in particular the thermal conductivity and the aging of the thermal conductivity, by forming it in a selective way, for example by the selection of the chain length of the polysiloxane or the degree of modification, or by the composition of the polyether residue. SUMMARY

[0007] Against this background, it is an object of the present invention to provide phenolic foams having better performance characteristics, in particular a better thermal conductivity, compared to phenolic foams prepared with conventional foam stabilizers.

[0008] This object is achieved by the subject matter of the present invention. The present invention provides a composition for the preparation of a phenolic foam, comprising at least one phenolic resin, at least one blowing agent, at least one catalyst and at least one polyether siloxane of formula 1,

[0009] M a M 1 b D c D 1 d (Formula 1)

[0010] wherein

[0011]

[0012] a = 0 to 2,

[0013] b = 0 to 2,

[0014] c = 1 to 100, preferably 6 to 80, more preferably 6 to 60,

[0015] d = 0 to 40, preferably 1 to 35, more preferably 1 to 30,

[0016] wherein

[0017] a + b = 2,

[0018] a + b + c + d = 5 to 140, preferably 9 to 100, more preferably 14 to 50,

[0019] (a + b + c + d) / (b + d) = 5 to 8.5, preferably 5 to 8.0, more preferably 5 to 7.5,

[0020] R = each independently alkyl having 1 to 16 carbon atoms, aryl having 6 to 16 carbon atoms, H, or -O-R 2 , preferably methyl, ethyl, phenyl or H, in particular methyl,

[0021] R 2 = each independently alkyl having 1 to 16 carbon atoms, aryl having 6 to 16 carbon atoms, or H,

[0022] R 1 = each independently alkyl having 6 to 18 carbon atoms, or a polyether group according to formula 2,

[0023]

[0024] R 3 = each independently divalent alkyl having 2 to 15 carbon atoms, preferably divalent alkyl having 3 to 6 carbon atoms, in particular -(CH2)3-,

[0025] R 4 = each independently alkyl having 1 to 18 carbon atoms, optionally comprising an ether function, or aryl having 6 to 18 carbon atoms, optionally comprising an ether function, or H, preferably H, methyl, ethyl or phenyl,

[0026] wherein the four R 4 groups in [CR 4 2CR 4 2O] are not all H,

[0027] and wherein [CR 4 2CR 4 2O] does not comprise methyl as one R 4 group and H as the remaining three R 4 groups,

[0028] R 5 = each independently selected from R 2 and C(O)R 2R1is a group of the formula -Si(R)3, preferably methyl, butyl, H or C(0)Me, more preferably H, methyl or C(0)CH3,

[0029] e = 0 to 100, preferably 0 to 80, in particular 0 to 60,

[0030] f = 0 to 100, preferably 0 to 80, in particular 0 to 60,

[0031] g = 0 to 100, preferably 0 to 80, in particular 0 to 60,

[0032] h = 0 to 100, preferably 0 to 60, more preferably 0,

[0033] wherein e + f + g + h = 5 to 100, preferably 10 to 90, more preferably 10 to 80,

[0034] wherein not more than 50 mol-% of R 1 each R1is independently the same or different alkyl group having 6 to 18 carbon atoms,

[0035] and wherein the at least one polyether siloxane of formula 1 is present in a total amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total phenolic resin used.

[0036] The subject matter of the present application is associated with various benefits. For example, it is possible to provide a phenolic foam which meets the known requirements. In particular, the phenolic foam has very good insulation properties and exhibits excellent long-term characteristics and a high surface quality. This advantageously makes it possible without adversely affecting other properties of the material. It is likewise possible to achieve a uniform foam structure with particularly fine cells having a low defect level.

[0037] The subject matter of the present application makes it possible to provide a phenolic foam having better performance characteristics, in particular a better thermal conductivity, compared to phenolic foams prepared with conventional foam stabilizers.

[0038] The present application preferably also allows for use together with Si-free surfactants known from the prior art, in particular alkoxylated vegetable oils and ethoxylated sorbitan fatty acid esters.

[0039] The composition according to the present application comprises at least one polyether siloxane of formula 1. In the following preferred embodiments of the present application, the usable polyether siloxanes which are preferably used for the purposes of the present application are described.

[0040] It is preferred that the at least one polyether siloxane of formula 1 has the following characteristics: all R1 less than 100 mole %, preferably less than 70 mole %, more preferably less than 50 mole % of R 1 The group comprises a polyether group of the general formula 2, wherein f + g + h = 0; It is particularly preferred that the at least one polyether siloxane of the formula 1 has the following features: no R 1 The group comprises a polyether group of the general formula 2, wherein f + g + h = 0.

[0041] It is furthermore preferred that the at least one polyether siloxane of the formula 1 has the following features: all R 1 at least 25 mole %, preferably at least 50 mole %, more preferably at least 75 mole % of R 1 The group comprises a polyether group of the general formula 2, wherein R 5 = H. It is particularly preferred that all R 1 80 mole % to 100 mole % of R 1 The group comprises a polyether group of the general formula 2, wherein R 5 = H.

[0042] It is likewise preferred that the at least one polyether siloxane of the formula 1 has the following features: all R 1 at least 30 mole %, preferably at least 40 mole %, more preferably at least 50 mole % of the group comprise a polyether group of the general formula 2, wherein

[0043] e + f + g = 17 to 60, preferably 19 to 40,

[0044] (f + g) / (e + f + g) > 0 to 0.6, preferably 0.1 to 0.5, more preferably 0.15 to 0.4, and

[0045] h = 0.

[0046] It is preferred that the at least one polyether siloxane of the formula 1 comprises at least two different R 1 groups.

[0047] It is preferred that the at least one polyether siloxane of the formula 1 has the following features: it comprises at least two different R 1 groups, wherein at least one R 1 group is a polyether group of the formula 2, and one R 1 group is an alkyl group having 6 to 18 carbon atoms, wherein all R 1 groups, preferably no more than 25 mole % of R 1 groups are alkyl groups having 6 to 18 carbon atoms.

[0048] The composition according to the present application comprises at least one blowing agent, preferably selected from the group consisting of:

[0049] - hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane and / or n-pentane

[0050] and

[0051] - halogenated hydrocarbons having 3, 4 or 5 carbon atoms, preferably isopropyl chloride, hydrofluoroolefins or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) and / or 1336mzz.

[0052] It is furthermore preferred that the composition according to the present application additionally comprises at least one silicon-free surfactant, 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, the at least one silicon-free surfactant preferably being selected from the group consisting of alkoxylated vegetable oils and ethoxylated sorbitan fatty acid esters.

[0053] Preferably, the alkoxylated vegetable oil is an ethoxylated vegetable oil, preferably an ethoxylated castor oil, and the alkoxylated vegetable oil is preferably present 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.

[0054] It is preferred that the alkoxylated vegetable oil comprises 15 to 50 moles of alkylene oxide, preferably 20 to 45 moles of alkylene oxide, based on 1 mole of the vegetable oil.

[0055] The ethoxylated sorbitan fatty acid ester is preferably polysorbate 20, polysorbate 40 and / or polysorbate 80, and the ethoxylated sorbitan fatty acid ester is preferably present 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.

[0056] The composition according to the present application comprises at least one catalyst. It is preferred that the at least one catalyst is selected from the group consisting of organic acids and inorganic acids, the at least one catalyst preferably being selected from the group consisting of sulfuric acid, phosphoric acid, benzenesulfonic acid, xylene sulfonic acid, p-toluenesulfonic acid, ethylbenzenesulfonic acid, naphthol sulfonic acid, cumenesulfonic acid and phenol sulfonic acid.

[0057] It is preferred that the at least one catalyst is present in a total amount of 1 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the total phenolic resin used.

[0058] The composition according to the present application comprises at least one phenolic resin. The at least one phenolic resin preferably has a water content of 1 to 25% by weight, preferably 4 to 19% by weight, based on the total phenolic resin used.

[0059] In the context of the present application, particularly preferred phenolic foam formulations give a foam density of 5 to 900 kg / m3 3 and preferably have a composition as shown in Table 1, which corresponds to a preferred embodiment of the present application:

[0060] Table 1: Composition of preferred phenolic foam formulations

[0061]

[0062] The present application additionally provides a process for the preparation of a phenolic foam using a reaction mixture comprising a composition of the present application as described above, in particular a composition as defined in any one of claims 1 to 14.

[0063] For further preferred embodiments and configurations of the process according to the present application, reference is also made to the above already given statements relating to the composition of the present application.

[0064] The present application additionally provides a phenolic foam prepared by the above process of the present application, preferably using a composition of the present application, in particular a composition as defined in any one of claims 1 to 14.

[0065] It is preferred that the phenolic foam has a density according to ASTM D1622-2020 of 5 to 500 kg / m3 3 , preferably 10 to 200 kg / m3 3 , particularly preferably 12 to 100 kg / m3 3 .

[0066] The present application additionally provides the use of the phenolic foam of the present application for thermal insulation.

[0067] The present application additionally provides the use of at least one polyether siloxane of formula 1 for the preparation of a phenolic foam, preferably using a composition of the present application, in particular a composition as defined in any one of claims 1 to 14.

[0068] The present application additionally provides the use of at least one polyether siloxane of formula 1 for the preparation of a phenolic foam for improving the insulating capacity of the phenolic foam, the phenolic foam preferably being a phenolic foam according to claim 16, the phenolic foam preferably being prepared using a composition of any one of claims 1 to 14. DETAILED DESCRIPTION

[0069] The following describes particularly preferred compositions according to the present application in more detail.

[0070] Particularly preferred compositions according to the present application comprise the following components:

[0071] - at least one phenolic resin,

[0072] - at least one blowing agent,

[0073] - at least one catalyst,

[0074] - at least one polyether siloxane of formula 1

[0075] - optionally further additives etc.

[0076] The preparation of phenolic foams, which can also be referred to synonymously as phenolic resin foams, is known per se to the person skilled in the art. For the preparation of phenolic foams, one or more phenolic resins, preferably one or more types known as resols, are used. The corresponding usable phenolic resins, preferably resols, are known per se. In particular, they can be prepared in a known manner by condensation of phenol or phenol-based compounds, such as cresols, xylenols, para-alkylphenols, para-phenylphenols, resorcinols, etc., and aldehydes, such as formaldehyde, furfural, acetaldehyde, etc., preferably under basic conditions, for example by using catalytic amounts of alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide or calcium hydroxide, or aliphatic amines, such as trimethylamine or triethylamine, preferably with an excess of aldehyde. This represents the usual way of preparing phenolic resins, preferably resols, although the present application is not limited to the chemicals just listed above.

[0077] The molar ratio of phenolic groups to aldehyde groups is not subject to any restrictions. Preferably, the ratio is in the range from 1 : 1 to 1 : 3, more preferably in the range from 1 : 1.5 to 1 : 2.5. The phenolic resins preferably have, but are not limited to, a free aldehyde content of from 0.1 to 0.5 wt.-%. This can be determined according to ISO 11402:2004 by potentiometric titration with hydroxylamine hydrochloride. Preferred phenolic resins usable for the preparation of foams are liquid at 25°C and standard pressure, preferably have a water concentration of about 1 to 25 wt.-%, preferably 5 to 20 wt.-%, and preferably have methylol groups as reactive substituents, as described for example in EP 0170357 B1. If desired, the viscosity of the phenolic resins can be adjusted by, inter alia, for example, the water content. Thus, for example, a high water content generally leads to a lower viscosity and can advantageously both the handling of the resin and its mixing during the preparation of the foam.

[0078] Standard pressure is understood to mean a pressure of 101325 Pa.

[0079] The preferred usable phenolic resins have a viscosity at 25 °C and standard pressure preferably in the range of 1000 to 28000 mPa*s and can be determined by usual methods known to the person skilled in the art, for example using a Brookfield viscosimeter. General information about the preparation and composition of phenolic resins can be found in the prior art and is described, for example, in EP 3830174 A1, EP 2898005 A1, WO 2022043561 A1 or EP 4073155 A1.

[0080] Blowing agents and their use for the preparation of phenolic foams are known to the person skilled in the art. The selection thereof can depend, for example, on the type of system and on the use of the phenolic foam obtained. Depending on the amount of blowing agent used, it is possible, for example, to prepare foams with high or low density. For example, foams with a density according to ASTM D1622-20 of, for example, 5 kg / m3to 900 kg / m3, preferably 5 to 500 kg / m3, more preferably 10 to 200 kg / m3, in particular 12 to 100 kg / m3, can be prepared. 3 3 3 3 3

[0081] Particularly preferred usable blowing agents have already been described above. The blowing agents that can be used can be, for example, one or more suitable compounds with a suitable boiling point, for example a hydrocarbon with 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane or n-pentane; a halogenated hydrocarbon, for example a chlorinated hydrocarbon, for example dichloroethane, 1,2-dichloroethylene, n-propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, amyl chloride, isamyl chloride, 1,1 -dichloroethylene, trichloroethylene or chloroethylene; or a hydrofluorocarbon (HFC), for example HFC 245fa, HFC 134a or HFC 365mfc; a hydrofluoroolefin (HFO) or a hydrohaloolefin, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz or mixtures thereof.

[0082] ​​​​​Especially preferred catalysts which can be used have been described above. Catalysts which can be used in the preparation of phenolic foams are known to the person skilled in the art, for example including from the prior art, and are described, for example, in EP 0170 357 A1 or, for example, DE 602004006376 T2. Conventional organic and inorganic acids known from the prior art can be used for this purpose. Preferably, one or more acids can be used. The following are especially preferred: sulfuric acid, phosphoric acid, benzenesulfonic acid, xylenesulfonic acid, p-toluenesulfonic acid, ethylbenzenesulfonic acid, naphthol sulfonic acid, cumenesulfonic acid and / or phenolsulfonic acid. The catalyst used can be especially a mixture of two or more of these compounds. The preferred amount of catalyst which can be used for complete reaction can be influenced, inter alia, by the water content of the phenolic resin and / or, when the catalyst is present as an aqueous solution, also by the water content of the catalyst. For example, a higher water content can require a higher acid concentration.

[0083] The phenolic foam can be formed in a known manner, i.e. especially by the reaction of a mixture comprising phenolic resin, blowing agent, foam stabilizer and catalyst. When the catalyst is added to the mixture of phenolic resin, blowing agent and foam stabilizer, an exothermic reaction between the methylol groups and the phenol occurs, resulting in the formation of methylene bridges and crosslinking. The condensation is accompanied by the release of water. The exothermicity of the reaction and the foam formation can be influenced, for example, by the nature and amount of the acid used, the nature of the blowing agent and the structure of the foam stabilizer.

[0084] As described above, the foam stabilizer and its use in the preparation of phenolic foams are generally known to the person skilled in the art. According to the application, at least one polyether siloxane of the formula 1 is used. The at least one polyether siloxane of the formula 1 acts as a foam stabilizer. In addition, additional foam stabilizers which assist in the preparation of the foam can also be used. These compounds are well known from the prior art. For example, EP 3830174 A1 describes the use of ethoxylated castor oil.

[0085] The optional additives used can be one or more substances which are generally used in the preparation of phenolic foams and are known from the prior art, for example viscosity reducers, plasticizers, hardeners, flame retardants, cell- refining additives, fillers, dyes, pigments and / or fragrances. Suitable optional additives are described, for example, in EP 3830174 A1, US 4444912 A and EP 1922357 A1.

[0086] The optional solid filler used can be, for example, a metal hydroxide, such as aluminum hydroxide or magnesium hydroxide; a metal carbonate, such as calcium carbonate, magnesium carbonate, barium carbonate or zinc carbonate; a metal oxide, such as aluminum oxide or zinc oxide; or a metal powder, such as zinc. The viscosity of the phenolic resin can optionally be reduced by using, for example, monoethylene glycol or a polyester polyol. The optional hardener can be, for example, a compound having an amino group, such as urea or dicyandiamide. Preferably, urea can be used. These can be used, for example, for foaming and for the preparation of the phenolic resin.

[0087] The process for the preparation of a phenolic foam according to the present application can be carried out by any known method. These are known to the person skilled in the art and are, for example, also described in the patent literature including, for example, EP 3830174 A1.

[0088] Any preferred or particularly preferred embodiment of the present application can be combined with one or more other preferred or particularly preferred embodiments of the present application, unless it is clear from the present description that this is not the case.

[0089] In case of recitation of a range of values, and / or a range of values and / or a category of items, unless otherwise stated, the recitation of a value and / or category to one constituent member, includes all values and / or categories between the lower and upper limits of that recited value and / or category to each constituent member. In the context of the present specification, reference to a document is a reference to the document as it existed on the date of the priority claim of the present application. In the context of the present specification, recitation of an average value is a recitation of a numerical average value, unless otherwise stated. In the context of the present specification, recitation of a parameter determined by measurement is a recitation of a measurement that has been carried out at a temperature of 23 °C and preferably at a pressure of 101 325 Pa, unless otherwise stated.

[0090] The present application is further described herein below with reference to the following reference examples, without limiting the present application in any way.

[0091] Example

[0092] A polyethersiloxane was prepared as described below and subjected to performance tests.

[0093] The catalyst used for the hydrosilylation was a xylene solution of platinum (0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (2 wt% of Pt). The CAS number of this complex is 68478-92-2. The catalyst was purchased from Sigma-Aldrich and used as received.

[0094] The SiH-functional siloxane used was prepared in a similar manner as described in Example 1 of patent application DE 10 2008 042 181.

[0095] The principle of the preparation of allyl polyethers is well known to the person skilled in the art and is described by way of example in patent application EP 4314111 A1, example 1. Similarly, the starting alcohol used is allyl alcohol.

[0096] All reactions were carried out with the aid of Schlenk techniques using nitrogen as inert gas.

[0097] Example 1 : Preparation of PES1

[0098] For the synthesis of the polyether siloxane PES1, in a 500 ml_ four-necked flask with precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 64 g of SiH-functional siloxane of the formula Me3SiO(SiMe2O) 38 (SiMeHO) 10 SiH-functional siloxane of the formula SiMe3(Me = methyl) was mixed together with 36 g of polyether of the formula CH2=CHCH2O(CH2CH2O)9(CH2CH(CH3)O)1 H, 106 g of polyether of the formula CH2=CHCH2O(CH2CH2O) 11 (CH2CH(CH3)O) 10 H and 94 g of polyether of the formula CH2=CHCH2O(CH2CH2O) 23 (CH2CH(CH3)O)4H. The mixture was heated to 90°C. Then, 0.15 g of a solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90°C for 2 hours. After this time, the degree of conversion of the SiH groups was determined by gas volumetry. It was 100%. A transparent product was obtained.

[0099] Example 2: Preparation of PES2

[0100] For the synthesis of the polyether siloxane PES2, in a 500 ml_ four-necked flask with precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 84 g of SiH-functional siloxane of the formula HMe2SiO(SiMe2O) 40 (SiMeHO)8SiMe2H was mixed together with 38 g of polyether of the formula CH2=CHCH2O(CH2CH2O)9(CH2CH(CH3)O)1 H and 178 g of polyether of the formula CH2=CHCH2O(CH2CH2O) 12The polyethers (CH2CH(CH3)0)7H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3- tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0101] Example 3: Preparation of PES 3

[0102] For the synthesis of the polyethersiloxane PES 3, in a 500 mL four-necked flask with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 58 g of the SiH-functional siloxane of formula Me3SiO(SiMe20) 14 SiH-functional siloxane of formula (SiMeHO)4SiMe3 and 112 g of the polyether of formula CH2=CHCH20(CH2CH20) 23 (CH2CH(CH3)0)4H and 130 g of the polyether of formula CH2=CHCH20(CH2CH20) 12 (CH2CH(CH3)0)7H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3- tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0103] Example 4: Preparation of PES 4

[0104] For the synthesis of the polyethersiloxane PES 4, in a 500 mL four-necked flask with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 61 g of the SiH-functional siloxane of formula Me3SiO(SiMe20) 14 SiH-functional siloxane of formula (SiMeHO)4SiMe3 and 101 g of the polyether of formula CH2=CHCH20(CH2CH20) 11 (CH2CH(CH3)0)4H and 138 g of the polyether of formula CH2=CHCH20(CH2CH20) 10 H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3- tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 12SiH-functional siloxane of formula (SiMeHO)4SiMe3 and 132 g of polyether of formula CH2=CHCH2O(CH2CH2O)5H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the degree of conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0105] Example 5: Preparation of PES 5

[0106] For the synthesis of polyethersiloxane PES 5, in a 500 mL four-necked flask with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 51 g of SiH-functional siloxane of formula Me3SiO(SiMe2O)3SiMe3 and 132 g of polyether of formula CH2=CHCH2O(CH2CH2O)5H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the degree of conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 38 10 SiH-functional siloxane of formula (SiMeHO)4SiMe3 and 132 g of polyether of formula CH2=CHCH2O(CH2CH2O)5H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the degree of conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 22 11 12 SiH-functional siloxane of formula (SiMeHO)4SiMe3 and 132 g of polyether of formula CH2=CHCH2O(CH2CH2O)5H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the degree of conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0107] Example 6: Preparation of PES 6

[0108] For the synthesis of polyethersiloxane PES 6, in a 500 mL four-necked flask with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 52 g of SiH-functional siloxane of formula Me3SiO(SiMe2O)3SiMe3 and 132 g of polyether of formula CH2=CHCH2O(CH2CH2O)5H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the degree of conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 14 22 11 12 ​​​​​​The polyethers (CH2CH(CH3)0)7H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the degree of conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0109] Example 7: Preparation of PES 7

[0110] For the synthesis of the polyethersiloxane PES 7, in a 500 mL four-necked flask with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 75 g of the polyether of formula HMe2SiO(SiMe20) 55 The SiH-functional siloxane of formula (SiMeHO)8SiMe2H was mixed together with 225 g of the polyether of formula CH2=CHCH20(CH2CH20) 23 The polyethers (CH2CH(CH3)0)4H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the degree of conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0111] Example 8: Preparation of PES 8

[0112] For the synthesis of the polyethersiloxane PES 8, in a 500 mL four-necked flask with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 57 g of the polyether of formula Me3SiO(SiMe20) 38 The SiH-functional siloxane of formula (SiMeHO) 10 was mixed together with 113 g of the polyether of formula CH2=CHCH20(CH2CH20) 23 and 130 g of the polyether of formula CH2=CHCH20(CH2CH20) 12 The polyethers (CH2CH(CH3)0)4H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the degree of conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0113] Example 9: Preparation of PES 9

[0114] For the synthesis of polyether siloxane PES 9, 66 g of the SiH-functional siloxane of the formula Me3SiO(SiMe2O) 123 (SiMeHO) 25 SiMe3, 108 g of the polyether of the formula CH2=CHCH2O(CH2CH2O) 23 (CH2CH(CH3)O)4H, and 125 g of the polyether of the formula CH2=CHCH2O(CH2CH2O) 12 (CH2CH(CH3)O)7H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0115] Example 10: Preparation of PES 10

[0116] For the synthesis of polyether siloxane PES 10, 131 g of the SiH-functional siloxane of the formula HMe2SiO(SiMe2O) 37.1 (SiMeHO) 2.9 SiMe2H, 168 g of the polyether of the formula CH2=CHCH2O(CH2CH2O) 12 (CH2CH(CH3)O)7CH3, and 125 g of the polyether of the formula CH2=CHCH2O(CH2CH2O) 51 (CH2CH(CH3)O)7H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0117] Example 11 : Preparation of PES 11

[0118] For the synthesis of polyether siloxane PES 11, 110 g of the SiH-functional siloxane of the formula Me3SiO(SiMe2O) 51SiH-functional siloxane of formula (SiMeHO)7SiMe3 and 190 g of polyether of formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O)3H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 13 SiH-functional siloxane of formula (SiMeHO)7SiMe3 and 190 g of polyether of formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O)3H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0119] Example 12: Preparation of PES12

[0120] For the synthesis of the polyether siloxane PES12, in a 500 mL four necked flask with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 148 g of siloxane of formula Me3SiO(SiMe2O)5SiMe3 and 190 g of polyether of formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O)3H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 65 SiH-functional siloxane of formula (SiMeHO)7SiMe3 and 190 g of polyether of formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O)3H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 10 SiH-functional siloxane of formula (SiMeHO)7SiMe3 and 190 g of polyether of formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O)3H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0121] Example 13: Preparation of PES13

[0122] For the synthesis of the polyether siloxane PES13, in a 500 mL four necked flask with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet, 126 g of siloxane of formula Me3SiO(SiMe2O)5SiMe3 and 190 g of polyether of formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O)3H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 108 SiH-functional siloxane of formula (SiMeHO)7SiMe3 and 190 g of polyether of formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O)3H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 10 SiH-functional siloxane of formula (SiMeHO)7SiMe3 and 190 g of polyether of formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O)3H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained. 11 SiH-functional siloxane of formula (SiMeHO)7SiMe3 and 190 g of polyether of formula CH2=CHCH2O(CH2CH2O)5(CH2CH(CH3)O)3H were mixed together. The mixture was heated to 90 °C. Then, 0.15 g of a xylene solution of platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. The exothermic reaction started. Then, the reaction mixture was stirred at 90 °C for 2 hours. After this time, the conversion of SiH groups was determined by gas volumetric analysis. It was 100 %. A transparent product was obtained.

[0123] Example 14: Preparation of PES14

[0124] For the synthesis of polyether siloxane PES14, 121 g of the formula Me3SiO (SiMe2O) was placed in a 500 mL four-necked flask equipped with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet. 21 The SiH-functional siloxane of (SiMeHO)2SiMe3 reacts with 89g of the formula CH2=CHCH2O(CH2CH2O). 12 The polyether of (CH2CH(CH3)O)7H and 89g of the formula CH2=CHCH2O(CH2CH2O) 12 The polyether (CH2CH(CH3)O)7Me was mixed together. The mixture was heated to 90°C. Then, 0.15 g of a xylene solution of a platinum(O)1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. An exothermic reaction 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. It was 100%. A transparent product was obtained.

[0125] Example 15: Preparation of PES15

[0126] For the synthesis of polyether siloxane PES15, 89 g of the formula Me3SiO (SiMe2O) was placed in a 500 mL four-necked flask equipped with a precision glass stirrer, thermometer, reflux condenser and nitrogen inlet. 28 (SiMeHO) 10 SiH-functionalized siloxanes of SiMe3 react with 211g of the formula CH2=CHCH2O(CH2CH2O). 10 The polyethers of H were mixed together. The mixture was heated to 90°C. Then, 0.15 g of a xylene solution of a platinum(O)1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added. An exothermic reaction 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. It was 100%. A transparent product was obtained.

[0127] Table 2: Composition of Polyether Siloxane (PES)

[0128]

[0129] *The reported values ​​correspond to theoretically obtained values ​​for compositions based on SiH-siloxanes and polyethers.

[0130] Preparation of phenolic foam

[0131] For performance comparison, the formulations shown in Table 3 were used. Comparative foaming was performed by hand mixing. This was done by weighing the phenolic resin (amount per run: 180 ± 5 g) and the foam stabilizer into a beaker and mixing with a disc stirrer (diameter 6 cm) at 20 °C and 1000 rpm for 15 s. Then, the blowing agent was added and the mixture was mixed at 1500 rpm for 30 s. Then, the acid was added and the mixture was stirred at 2500 rpm for 30 s and transferred into a 25 cm x 25 cm x 7 cm aluminum mold lined with a polyethylene film and thermostatically controlled at 60 °C. After 30 min, the foam body was demolded and hardened in an oven heated to 60 °C for 42 h.

[0132] Using an AccuPyc II series pycnometer at 100 cm 3 The open cell content was determined in a measurement chamber with 5 x 3 x 3 cm test samples. Immediately after cooling to room temperature after hardening in an oven, the initial thermal conductivity coefficient (lambda value in mW / m-K) was measured on a 2.5 cm thick disc at an average temperature of 23 °C according to the specifications of standard EN 12667:2001 by using a LaserComp FOX 200 instrument. For the determination of its aged value, the test sample was stored in an oven at 70 °C for 7 days and the thermal conductivity was then determined again as described above.

[0133] Table 3: Formulations for the preparation of phenolic foams

[0134] Components Parts by weight Phenol formaldehyde resin 100 Foam stabilizer 4.5 Cyclopentane / isopentane 85 / 15 10 65% by weight of phenolsulfonic acid in water 18

[0135] * Phenolic resin from Bakelite J6014L

[0136] ** parts by weight of the cyclopentane / isopentane mixture

[0137] The polyether siloxane foam stabilizers according to the application were investigated individually and in combination with surfactants not containing Si. This was done using CH 40 and polysorbate 80 from Evonik Operations GmbH as ethoxylated castor oil.

[0138] Table 4: Properties of phenolic foams

[0139]

[0140]

[0141] * Mixing ratio corresponds to parts by weight.

[0142] The results show that the inventive foam stabilizers can achieve higher foam quality and thermal conductivity compared to those of non-inventive foam stabilizers. In particular, the lambda value after aging, which is crucial for the use, shows a significant improvement. All other use-related foam properties are only insignificantly affected, if at all, by the foam stabilizers according to the invention.

Claims

1. A composition for preparing phenolic foam, comprising at least one phenolic resin, at least one blowing agent, at least one catalyst, and at least one polyether siloxane of formula 1. M a M 1 b D c D 1 d (Equation 1) in a = 0 to 2, b = 0 to 2, c = 1 to 100, preferably 6 to 80, more preferably 6 to 60. d = 0 to 40, preferably 1 to 35, more preferably 1 to 30. in a+b=2, a+b+c+d = 5 to 140, preferably 9 to 100, and more preferably 14 to 50. (a+b+c+d) / (b+d) = 5 to 8.5, preferably 5 to 8.0, more preferably 5 to 7.

5. R = alkyl groups having 1 to 16 carbon atoms, aryl groups having 6 to 16 carbon atoms, H, or -OR, each independently identical or different. 2 Preferably, it is methyl, ethyl, phenyl, or H, especially methyl. R 2 = Each independently identical or different alkyl group having 1 to 16 carbon atoms, identical or different aryl group having 6 to 16 carbon atoms, or H, R 1 = Each of the same or different alkyl groups having 6 to 18 carbon atoms, or the same or different polyether groups according to Formula 2, R 3 = Each of the same or different divalent alkyl groups having 2 to 15 carbon atoms, preferably the same or different divalent alkyl groups having 3 to 6 carbon atoms, and particularly preferably -(CH2)3-. R 4 = Each independently identical or different alkyl group having 1 to 18 carbon atoms, optionally containing an ether functional group, or identical or different aryl group having 6 to 18 carbon atoms, optionally containing an ether functional group, or H, preferably H, methyl, ethyl, or phenyl. Among them [CR 4 2CR 4 The four R's in 2O] 4 Not all functional groups are H. And among them [CR 4 2CR 4 [2O] does not include methyl as an R 4 The group and H as the other three R 4 The situation of functional groups, R 5 = Each independently selected from the same or different R 2 and C(O)R 2 The radical group is preferably methyl, butyl, H or C(O)CH3, more preferably H, methyl or C(O)CH3. e = 0 to 100, preferably 0 to 80, especially 0 to 60. f = 0 to 100, preferably 0 to 80, especially 0 to 60. g = 0 to 100, preferably 0 to 80, especially 0 to 60. h = 0 to 100, preferably 0 to 60, more preferably 0. Where e+f+g+h = 5 to 100, preferably 10 to 90, and more preferably 10 to 80. The polyether siloxane of formula 1 contains no more than 50 mol% of R. 1 Each group is independently an alkyl group having 6 to 18 carbon atoms, either the same or different. Furthermore, the at least one polyether siloxane of Formula 1 is present in a total amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of total phenolic resin used.

2. The composition according to claim 1, characterized in that, The at least one polyether siloxane of formula 1 has the following characteristics: all R 1 The percentage of R in the group is less than 100 mol%, preferably less than 70 mol%, more preferably less than 50 mol%. 1 The group contains a polyether group of general formula 2, where f+g+h=0; Particularly preferably, the at least one polyether siloxane of formula 1 has the following characteristics: no R 1 The group contains a polyether group of general formula 2, where f+g+h=0.

3. The composition according to claim 1 or 2, characterized in that, The at least one polyether siloxane of formula 1 has the following characteristics: All R 1 At least 25 mol% of the group, preferably at least 50 mol%, more preferably at least 75 mol% of R 1 The group comprises a polyether group of general formula 2, wherein R 5 =H.

4. The composition according to any one of claims 1 to 3, characterized in that, The at least one polyether siloxane of formula 1 has the following characteristics: All R 1 At least 30 mol% of the group, preferably at least 40 mol%, more preferably at least 50 mol% of R 1 The group comprises a polyether group of general formula 2, wherein e+f+g = 17 to 60, preferably 19 to 40. (f+g) / (e+f+g) > 0 to 0.6, preferably 0.1 to 0.5, more preferably 0.15 to 0.4, and h＝0。 5. The composition according to any one of claims 1 to 4, characterized in that, The at least one polyether siloxane of formula 1 has the following characteristics: It contains at least two different Rs 1 Group.

6. The composition according to any one of claims 1 to 5, characterized in that, The at least one polyether siloxane of formula 1 has the following characteristics: It contains at least two different Rs 1 Groups, wherein at least one R 1 The group is a polyether group of formula 2, and an R 1 The group is an alkyl group having 6 to 18 carbon atoms, wherein all R 1 The R group contains no more than 50 mol%, preferably no more than 25 mol%, of the group. 1 The group is an alkyl group having 6 to 18 carbon atoms.

7. The composition according to any one of claims 1 to 6, characterized in that, The at least one foaming agent is selected from: - Hydrocarbons having 3, 4, or 5 carbon atoms, preferably cyclopentane, isopentane, or n-pentane and - A haloalkane having 3, 4 or 5 carbon atoms, preferably isopropyl chloride, hydrofluoroolefin or hydrohaloolefin, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz.

8. The composition according to any one of claims 1 to 7, characterized in that, In addition, at least one silicone-free surfactant is present, based on 100 parts by weight of total phenolic resin used, wherein the at least one silicone-free surfactant is preferably present in a total amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, and wherein the at least one silicone-free surfactant is preferably selected from alkoxylated vegetable oils and ethoxylated dehydrated sorbitol fatty acid esters.

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

10. The composition according to claim 8 or 9, characterized in that, Based on 1 mole of vegetable oil, the alkoxylated vegetable oil contains 15 to 50 moles of alkylene oxides, preferably 20 to 45 moles of alkylene oxides.

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

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

13. The composition according to any one of claims 1 to 12, characterized in that, Based on 100 parts by weight of total phenolic resin used, the at least one catalyst is present in a total amount of 1 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably 3 to 20 parts by weight.

14. The composition according to any one of claims 1 to 13, characterized in that, Based on the total phenolic resin used, the at least one phenolic resin has a water content of 1% to 25% by weight, preferably 4% to 19% by weight.

15. A method for preparing phenolic foam, characterized in that, It is carried out using a reaction mixture comprising the composition defined in any one of claims 1 to 14.

16. The phenolic foam prepared by the method of claim 15, characterized in that, The phenolic foam preferably has a content of 5 to 500 kg / m³. 3 Preferably 10 to 200 kg / m 3 Particularly preferred is 12 to 100 kg / m 3 The density is based on ASTM D1622-20.

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