Multi-component polyurethane foam compositions

Abstract

The present invention describes a multi-component polyurethane foam composition comprising: (i) a first component, comprising one or more phenolic resins of the benzyl ether type, wherein a) the first component comprises free phenol and free hydroxybenzyl alcohol, wherein at least about 1.2 parts by weight of free hydroxybenzyl alcohol per 1 part by weight of free phenol are comprised in the first component; and / or b) the first component comprises free phenol and free saligenin (o-hydroxybenzyl alcohol), wherein at least about 1.1 parts by weight of free saligenin (o-hydroxybenzyl alcohol) per 1 part by weight of free phenol are comprised in the first component; (ii) a second component, comprising an isocyanate formulation consisting of one or more isocyanate compounds, wherein at least one isocyanate compound has at least 2 isocyanate groups per molecule; and (iii) optionally, a third component, comprising one or more (halogen)hydrocarbon- containing blowing agents and / or water, wherein, if the multi-component polyurethane foam composition does not include a third component, then the first component comprises at least 0.95% by weight, preferably at least 1.0% by weight, and especially preferably at least 2.0% by weight of water.

Description

[0001] New PCT application

[0002] based on DE 102024004417.5

[0003] ASK Chemicals GmbH

[0004] Vossius Ref.: AJ1865 PCT

[0005] Multi-component polyurethane foam compositions

[0006] Technical Field

[0007] The present invention relates to a multi-component polyurethane foam composition. The multicomponent polyurethane foam composition can be used, for example, as cavity sealing (in particular for motor vehicles), as insulation foam in sandwich panels, for pipe insulation, in refrigerators, for house and vehicle insulation, as spray insulation in mines, or as impact sound insulation.

[0008] Background of the invention

[0009] Two-component (2C) polyurethane foam compositions based on polyols are well known. For example, addition products made of ethylene and / or propylene oxide with polyvalent alcohols or polyester polyols, polyvalent amines and thiol compounds or mixtures of the respective components are used as polyol components. Typical starter molecules are also polyols, such as for example glycerol, sorbitol, sucrose, trimethylolpropane, pentaerythritol or triethanolamine. A foam structure is built up with the help of water and / or highly volatile blowing agents. Isocyanate can react with both water and the polyol component, forming CO2 in the former case. As a result, the resulting polyurethane is foamed and polyurea is partially formed. Due to an excess of isocyanate groups, polyisocyanurate is formed by trimerization. For the purposes of the present invention, reference is always made to polyurethane (PUR) / polyisocyanurate foams (PI ) even though only the term polyurethane foam is used hereinafter.

[0010] JP S61 -223035 A describes a foam composition based on a phenolic resin of the benzyl ether type, polyisocyanate, an aromatic sulfonic acid, boron trifluoride and water for the primary use in thermal insulation. JP S61-223035 A describes the addition of a curing agent and reports strong heat development and foaming when benzyl ether resins are used. There is no mention of hardening without curing agents. The foam is particularly foamed and brittle. Boron trifluoride is added to improve corrosion protection, and resorcinol is used to increase mechanical strengthand adhesion. Water has to be added to improve the foam quality in the molded body. The composition and molecular structure of the benzyl ether resin used are not specified further.

[0011] EP 0590638 A describes a process for the preparation of a polyurethane-polycarbodiimide foam, said process comprising reacting a polyol component containing a benzyl ether type phenolic resin having hydroxymethylene groups with an organic polyisocyanate component in the presence of an organotin catalyst and a carbodiimidating catalyst. It is noted that the hydroxymethylene group in the benzyl ether resin used in the process reacts with isocyanates in the presence of tin to generate carbon dioxide gas and foams up “automatically”. The carbodiimidation step of two NCO groups, which takes place concurrently, releases additional CO2 which further contributes to foaming. The benzyl ether resin has a hydroxyl number (OHN) of 300 to 700, preferably 450 to 600 mg KOH / g. The benzyl ether resins can be mixed with polyols to reduce the curing rate; 20 to 100% by weight of benzyl ether resin, preferably 30 to 80% by weight, based on the total weight of the polyols, can be used for this purpose. 0.1 to 4% by weight, preferably 0.5 to 2% by weight, of water can be present, based on the polyisocyanates. The patent application states that benzyl ether resin foams are prone to cracking. The composition and molecular structure of the benzyl ether resin used are not specified further.

[0012] EP 0650991 A describes a process for producing a polyurethane foam, which comprises reacting a polyol component containing a benzyl ether type phenolic resin having hydroxymethylene groups with an organic polyisocyanate component in the presence of an organotin type urethanization catalyst, a tertiary amine type blowing catalyst and water. The benzyl ether resin preferably has a free water content of at most 0.5% by weight and a viscosity of 1 to 20 Pa s (no temperature given). At most, 4% by weight, preferably at most 2% by weight, of water, based on the polyisocyanates, can be present. This application states that the formation of cracks in benzyl ether foams can be prevented by the addition of polyols. The composition and molecular structure of the benzyl ether resin used are not specified further.

[0013] GB 2074 176 A describes a polyurethane-modified polyisocyanurate foam obtained by reacting a special benzyl ether resin with a polyisocyanate component in the presence of a trimerization catalyst for the polyisocyanate component(s) and a blowing agent. Dibutyltin dilaurate can be used as a reaction promoter. At least 20% benzyl ether resin should be contained in the formulation. Silicone surfactants are added in an amount of 0.2 to 5%, based on the polyol / isocyanate. The composition and molecular structure of the benzyl ether resin used are not specified further.US 3,948,824 A describes describes foams based on a phenolaldehyde-benzyl ether resin, a polyisocyanate and a gaseous blowing agent. Example 3 shows a condensation product of a benzyl ether resin and an adipic acid polyol as a polyol component. The resulting benzyl ether resin contains about 1% of free formaldehyde. In addition to phenol as a monomer for the production of the benzyl ether resin, alkyl phenols are mentioned. In a list, o-cresol is not mentioned, since the free ortho-position is needed to polymerize the benzyl ether resin with formaldehyde. The composition and molecular structure of the benzyl ether resin used are not specified further.

[0014] US 4,448,951 A describes foams based on modified benzyl ether-containing resol polyols obtained from phenol, paraformaldehyde, and an aliphatic hydroxyl compound using a metal catalyst. The benzyl ether resin contains 1 to 50 mol-%, preferably 10 to 25 mol-%, free OH groups and 5 to 35 mol-% etherified OH groups. Monovalent or polyvalent alcohols with a C-chain up to C12 are mentioned as etherification alcohol. Examples 20 and 21 contain syntheses with monohydric alcohols, such as methanol and n-butanol. Phenolic monomers that are substituted at the ortho position(s) are excluded.

[0015] US 3,242,107 A describes special novolaks from para-tert. butylphenol-formaldehyde resin or its adducts with alkylene oxides, which together with isocyanates are suggested for use in foams, casting compounds and coatings. It is mentioned that solvents and other polyols can be added.

[0016] GB 2033413 A describes a process for the preparation of a phenol-aldehyde condensate wherein a phenol is reacted with an aliphatic aldehyde under non-aqueous conditions in the presence of an aliphatic polyol. In one embodiment, the reaction can be performed at a pH value of less than 6 using an organic acid to adjust the pH.

[0017] EP 1 209 181 A claims at least 3% of unspecified benzyl ether resins in foam applications mixed with other polyols and surfactants. The benzyl ether resin is manufactured by Hodogaya Chemical Co. Ltd under the name BEP2100M and is not specified in more detail.

[0018] JP 2000-281744 A claims resols or benzyl ether resins with a high reactivity, containing 10 to 50% benzyl ether resin. This is provided by the company Showa and is free of o-cresol and, if at all, only derivatized at the meta position. The structure is not specified in more detail.J P 2000-1240649 A describes benzyl ether resins in combination with glycols and polyols and uses a benzyl ether resin from Hodogaya Chemical Co. Ltd under the name BEP2100EM, which is not specified in more detail.

[0019] J P 2003-048948 A mentions benzyl ether resins, which can contain o-cresol and other monomers, in combination with sulfonic acids.

[0020] JP 2000-6152218 A describes benzyl ether resins as copolymers of phenol and o-cresol in a weight ratio of 10 : 90 to 90 : 10 and mentions CNSL and other modifiers. The average molar weight is between 250 to 1000 g / mol. What is meant by molar weight (Mn or Mw) is not explained. Here as well, the document mentions that benzyl ether resins are prone to cracking. There is no mention of the etherification of free hydroxymethylol groups of the benzyl ether resin with alcohols.

[0021] J PH 09208657 A describes benzyl ether resins for foam applications with 8% hydroxymethylene groups; BEP 1000 from Hodogaya Chemical Co. Ltd. is mentioned as an example. Benzyl ether resins react too quickly and form cracks and open cells, so more polyols are added.

[0022] JPS 6397641 A describes benzyl ether resins with the formula

[0023]

[0024] wherein m and n are numbers of at least 2 and the ratio of m to n is at least 1, X=H or a terminal methylol group. The ratio of both is at least 1. In a benzyl ether phenol resin, R=H.

[0025] None of the above-mentioned documents defines the resulting benzyl ether resins by means of the free monomeric phenol which is (inevitably) still present after synthesis and / or the first condensation stage of phenol with formaldehyde (saligenin / homosaligenin).

[0026] Some patent specifications mention disadvantageous cracking in foams produced with benzyl ether resins. Nevertheless, there has been no lack of effort to use benzyl ether resins in PU foams, as they are hard, brittle, and resilient, have low shrinkage, low flammability, and low smoke development.DE 102021 003264 A1 describes casting resins consisting of benzyl ether resins with a defined monomeric phenol / saligenin ratio. The goal is to obtain a casting resin free of bubbles / foam. Therefore, no blowing agent is added and the water content is 0.90% by weight, more preferably at a maximum of about 0.85% by weight, and especially preferably at a maximum of about 0.750% by weight, based on the benzyl ether resin.

[0027] WO 2018 / 113853 A1 discloses binders that can be used to cure molding material mixtures. The molding material mixtures can be used to produce cores, molds and feeders for metal casting.

[0028] The inventors have set themselves the task of developing new Pll foam compositions with a homogeneous pore distribution and no blowholes. Another object is to provide Pll foam compositions that show little to no cracking.

[0029] Summary of the invention

[0030] Accordingly, the present invention relates to:

[0031] (1) A multi-component polyurethane foam composition comprising:

[0032] (i) a first component, comprising one or more phenolic resins of the benzyl ether type, wherein

[0033] a) the first component comprises free phenol and free hydroxybenzyl alcohol, wherein at least about 1.2 parts by weight of free hydroxybenzyl alcohol per 1 part by weight of free phenol are comprised in the first component; and / or

[0034] b) the first component comprises free phenol and free saligenin (o-hydroxybenzyl alcohol), wherein at least about 1.1 parts by weight of free saligenin (o-hydroxybenzyl alcohol) per 1 part by weight of free phenol are comprised in the first component;

[0035] (ii) a second component, comprising an isocyanate formulation consisting of one or more isocyanate compounds, wherein at least one isocyanate compound has at least 2 isocyanate groups per molecule; and

[0036] (iii) optionally, a third component, comprising one or more (halogen)hydrocarbon- containing blowing agents and / or water,

[0037] wherein, if the multi-component polyurethane foam composition does not include a third component, then the first component comprises at least 0.95% by weight, preferably at least 1.0% by weight, and especially preferably at least 2.0% by weight of water.(2) The multi-component polyurethane foam composition according to number (1), wherein the weight ratio of free phenol to free hydroxybenzyl alcohol in the first component is

[0038] • 1 : greater than 1.2 to 1 : 10,

[0039] • preferably 1 : 1.2 to 1 : 8, and

[0040] • more preferably 1 : 1.3 to 1 : 6, and

[0041] • especially preferably 1 : 1.5 to 1 : 4.

[0042] (3) The multi-component polyurethane foam composition according to number (1) or (2), wherein the weight ratio of free phenol to free saligenin in the first component is

[0043] • 1 : 1.1 to 1 : 8,

[0044] • preferably 1 : 1.1 to 1 : 6, and

[0045] • more preferably 1 : 1.2 to 1 : 4,

[0046] • especially preferably 1 : 1.4 to 1 : 2.5.

[0047] (4) The multi-component polyurethane foam composition according to any of numbers (1) to (3), wherein the multi-component polyurethane foam composition comprises water in a total amount of about 0.3% by weight to about 10% by weight, preferably about 0.5% by weight to about 7% by weight, more preferably about 1.0% by weight to about 6% by weight, based on the multi-component polyurethane foam composition.

[0048] (5) The multi-component polyurethane foam composition according to any of numbers (1) to (4), wherein the water content of the first component is 0.2 to 30% by weight, more preferably 0.4 to 25% by weight, and especially preferably 0.5 to 20% by weight.

[0049] (6) The multi-component polyurethane foam composition according to any of numbers (1) to (5), wherein the multi-component polyurethane foam composition comprises one or more (halogen)hydrocarbon-containing blowing agents in a total amount of about 0.5% by weight to about 25% by weight, preferably about 1% by weight to about 20% by weight, more preferably about 2% by weight to about 10% by weight, based on the multi-component polyurethane foam composition.

[0050] (7) The multi-component polyurethane foam composition according to any of numbers (1) to (6), wherein the (halogen)hydrocarbon-containing blowing agent is selected from n- pentane, isopentane, cyclopentane, hexane, chloropropane, and hydrofluoroolefins, or mixtures thereof.(8) The multi-component polyurethane foam composition according to any of numbers (1) to (7), wherein the first component comprises at most about 12.0% by weight of free phenol, preferably at most about 8.0% by weight of free phenol, more preferably at most about 5.0% by weight, especially preferably at most about 2.0% by weight of free phenol.

[0051] (9) The multi-component polyurethane foam composition according to any of numbers (1) to (8), wherein the multi-component polyurethane foam composition, based on the weight of the first component, comprises free saligenin (o-hydroxybenzyl alcohol) in an amount of about 1.0 to about 21.0% by weight, or about 2.0 to about 18.0% by weight, and / or free hydroxybenzyl alcohol in an amount of about 2.0 to about 30.0% by weight, preferably about 2.5 to about 28.0% by weight.

[0052] (10) The multi-component polyurethane foam composition according to any of numbers (1) to (9), wherein the phenolic resin of the benzyl ether type comprises structural units selected from o-cresol, cardanol and / or cardol.

[0053] (11) The multi-component polyurethane foam composition according to any of numbers (1) to (10), wherein the multi-component polyurethane foam composition comprises one or more silicone surfactants.

[0054] (12) The multi-component polyurethane foam composition according to number (11), wherein the content of silicone surfactants is 0.01 to 1.0% by weight, preferably 0.02 to 0.50% by weight, more preferably 0.03 to 0.30% by weight, especially preferably 0.05 to 0.20% by weight, based on the multi-component polyurethane foam composition.

[0055] (13) The multi-component polyurethane foam composition according to any of numbers (1) to (12), wherein the multi-component polyurethane foam composition, based on the total weight of the multi-component polyurethane foam composition, comprises:

[0056] • about 8 to about 70% by weight, preferably about 10 to about 62% by weight of phenolic resin of the benzyl ether type, and / or

[0057] • about 13 to about 90% by weight, preferably about 17 to about 80% by weight of isocyanate formulation.

[0058] (14) The multi-component polyurethane foam composition according to any of numbers (1) to (13), wherein the weight ratio of the first to the second component ranges from about 1 : 1.2to about 1 : 5, preferably about 1 : 1.4 to about 1 : 4.5, more preferably about 1 : 1.5 to about 1 : 4.

[0059] (15) The multi-component polyurethane foam composition according to any of numbers (1) to (14), wherein the molar ratio of the isocyanate-reactive groups to the isocyanate groups ranges from about 1 : 1.2 to about 1 : 4.5, preferably about 1 : 1.4 to about 1 : 4, more preferably about 1 : 1.5 to about 1 : 3.7.

[0060] (16) The multi-component polyurethane foam composition according to any of numbers (1) to (15), wherein the density of the hardened foamed composition is at least about 10 kg / m3, preferably at least about 20 kg / m3and more preferably at least 30 kg / m3, and is at most about 75 kg / m3, preferably at most about 70 kg / m3, more preferably at most about 60 kg / m3.

[0061] (17) A method for producing a polyurethane foam, wherein the first component, the second component and, optionally, the third component of the multi-component polyurethane foam composition as well as optional additives according to any of numbers (1) to (10) are mixed into a mixture.

[0062] (18) The method according to number (17), wherein the mixture is placed into a mold or the mixture is applied to the surface of a substrate.

[0063] (19) The method according to number (17) or (18), wherein the polyurethane foam is hardened.

[0064] (20) A polyurethane foam obtainable by the method of any of numbers (17) to (19).

[0065] (21) Use of the multi-component polyurethane foam composition according to any of numbers (1) to (16) as a cavity sealant (in particular for motor vehicles), as an insulating foam in sandwich panels, for pipe insulation, in refrigerators, for house insulation, as spray insulation in mines or as impact sound insulation.

[0066] (22) Use of the multi-component polyurethane foam composition according to any of numbers (1) to (16) for sound insulation, heat insulation, or for rust protection.

[0067] (23) Use of the multi-component polyurethane foam composition according to any of numbers (1) to (16) for coating the surface of a substrate.(24) Use of a phenolic resin of the benzyl ether type to produce a polyurethane foam, wherein a) the phenolic resin comprises free phenol and free hydroxybenzyl alcohol, wherein at least about 1.2 parts by weight of free hydroxybenzyl alcohol per 1 part by weight of free phenol are comprised in the phenolic resin; and / or

[0068] b) the phenolic resin comprises free phenol and free saligenin (o-hydroxybenzyl alcohol), wherein at least about 1.1 parts by weight of free saligenin (o-hydroxybenzyl alcohol) per 1 part by weight of free phenol are comprised in the phenolic resin.

[0069] (25) The use according to any of numbers (21) to (24) to improve the homogeneity of the pore distribution in the polyurethane foam.

[0070] Detailed description

[0071] For the purposes of this invention, multi-component polyurethane foam compositions are understood to encompass all compositions comprising at least two components which, when mixed, polymerize to form a polyurethane / polyisocyanurate and form a foam. Thus, the multicomponent polyurethane foam compositions are multi-component compositions for forming a polyurethane foam (which also encompasses a polyurethane / polyisocyanurate foam). In other words, the term “multi-component polyurethane foam composition” as used in the present invention refers to a kit comprising separately the first component, the second component and optionally the third component. A polyurethane / polyisocyanurate foam is formed upon mixing the separate components of the kit. During the reaction, the reactive components of the composition change into a solid state.

[0072] It was found that in the compositions of the present invention, the phenolic resins of the benzyl ether type according to claim 1 :

[0073] - show a finer-pored, more homogeneous foam pattern, and

[0074] - show higher compatibility with blowing agents.

[0075] These effects are surprising and could not be foreseen by the person skilled in the art or inferred from the prior art.

[0076] Foam structure:

[0077] Benzyl ether resins according to the present invention show an even, homogeneous pore distribution in the foamed state as PU, both lengthwise and crosswise. This also applies to themold edge area (usually less foam structure) and to the center (usually burning, discoloration). This is achieved by including at least about 1.2 parts by weight of free hydroxybenzyl alcohol per 1 part by weight of free phenol in the first component, and / or at least about 1.1 parts by weight of free saligenin (o-hydroxybenzyl alcohol) per 1 part by weight of free phenol in the first component.

[0078] First

[0079] The first component comprises one or more phenolic resins of the benzyl ether type.

[0080] The first component preferably does not comprise any isocyanate compounds since they tend to react prematurely with the phenolic resin of the benzyl ether type.

[0081] Phenolic resin of the benzyl ether type

[0082] In the first component, at least one phenolic resin of the benzyl ether type is used. In the following, for the sake of simplicity, this component is referred to as "phenolic resin of the benzyl ether type". However, it is self-evident that mixtures of several phenolic resins of the benzyl ether type are encompassed by this designation as well. Furthermore, the terms "phenolic resin of the benzyl ether type", "benzyl-ether-type phenolic resin" and "benzyl ether resin" are used equivalently in the present application.

[0083] All conventionally used phenolic compounds are suitable for preparing the phenolic resins of the benzyl ether type. In addition to unsubstituted phenols, substituted phenols or mixtures thereof can be used. The phenolic compounds are preferably not substituted either in both ortho positions or in one ortho and the para position. The remaining ring carbon atoms can be substituted. The selection of the substituent is not particularly limited, provided that the substituent does not adversely affect the reaction of the phenol with the aldehyde.

[0084] Examples of substituted phenols are alkyl-substituted, alkoxy-substituted, aryl-substituted and aryloxy-substituted phenols.

[0085] In addition to -CH2- linked phenol units, the basic structure of a phenolic resin of the benzyl ether type comprises -CH2-O-CH2- linked phenol units and can be illustrated for example (with regard to a product reacted only with formaldehyde) as follows

[0086]

[0087] The different units are typically statistically distributed (i.e. linked in a different order than shown above). The phenol unit can also be partially para-linked. Here, each R1is independently (in particular of m and n) hydrogen or an alkyl and / or alkenyl substituent of C1-C26 (saturated or unsaturated, straight-chain or branched) in ortho-, meta- or para-position to the phenolic hydroxy group; the sum of m and n is at least about 2 and the ratio m / n is at least about 1 , preferably from about 9 : 1 to about 1 : 9 (mol : mol); R is independently hydrogen, -CH3, -CH2OH or -CH2O-R2wherein R2= a C1 to C9 hydrocarbon. The group R2can be straight-chain or branched, saturated or unsaturated. In a preferred embodiment, R2is a methyl, ethyl or n-butyl group or a mixture thereof. About 1 to about 49 mol-%, preferably about 2 to about 35 mol-%, and more preferably about 2.5 to about 25 mol-% of the -CH2OH groups can be etherified with R2.

[0088] The substituents mentioned above, for example, have about 1 to about 26, preferably about 1 to about 15 carbon atoms. Examples of suitable phenols include o-cresol, m-cresol, p-cresol, 3.5-xylenol, 3,4-xylenol, 3,4,5-trimethylphenol, 3-ethylphenol, 3,5-diethylphenol, p-butylphenol, 3.5-dibutylphenol, p-amylphenol, cyclohexylphenol, p-octylphenol, p-nonylphenol, cardanol, 3.5-dicyclohexylphenol, p-crotylphenol, p-phenylphenol, 3,5-dimethoxyphenol and p-phenoxyphenol.

[0089] Phenol and / or o-cresol, and / or cardanol and / or cardol are especially preferred phenolic components for the synthesis of the benzyl ether resin.

[0090] Higher condensed phenols, such as bisphenol A, are also suitable. In addition, polyvalent phenols which have more than one phenolic hydroxyl group are suitable as well.

[0091] Preferred polyvalent phenols have 2 to 4 phenolic hydroxyl groups. Special examples of suitable polyvalent phenols are pyrocatechol, resorcinol, hydroquinone, pyrogallol, phloroglucin, 2.5-dimethyl resorcinol, 4,5-dimethyl resorcinol, 5-methyl resorcinol, cardol or 5-ethyl resorcinol. Mixtures of various monovalent and polyvalent and / or substituted and / or condensed phenolic components can also be used for the preparation of the phenolic resin of the benzyl ether type.In one embodiment, phenols of the general formula I

[0092]

[0093] are used for the preparation of the phenol formaldehyde resin component, wherein A, B and C are independently selected from: a hydrogen atom, a branched or unbranched alkyl or alkenyl group, which can have, for example, about 1 to about 26, preferably about 1 to about 15 carbon atoms (wherein the alkenyl group can contain up to about 3 conjugated and / or isolated double bonds), a branched or unbranched alkoxy group which can have, for example, about 1 to about 26, preferably about 1 to about 15 carbon atoms, a branched or unbranched alkoxy group, which can have, for example, about 1 to about 26, preferably about 1 to about 15 carbon atoms (where the alkoxy group can contain up to about 3 conjugated and / or isolated double bonds).

[0094] In a preferred embodiment, the phenolic resin of the benzyl ether type consists of phenol, o-cresol and cardanol structural units. The preferred molar ratios of the individual structural units in the benzyl ether resin structure are as follows:

[0095] Phenol to cardanol in the range of about 10 : 1 to about 99 : 1, preferably from about 15 : 1 to about 60 : 1; and / or

[0096] phenol to o-cresol in the range of about 1 : 1 to about 10 : 1, preferably from about 1.5 : 1 to about 3.5 : 1; and / or

[0097] o-cresol to cardanol in the range of about 5 : 1 to about 30 : 1, preferably from about 10 : 1 to about 20 : 1.

[0098] In addition to formaldehyde, aldehydes of the following formula are also suitable as further aldehyde for the production of phenolic resins of the benzyl ether type:

[0099] R-CHOwherein R is a carbon atom group with 1 to 3 carbon atoms, preferably one carbon atom. Specific examples are acetaldehyde and propionaldehyde. Formaldehyde is especially preferred, either in its aqueous form, as para-formaldehyde, or trioxane.

[0100] In order to obtain phenolic resins of the benzyl ether type, a molar amount of aldehyde compounds at least equivalent to the molar amount of the phenol compounds is preferably used. Preferably, the molar ratio of aldehyde compound to phenol compound is about 1.05 : 1.0 to about 2.5 : 1, more preferably about 1.1 : 1 to about 2.2 : 1, especially preferably about 1.2 : 1 to about 2.0 : 1.

[0101] The production of phenolic resin of the benzyl ether type is carried out according to a method known to the person skilled in the art. In this method, the phenol and the aldehyde are reacted in the presence of a divalent metal ion, at temperatures of preferably at most about 130 °C. The resulting water is distilled off. For this purpose, a suitable entrainer can be added to the reaction mixture, such as toluene or xylene, or distillation can be carried out at a reduced pressure.

[0102] Catalysts suitable for the production of phenolic resins of the benzyl ether type are salts of divalent ions of metals, such as Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba, especially Zn salts. Preferably, zinc acetate is used. The amount used is not critical. Typical amounts of metal catalysts are about 0.02 to about 0.3% by weight, preferably about 0.02 to about 0.18% by weight, based on the total amount of phenol compound and aldehyde compound.

[0103] Such resins are described, for example, in US 3,485,797 and in EP 1 137500 , the disclosure of which is hereby expressly referred to both with regard to the phenolic resins of the benzyl ether type themselves and with regard to their preparation. Analyses of these resins show that the weight ratio of free phenol (hydroxybenzene) to free hydroxybenzyl alcohol is always 1 : <1.

[0104] In another preferred embodiment of the phenolic resin of the benzyl ether type, the ratio of free phenol to saligenin can be adjusted:

[0105] The first reaction stage of the formaldehyde addition, consisting of one mole of phenol and one mole of formaldehyde, forms hydroxybenzyl alcohols, in particular saligenin. Due to the orthoortho directing effect of the metal catalyst,

[0106]

[0107] Saligenin (2-hydroxybenzyl alcohol or o-hydroxybenzyl alcohol)

[0108] Mw: 124.14 g / mol

[0109] is mainly formed. However, the formation of homosaligenin

[0110]

[0111] Homosaligenin (4-hydoxybenzyl alcohol or p-hydroxybenzyl alcohol)

[0112] is possible as well. Mixtures of positional isomers are also possible; thus, the -CH2-OH group can be located at the ortho and / or the para position, e.g. be linked to the ortho and ortho, to the ortho and para and to the ortho, ortho and para positions. In another embodiment, one, two, or three -CH2-OH groups can be etherified with a C1 to C9 monoalcohol. This monoalcohol can be straight-chain or branched, saturated or unsaturated.

[0113] The statements made in connection with the example of phenol also apply to the phenolic basic body o-cresol and m-cresol. Possible mixtures of positional isomers of the -CH2-OH group are at the ortho- or para- and at the ortho- and para-positions. In another embodiment, one or two -CH2-OH groups can be etherified with a C1 to C9 monoalcohol. This monoalcohol can be straight-chain or branched, saturated or unsaturated. In a preferred embodiment, it is methanol, ethanol or n-butanol.

[0114] If cardanol and / or cardol are used as phenolic basic bodies, the -CH2-OH group can be located at an ortho and / or para position, e.g. be linked to the ortho and ortho, to the ortho and para and to the ortho, ortho and para positions. In another embodiment, one, two, or three -CH2-OH groups can be etherified with a C1 to C9 monoalcohol.

[0115] This monoalcohol can be straight-chain or branched, saturated or unsaturated. In a preferred embodiment, it is methanol, ethanol or n-butanol.Monomeric addition products (also referred to as "monomeric condensation products") are defined as the first reaction stage of a phenolic basic body with formaldehyde, wherein up to three ring hydrogens of the phenolic basic body can be substituted with a -CH2-OH group. Monomeric addition products based on phenol have a molar mass of 124 g / mol (hydroxybenzyl alcohol) to 184 g / mol (phenol plus up to 3 -CH2OH). Any C1 to C26-alkyl groups that are bound to the phenolic base body and / or as an alkyl group to an etherified -CH2-OH group are not included in the given molar weights.

[0116] The multi-component polyurethane foam composition preferably comprises free phenol and free hydroxybenzyl alcohol, wherein at least about 1.2 parts by weight of free hydroxybenzyl alcohol per 1 part by weight of free phenol are comprised in the multi-component polyurethane foam composition. Preferably, about 1.2 to about 10, more preferably from about 1.2 to about 8, especially preferably from about 1.3 to about 6 and particularly preferably from about 1.5 to about 4 parts by weight of free hydroxybenzyl alcohol per 1 part by weight of free phenol are comprised in the multi-component polyurethane foam composition.

[0117] For the purposes of the invention, the term "hydroxybenzyl alcohol" refers to ortho-hydroxybenzyl alcohol, meta-hydroxybenzyl alcohol and para-hydroxybenzyl alcohol:

[0118]

[0119] In another preferred embodiment, the multi-component polyurethane foam composition comprises free phenol and free saligenin (o-hydroxybenzyl alcohol), wherein at least about 1.1 parts by weight of free saligenin (o-hydroxybenzyl alcohol) per 1 part by weight of free phenol are comprised in the multi-component polyurethane foam composition. Preferably, from about 1.1 to about 8, more preferably from about 1.1 to about 6, especially preferably from about 1.2 to about 4, and particularly preferably from about 1.4 to about 2.5 parts by weight of free saligenin (o-hydroxybenzyl alcohol) per 1 part by weight of free phenol are comprised in the multi-component polyurethane foam composition.The content of free phenol, hydroxybenzyl alcohol and saligenin can for example be determined by gas chromatography (injector temperature 280 °C, Agilent 7890A, capillary column HP5MS, l=50 m, d=0.2 mm, 0.3 pm coating, temperature ramp T=50 °C - 325 °C).

[0120] In particular, the "weight of phenolic resin of benzyl ether type" refers to the sum of the weights of the phenolic resin and the associated (free) monomers and hydroxybenzyl alcohols (including added hydroxybenzyl alcohols, e.g. saligenin), wherein the phenolic resin is the reaction product of at least one formaldehyde compound and one phenol compound, including polymeric analogous reaction products, such as the alkoxylation of the end groups.

[0121] The content of free phenol, based on the weight of the phenolic resin of the benzyl ether type, is preferably at most about 15.0% by weight, preferably at most about 10.0% by weight, more preferably at most about 8.0% by weight, especially preferably at most about 3.0% by weight.

[0122] The content of free phenol in the first component is preferably at most about 12.0% by weight, preferably at most about 8.0% by weight, more preferably at most about 5.0% by weight, and especially preferably at most about 2.0% by weight.

[0123] The content of free phenol in the multi-component polyurethane foam composition is preferably at most about 10.0% by weight, preferably at most about 8.0% by weight, more preferably at most about 4.0% by weight, especially preferably at most about 2% by weight, most preferably at most about 1.5% by weight.

[0124] In a preferred embodiment, the content of free saligenin (o-hydroxybenzyl alcohol) in the multicomponent polyurethane foam composition is e.g. about 2.0 to about 30.0% by weight, preferably about 3.0 to about 26.0% by weight, and / or the content of free hydroxybenzyl alcohol is e.g. about 2.5 to about 40.0% by weight, preferably about 3.5 to about 30.0% by weight, each based on the weight of the phenolic resin of the benzyl ether type.

[0125] In a preferred embodiment, the content of free saligenin (o-hydroxybenzyl alcohol) in the multicomponent polyurethane foam composition is e.g. about 1.0 to about 21.0% by weight, preferably about 2.0 to about 18.0% by weight, and / or the content of free hydroxybenzyl alcohol is e.g. about 2.0 to about 30.0% by weight, preferably about 2.5 to about 28.0% by weight, each based on the first component.In a preferred embodiment, the content of free saligenin is e.g. about 0.20 to about 15.0% by weight or about 0.50 to about 10.0% by weight or about 1.0 to about 8.0% by weight and / or the content of free hydroxybenzyl alcohol is e.g. about 0.30 to about 20% by weight or about 0.60 to about 15.0% by weight or about 1.50 to about 10.0% by weight, each based on the multicomponent polyurethane foam composition.

[0126] The phenolic resins of the benzyl ether type can contain the required content of free hydroxybenzyl alcohol, in particular free saligenin, either by control during or after the formation reaction of the phenolic resin of the benzyl ether type, or by the addition of hydroxybenzyl alcohol, in particular saligenin, before, after or during the formation of the phenolic resin, in particular after the formation of the phenolic resin, by adding it to the first component or as a further component to the multi-component polyurethane foam composition. In the present composition, when reference is made to the amount of free hydroxybenzyl alcohol or free saligenin "in the first component", this amount also includes the free hydroxybenzyl alcohol or the free saligenin which is added as a further component to the multi-component polyurethane foam composition. In other words, the added hydroxybenzyl alcohol or the added saligenin is attributed to the first component.

[0127] It is also possible to control the ratio of free phenol to free hydroxybenzyl alcohol, in particular to saligenin, in the phenolic resin of the benzyl ether type by subsequently removing the free phenol (or preferably the free phenol) from the phenolic resin of the benzyl ether type, e.g. by steam distillation, azeotropic distillation or leaching with water according to DIN 53704. If desired, hydroxybenzyl alcohol, especially saligenin, can also be added after this step. The phenoksaligenin ratio is preferably adjusted by controlling the benzyl ether resin synthesis.

[0128] If other phenolic basic bodies are used in addition to phenol, these may also be present in small quantities based on the benzyl ether resin monomer. It is possible, for example, that the multicomponent polyurethane foam composition includes free cresol and / or cardanol and / or cardol or other monomers in addition to free phenol.

[0129] Due to the reaction, the phenolic resin of the benzyl ether type still contains water. This water can interfere with the hardening process to polyurethane and promotes polyurea formation. Water can also be added separately to increase the foam volume. The water content of the first component is preferably 30% by weight or less, preferably 25% by weight or less, and especially preferably 20% by weight or less. In a preferred embodiment, the water content of the first component is 0.02 to 15% by weight, more preferably 0.03 to 12% by weight, and especially preferably 0.05 to10% by weight. If the multi-component polyurethane foam composition comprises the third component, the water content of the first component is preferably 0.02 to 1.5% by weight, more preferably 0.03 to 1.2% by weight, and especially preferably 0.05 to 1.0% by weight. The water content can be quantified by Karl Fischer titration. By adding water or an optional desiccant (e.g. zeolites / phyllosilicates or other molecular sieves or ortho-formic acid esters), the free water content can be adjusted.

[0130] Due to the reaction, the phenolic resin of the benzyl ether type optionally still contains free alcohol from, for example, R2. This content of free alcohol should preferably be low. The content of free alcohol, based on the phenolic resin of the benzyl ether type, is preferably a maximum of about 8.0% by weight, preferably a maximum of about 6.0% by weight and especially preferably a maximum of about 5% by weight. The content of free alcohol can, for example, can be determined by gas chromatography (injector temperature 250 °C, Agilent 7890A, capillary column HP5MS, l=50 m, d=0.2 mm, 0.3 pm coating, temperature ramp T=50 °C - 325 °C).

[0131] The content of free formaldehyde, based on the weight of the phenolic resin of the benzyl ether type, is preferably at most about 0.9% by weight, preferably at most about 0.7% by weight, more preferably at most about 0.5% by weight, and especially preferably at most about 0.3% by weight (KCN-method, DIN EN ISO 11402). The content can be kept in this range by controlling the reaction of the benzyl ether resin. However, it is also possible to subsequently reduce the free formaldehyde content by means of a suitable formaldehyde scavenger in the first component. CH-acid compounds such as malonic acid, malonic acid esters, acetoacetates (with different alkyl or aryl groups, e.g. ethyl acetoacetate), but also amino functional compounds such as urea, ethylene urea, monoethanolamine, aminosilanes or certain amino acids have been found to be suitable formaldehyde scavengers.

[0132] The weight average of the molar mass (Mw) (determined by gel permeation chromatography: HPLC Agilent 1100, Rl Detector, PSS SDV pre-column 5 pm, PSS SDV column 5 pm 1000 A, PSS SDV column 5 pm 100 A, flux THF, column temperature 35 °C, calibration against PSS polystyrene ReadyCal-Kit low (Mp 266-67500 Da, internal standard PSS polystyrene ReadyCal-Kit low (Mp 266-67500 Da)), of the phenolic resin of the benzyl ether type, without monomeric phenol / o-cresol and without monomeric condensation products is preferably from about 230 to about 4000 g / mol, more preferably from about 350 to about 3000 g / mol and especially preferably from about 400 to about 2000 g / mol.The OHN (OH number, determined according to DIN 53240) of the phenolic resin of the benzyl ether type, which is preferably from about 400 to about 900 mg KOH / g, more preferably from about 420 to about 850 mg KOH / g and especially preferably from about 450 to about 750 mg KOH / g, can serve as a further characterization.

[0133] Optionally, polyols can be added to the first component.

[0134] Polyols are divided into polymeric polyols and non-polymeric polyols.

[0135] The first component optionally comprises one or more polyols that are different from the one or more phenolic resins of the benzyl ether type and typically comprise at least two primary and / or secondary hydroxyl groups.

[0136] The polymeric polyols are not particularly limited and can be selected from polyether polyols, polyester polyols, polycarbonate polyols, polylactides, hydroxyfunctional polybutadienes, acrylate polyols, polytetramethylene glycols, polysiloxane polyols, novolaks and combinations thereof. The polyols are preferably selected from polyether polyols, polyester polyols, polycarbonate polyols and combinations thereof. Polyether polyols and polyester polyols are especially preferred.

[0137] Polymeric polyols are composed of at least 4 monomer units (3+1 rule). The weight average molecular weight of the polymeric polyols is preferably from about 500 to about 10,000 Da, more preferably from about 750 to about 9000 Da, especially preferably from about 1000 to about 5000 Da, even more preferably from about 1500 to about 4500 Da. The weight average molecular weight can be determined by gel permeation chromatography (see above).

[0138]

[0139] Polyether polyols such as e.g. hydroxyfunctional polyethers that can be obtained by alkoxylation of multifunctional alcohols (such as glycerol, glycols, trimethylolpropane, sorbitol, sucrose or pentaerythritol) with alkylene oxide (such as ethylene oxide (EO), propylene oxide (PO) or butylene oxide (BO)) under anhydrous alkaline conditions (such as KOH) are suitable as polymeric polyols. Amino compounds, such as ethylenediamine and triethanolamine, or mixtures thereof can also serve as starter molecules. The molecular weight can be influenced by theconcentration of alkalis (e.g. KOH). Water can also be used as a starter molecule, so that e.g. polyethylene glycols or polypropylene glycols are obtained. The weight average molecular weight is e.g. from about 500 to about 10,000 Da, preferably from about 750 to about 9000 Da, more preferably from about 1000 to about 5000 Da, especially preferably from about 1500 to about 4500 Da.

[0140] By varying the starter molecule and the alkoxylation components, numerous compounds can be obtained. For example, homopolymers can be formed by using only one alkoxylating agent. Mixtures of EO and / or PO and / or BO result in statistically distributed copolymers. Block copolymers are obtained by adding a single alkoxylating agent at different times. In addition to anionic polymerization using KOH, the use of DMC catalysts is possible as well.

[0141] The polyether polyols can comprise about 1.5 to about 8 primary and / or secondary hydroxyl groups, preferably about 2 to about 8 primary and / or secondary hydroxyl groups per molecule.

[0142] The OHN (OH number) (mg KOH / g) can, for example, be in the range of about 30 to about 800, preferably about 60 to about 750 and more preferably from about 100 to about 700.

[0143]

[0144] Suitable polyester polyols can be prepared by the esterification of polyvalent carboxylic acids (e.g. phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, sebacic acid, fumaric acid, hexahydrophthalic acid or tetrahydrophthalic acid) or their anhydrides with polyvalent alcohols, the ring opening of cyclic esters such as lactones or cyclic carbonates, or from the transesterification of e.g. dimethyl esters of dicarboxylic acids with polyvalent alcohols. In some cases, the reaction is autocatalytic, or metal catalysts or organic sulfonic acids are used as catalysts.

[0145] The polyester polyols have at least two OH groups so that a network can form. Preferably, the average number of OH groups per polyester polyol molecule is about 2.1 to about 3.5. The remaining amount of residual acid (calculated as acid value AV in mg KOH / g) should be kept low, as it can lead to undesirable bubble formation with NCO groups. It is desirable to aim for an AV (determined according to EN ISO 2114) of at most about 2.0, preferably at most about 1.5.The weight average molecular weight is e.g. from about 500 to about 10,000 Da, preferably from about 750 to about 9000 Da, more preferably from about 1000 to about 5000 Da, especially preferably from about 1500 to about 4500 Da.

[0146]

[0147] Polycarbonate polyols are also suitable as polymeric polyols. They can be prepared from polyols and dialkyl, cycloalkyl or diaryl carbonates in the presence of suitable Sn and Ti compounds or DMC catalysts and elevated temperatures in the range of 200 °C. The molar ratio of the carbonate and polyol components used determines the resulting molar mass distribution of the polycarbonate polyol. Common carbonate compounds are diphenyl carbonate, trimethylene carbonate, neopentyl glycol carbonate, 2,2,4-trimethyl-1,3-pentanediol carbonate, 2,2-dimethyl-1,3-butanediol carbonate, 1,3-butanediol carbonate, 2-methyl-1,3-propanediol carbonate, 2,4-pentanediol carbonate, 2-methylbutane-1,3-diol carbonate, TMP-monoallyl ether carbonate and pentaerythritol diallyl ether carbonate. Classic polyols for the preparation of polycarbonate polyols are, for example, aliphatic or cycloaliphatic dihydroxy compounds such as diethylene glycol, triethylene glycol, oligoethylene glycol, thiodiglycol, the di- or polyglycols prepared from 1,2-propylene oxide, propylene glycols, di-, tri- and tetrabutylene glycol, 1,5-pentanediol, 1,6-hexanediol, di-, tri- and tetrahexylene etherglycol, 1,8-octanediol, neopentyl glycol, 2-ethyl-1 ,6-hexanediol, 3-methyl-1,5-pentanediol-, 1,4-cyclohexanediol, 1,3-cyclohexanediol, trimethylolpropane, trimethylolethane, glycerol, as well as their reaction products with ethylene and propylene oxide or aromatic diols such as p-xylylene glycol. An OH functionalization of the final polycarbonate polyol is provided by an excess of polyol.

[0148] The weight average molecular weight is e.g. from about 500 to about 10,000 Da, preferably from about 750 to about 9000 Da, more preferably from about 1000 to about 5000 Da, especially preferably from about 1500 to about 4500 Da.

[0149] Other

[0150]

[0151] Furthermore, polylactides, hydroxyfunctional polybutadienes, acrylate polyols, polytetramethylenes, glycols, polysiloxane polyols and urea resins can be used as polymeric polyols in the first component. The compounds mentioned above typically comprise 2 to 8 aliphatic hydroxyl groups.

[0152] Mixtures of different polymeric polyols can of course be used as well.Non-polymeric hydroxy-functional natural or ring-opened epoxidation products of triglycerides such as castor oil can be used. They can be added if necessary to achieve desired properties. They comprise at least 2 to 8 hydroxyl groups.

[0153] For the characterization and preparation of the polyol classes mentioned, reference is made to the book "Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition" Volume 1 by Mihail lonescu.

[0154] The quantities of the optional polymeric polyols used are not particularly limited. The quantities of the optional inert and optional reactive solvents, additives and polyols, together with the benzyl ether type phenolic resin explained above, make up a first component.

[0155] The polymeric polyols are preferably comprised in the first component in an amount of about 0 to about 95% by weight, more preferably from about 2 to about 90% by weight and especially preferably from about 5 to about 80% by weight. The first component preferably comprises from about 2 to about 100% by weight of one or more phenolic resins of the benzyl ether type, more preferably from about 5 to about 95% by weight, especially preferably from about 8 to about 92% by weight. The first component may also consist of only one or more phenolic resins of the benzyl ether type and optionally added hydroxybenzyl alcohol or saligenin. Optionally, the first component can still comprise inert and / or reactive solvents in quantities ranging from 0 to about 50% by weight, preferably from about 1 to about 45% by weight and especially preferably from about 2 to about 40% by weight. It is also possible to mix several inert and / or reactive solvents, polyols or phenolic resins of the benzyl ether type from each of the above-mentioned substance classes.

[0156] Second component

[0157] The second component comprises an isocyanate formulation consisting of one or more isocyanate compounds, where at least one isocyanate compound comprises at least 2 isocyanate groups per molecule.

[0158] The second component preferably does not comprise a phenolic resin of the benzyl ether type or polyol, monomeric phenol, cresol, cardanol or cardol and no free saligenin / homosaligenin, as they tend to react prematurely with the isocyanate compound. Preferably, the second component is essentially free of water. In particular, the second component preferably comprises less than 0.2%by weight of water, especially less than 0.1% by weight, more preferably less than 0.05% by weight, and especially preferably less than 0.025% by weight.

[0159] Isocyanate formulation

[0160] The isocyanate formulation consists of one or more isocyanate compounds and comprises one or more isocyanate compounds with at least 2 isocyanate groups per molecule.

[0161] The isocyanate compounds with at least 2 isocyanate groups per molecule can be monomeric, oligomeric or polymeric and have the general formula R(NCO)Z, where R is a polyvalent organic group that has an aromatic, aliphatic, cycloaliphatic or araliphatic group and z is an integer of at least 2 (e.g. 2 to 4). Examples include ethylene diisocyanate, 1,4-butylene diisocyanate, 1,5-pentane diisocyanate, 1 ,6-hexamethylene diisocyanate, 1,12-decane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate and mixtures of these isomers, isophorone diisocyanate, 2,4- and 2,6-hexane hydrotoluylene diisocyanate and mixtures of these isomers, 2,2,4- and / or2,4,4-Trimethylhexamethylene diisocyanate, bis(4,4',2,4' and 2,2'-isocyanatocyclohexyl)methane or mixtures of these isomers, 1,3-diisocyanato-o-xylene and mixtures of other xylene isomers, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate (TDI), monomeric MDI such as 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane isocyanate, 4,4'-diphenylmethane diisocyanate, oligomeric MDI, which has at least three aromatic nuclei, 1,5-naphthalene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, 3,3'-dimethyldiphenylmethane-4-4'-diisocyanate, triisocyanates, such as 4,4,4'"-triphenylmethane triisocyanate and 2,4,6-toluene-triisocyanate, tetraisocyanates, such as 4,4'-dimethyl-2,2'-5,5'-diphenylmethanetetraisocyanate as well as 1,3-and / or 1,4-bis-(2-isocyanato-prop-2yl-)-benzene (TMXDI) and 1,3-bis-(isocyanatomethyl)benzene (XDI).

[0162] The NCO content of the polyisocyanate used (weight of the NCO group based on the weight of the isocyanate molecule) is preferably at least about 17% by weight, more preferably at least about 27% by weight and especially preferably at least about 30% by weight. The viscosity (25 °C, according to DIN 53019-1) of the isocyanate should be at most about 3000 mPa s, preferably at most about 2500 mPa s and especially preferably at most about 1500 mPa s.

[0163] Depending on the desired properties, mixtures of isocyanates can also be used.The isocyanates can also be derivatized by reacting divalent isocyanates in such a way that some of their isocyanate groups are derivatized into biuret, allophanate, uretdione, isocyanurate, carbodiimide, urethonimine groups. Dimerization products exhibiting uretdione groups, e.g. of monomeric or oligomeric MDI or TDI, are of interest. However, such derivatized isocyanates are preferably used only as a component in addition to the above-mentioned non-derivatized isocyanates.

[0164]

[0165] termination

[0166] In addition to monomeric and polymeric polyisocyanates, isocyanate-terminated prepolymers can also be used. For example, such prepolymers are obtained by reacting OH-, NH-, NH2- and SH-containing polymers or monomers with an excess of diisocyanate. These prepolymers are characterized by excellent compatibility with other isocyanates or other reaction components and can also increase the degree of crosslinking of the isocyanate component. As a result, a robust and homogeneous polyurethane network is formed. These prepolymers can be prepared, for example, from monomers of components containing HO, HN, H2N and / or HS, such as castor oil, as well as from polymers containing HO, HN, H2N and / or HS by reaction with polyisocyanates. The following types of isocyanate termination, e.g. aliphatic and / or cycloaliphatic and / or aromatic or mixtures thereof are conceivable. Partial isocyanate terminations are also conceivable. The amount of isocyanate-terminated prepolymers, for example, can be up to 100%. Mixtures of different prepolymers with isocyanate termination, and with other isocyanate compounds or derivatizations are possible.

[0167] Furthermore, blocked isocyanates and / or monoisocyanates can also be comprised by the isocyanate formulation, whereby the amount, as a rule, should not exceed about 10% by weight based on the weight of the isocyanate formulation.

[0168] The ratio of the isocyanate-reactive groups (i.e. the sum of the HO, H2N, HN and HS groups) to isocyanate groups in the multi-component polyurethane foam composition is usually selected such that the molar ratio of isocyanate-reactive groups to isocyanate groups is from about 1 : 1.2 to about 1 : 4.5, preferably about 1 : 1.4 to about 1 : 4, more preferably about 1 : 1.5 to about 1 : 3.7.

[0169] The weight ratio of the first to the second component in the multi-component polyurethane foam composition is usually selected to be from about 1 : 1.2 to about 1 : 5, preferably about 1 : 1.4 to about 1 : 4.5, more preferably about 1 : 1.5 to about 1 : 4.Preferably, the multi-component polyurethane foam composition comprises, based on the total weight of the multi-component polyurethane foam composition:

[0170] • about 8 to about 70% by weight, in particular about 10 to about 62% by weight, of phenolic resin of the benzyl ether type; and / or

[0171] • about 13 to about 90% by weight, in particular about 17 to about 80% by weight, of isocyanate formulation.

[0172] The second component preferably comprises isocyanate formulation in an amount of from about 50% by weight to about 100% by weight, more preferably from about 60% by weight to about 100% by weight. Optionally, the second component can comprise inert and / or reactive solvents in amounts of from 0% by weight to about 50% by weight, preferably from about 0% by weight to about 40% by weight and especially preferably from about 0% by weight to about 30% by weight. It is possible to mix several inert and / or reactive solvents or isocyanates from each of the above-mentioned substance classes.

[0173] Solvents

[0174] Both the first and second components can comprise solvents. This influences the subsequent properties of the hardened multi-component polyurethane foam composition and, for example, the viscosities of the two components.

[0175] Inert solvents

[0176] The solvents can be inert solvents. Inert solvents are solvents that cannot be incorporated directly into the polyurethane network, i.e. they are free of hydroxyl, mercaptan, epoxy, amino, and isocyanate groups. Polar and / or non-polar solvents or mixtures thereof are suitable solvents. Suitable solvents are, for example, the aromatic solvents known as solvent naphtha. Starting from benzene, alkyl and / or alkenyl groups are substituted independently of each other on the aromatic ring, which have a chain length of C1 to C30, preferably from C1 to C20 and especially preferably from C1 to C16. Independently of each other, one to six ring hydrogen atoms of the benzene can be substituted with an alkyl and / or alkenyl group, preferably 1 to 4, and especially preferably 1 to 3 ring hydrogen atoms are substituted. Notwithstanding the above, the alkyl or alkenyl chain can be straight-chain or branched.

[0177] (Halogen)hydrocarbon-containing blowing agents are not inert solvents.Furthermore, oxygen-rich organic solvents can be used. Aliphatic, aromatic, or cycloaliphatic dicarboxylic acid esters, glycol ether esters, glycol diesters, glycol diethers, cyclic ketones, cyclic esters (lactones), cyclic carbonates, acetals, hemiacetals, and silica esters are particularly suitable.

[0178] For example, fatty acid esters with a C-chain in the fatty acid from C6 to C22 and a C-chain in the esterified alcohol from C1 to C18 such as fatty acid methyl ester, ethylhexyl laurate, oleic acid butyl ester or isopropyl ester of various fatty acids are suitable. However, dimer fatty acid esters, Guerbet alcohol esters and triglycerides can also be considered.

[0179] Preferred non-limiting solvents are e.g. propylene carbonate, dioctyl adipate, dimethyl ester of dicarboxylic acids. These solvents are inert solvents that do not negatively affect foam development and foam structure and are compatible in the hardened foam structure and do not migrate to the surface.

[0180] Different classes of inert solvents can be mixed with each other and in the respective component of the multi-component polyurethane foam composition.

[0181] Based on the multi-component-polyurethane foam composition, 0 to about 40% by weight of inert solvents, preferably 0 to about 30% by weight, and especially preferably 0 to about 25% by weight of inert solvents can be included. In one embodiment, the multi-component polyurethane foam composition comprises inert solvents.

[0182] If an inert solvent is used in the first component, 0 to about 50% by weight of inert solvents, preferably about 1 to about 45% by weight, and especially preferably about 2 to about 40% by weight of inert solvent, based on the first component, can be used. In one embodiment, the first component comprises an inert solvent.

[0183] Reactive solvents

[0184] In addition to the benzyl ether resin and the optional polymeric polyol and optional inert solvent, the first component can optionally comprise a reactive solvent. A reactive solvent is a solvent that is incorporated into the polyurethane network, reduces the viscosity and / or possibly improves the reaction flow, i.e. they contain hydroxyl and / or mercaptane and / or amino groups.Suitable reactive solvents are e.g. diacetone alcohol, glycerol, polyglycerol, partially esterified glycerol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, methylpropanediol, free cardanol, free cardol, organic carbonates or castor oil fatty acid esters. Monoalcohols with a hydroxyl group and a saturated or unsaturated, straight-chain or branched chain of about 2 to about 36 carbon atoms, such as ethanol, ethylhexanol, oleyl alcohol, Guerbet alcohols or dimer diols, are also suitable.

[0185] Different classes of inert or reactive solvents can be mixed with each other and in the respective component of the multi-component-polyurethane foam composition.

[0186] Reactive solvents that do not negatively affect foam development and foam structure and are compatible in the hardened foam structure are preferred.

[0187] If a reactive solvent is used in the first component, 0 to about 50% by weight of reactive solvents, preferably about 1 to about 45% by weight, and especially preferably about 2 to about 40% by weight of reactive solvents, based on the first component, can be used. In one embodiment, the first component comprises a reactive solvent.

[0188] Silicone surfactants

[0189] Silicone surfactants can preferably be added to improve the foam structure. Silicone surfactants are ethoxylated or propoxylated, straight-chain or cyclic polydimethylsiloxanes. They facilitate the mixing of the polyol component, the isocyanate component, and the blowing agent and form a fine-cell foam structure. Suitable silicone surfactants are available, for example, under the trade name Niax from Momentive or under the trade name of the Tegostab B Series from Evonik. The silicone surfactants can be added to the first or second component or when mixing the first, second, and possible additional components.

[0190] The content of silicone surfactants is preferably about 0.01 to 1.0% by weight, more preferably about 0.02 to 0.50% by weight, especially preferably about 0.03 to 0.30% by weight, and particularly preferably about 0.05 to 0.20% by weight, based on the multi-component polyurethane foam composition.Third

[0191] Optionally, the multi-component polyurethane foam composition can comprise a third component, which includes a (halogen)hydrocarbon-containing blowing agent and / or water. If the multicomponent polyurethane foam composition does not comprise a third component, then the first component comprises at least 0.95% by weight, preferably at least 1.0% by weight, more preferably at least 2.0% by weight, especially preferably at least 3.0% by weight, particularly preferably at least 4.0% by weight of water. The third component can also be added if the first component has a higher water content.

[0192]

[0193] Blowing agents are used to increase the volume of the foam and the formation of pores. Blowing agents are divided into CO2 produced in situ, which is formed from water and the isocyanate component, and (halogen)hydrocarbon-containing blowing agents. Water, which produces CO2 in situ, and (halogen)hydrocarbon-containing blowing agents can also be used together as blowing agents. If the multi-component polyurethane foam composition comprises a (halogen)hydrocarbon-containing blowing agent, no addition of water is needed.

[0194] The water can be comprised in the first component and / or in a third component of the multicomponent polyurethane foam composition. Depending on the desired degree of foaming or foam volume, water is used in a total amount of about 0.3% by weight to about 10% by weight, preferably about 0.5% by weight to about 7% by weight, especially preferably about 1.0% by weight to about 6% by weight, based on the multi-component polyurethane foam composition. The total amount of water is the sum of the water contained in the first component and in the third component of the multi-component polyurethane foam composition.

[0195] Preferably, distilled or demineralized water is used since impurities can interfere with the foam reaction.

[0196] The (halogen)hydrocarbon-containing blowing agent can be comprised in the first or second component and / or in a third component of the multi-component polyurethane foam composition. Preferably, the (halogen)hydrocarbon-containing blowing agent is comprised in the third component. Depending on the desired degree of foaming, the amount of (halogen)hydrocarbon-containing blowing agents ranges from about 0.5% by weight to about 25% by weight, preferably about 1% by weight to about 20% by weight, and especially preferable from about 2% by weightto about 10% by weight, based on the multi-component polyurethane foam composition. If water is added in addition to the (halogen)hydrocarbon-containing blowing agent, the total amount of water is from about 0.2% by weight to about 10% by weight, preferably about 0.3% by weight to about 7% by weight, especially preferably about 0.5% by weight to about 5% by weight, based on the multi-component polyurethane foam composition.

[0197] (Halogen)hydrocarbon-containing blowing agents evaporate quickly at room temperature alone or in the exothermic polyaddition reaction. (Halogen)hydrocarbon-containing blowing agents contain hydrocarbons which may be halogenated. Examples of hydrocarbons that may be halogenated include non-halogenated hydrocarbons, chlorinated hydrocarbons, fluorocarbons and chlorofluorocarbons, and mixtures thereof. "Hydrocarbons" refers to organic compounds consisting exclusively of the elements carbon (C) and hydrogen (H). "Chlorinated hydrocarbons" refers to organic compounds consisting exclusively of the elements carbon (C), hydrogen (H) and chlorine (Cl). "Fluorocarbons" refers to organic compounds consisting exclusively of the elements carbon (C), hydrogen (H) and fluorine (F). "Chlorofluorocarbons" refers to organic compounds consisting exclusively of the elements carbon (C), hydrogen (H), fluorine (F) and chlorine (Cl). Hydrofluorocarbons are preferably hydrofluoroolefins (HFO), i.e., fluorinated unsaturated hydrocarbons. Chlorofluorocarbons are preferably chlorinated hydrofluoroolefins (HCFO). Mixtures of several (halogen)hydrocarbon-containing blowing agents can also be used.

[0198] Usually, low-boiling (halogen)hydrocarbons are used as blowing agents. Low-boiling (halogen)hydrocarbons are preferably (halogen)hydrocarbons with a boiling point under normal pressure (1013 mbar) below 130 °C, preferably below 100 °C, more preferably below 70 °C.

[0199] Low-boiling hydrocarbons include, for example, n-pentane, iso-pentane, cyclopentane, or hexane. Low-boiling chlorinated hydrocarbons include, for example, chloropropane. Examples of low-boiling HFO include pentafluoropropene, tetrafluoropropene, 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene (HFO-1234ze), trifluoropropene, tetrafluorobutene, pentafluorobutene, hexafluorobutene, heptafluorobutene, heptafluoropentene, octafluoropentene, and nonafluoropentene (Z)-1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzzZ, available from Chemours as Opteon™ 1100 and Opteon™ 1150). Examples of chlorinated hydrofluoroolefins are 1-chloro-3,3,3-trifluoropropene (HCFO1233zd), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, E and / or Z isomer), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1,2-dichloro-1,2-difluoroethene (E and / or Z isomer), 3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (E and / or Z isomer), 2-chloro-1,1,3,4,4,4-heptafluoro-2-butene (E and / or Z isomer).Preferably, blowing agents containing hydrocarbons or HFO are used.

[0200] additives

[0201] The multi-component-polyurethane foam composition can comprise additives if needed. The optional additives can be present in the first component and / or in the second component, or they can be added separately from the first and second components.

[0202] Optionally, other common additives such as other wetting aids (e.g. surfactants, especially silicone surfactants), flow control agents (e.g. silicone-based additives such as polysiloxanes), processing time regulators (acids and bases), or water-repellant agents (waxes), foam stabilizers or yellowing agents can be used to improve processing properties. It is also possible to add pigments and / or color pastes for color identification.

[0203] Common reaction retardants can be added to the first and / or second component of the multicomponent polyurethane foam composition, such as phosphorus oxychloride, phenylphosphonic acid dichloride, acid chlorides, salicylic acid, sulfonic acids, carboxylic acids or phosphoric acid half esters to extend the pot life.

[0204] To increase adhesion to inorganic, organic, or hybrid surfaces, it can be advantageous to use e.g. silane compounds as adhesion promoters in the multi-component polyurethane foam composition. All common silanes that can be dissolved in the composition are suitable here. Gamma-propyl or alpha-silanes, which comprise one or two silyl groups, with at least one organic functional group, such as epoxy, isocyanate, vinyl, primary or secondary amino, ureido, mercapto or methacrylic groups, as well as acidic silane hydrolysates of these silanes, can be mentioned in this connection.

[0205] An organic and / or inorganic flame retardant can be added to the multi-component polyurethane foam composition to improve flame retardancy. These can, for example, be chlorine, bromine and / or phosphorus-containing, intumescent compounds or inorganic solids. Common flame retardants are e.g. trichloropropyl phosphate, decabromodiphenyl ether, tetrabromobisphenol A, bis(pentabromophenyl) ethane, hexabromocyclododecane, resorcinol-bis-diphenyl-phosphate, melamine cyanurate. They can be added to the multi-component polyurethane foam composition in an amount of up to 15% by weight.It is preferred that the multi-component polyurethane foam composition does not contain a compound with epoxy groups.

[0206]

[0207] Catalysts known from the polyurethane coating can be used to harden the multi-component polyurethane foam composition. The catalyst can either be present in the first component, mixed with the first component before mixing with the second component, or added to the first and second components (and optionally additional components) during mixing. Amine catalysts and metal catalysts can be mentioned as examples, with amine catalysts being preferred. The amine catalysts can both be substances that are incorporated into the resin and those whose chemical structure does not allow this.

[0208] In principle, all amino-functional substances such as aliphatic, cycloaliphatic, heterocyclic and / or aromatic amines are suitable as amine catalysts. Primary, secondary and tertiary monoamines as well as polyamines with primary, secondary and tertiary amino groups can be used. Mixtures of the individual amines are also possible.

[0209] Non-limiting examples of liquid amine catalysts include triethanolamine, dimethylethanolamine, vinylimidazole, 2(-2-dimethylaminoethoxy)ethanol, 1,3-propanediamine, 3'-iminobis(N,N-dimethylpropylamine), tetramethylguanidine, N,N,N'-trimethylaminoethyl-ethanolamine, 4,4-phenylpropylpyridine, 1 ,3,5-tris-(3-(dimethylamino)propyl)-hexahydro-s-triazine, 2,2'-Dimorpholinodiethyl ether, N-methylmorpholine, N-ethylmorpholine, benzyl dimethylamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl dipropylenetriamine, bis-(2-methylaminoethyl)ether, diazabicyclooctane, and N,N-diisopropylamine. A general definition can be derived, for example, from the following structure, in which only the catalytically effective centers are shown:

[0210]

[0211] wherein R1, R2, R3, R1*, and R2* are independently selected from H, C6-C12 aryl, C1-C18 alkyl, C1-C18 alkylene-C6-C12 aryl, C1-C8 alkylene-O-C1-C8 alkyl, C1-C8 alkylene-O-C1-C8 alkyl-OH, C2-C18 alkenyl, C1-C18 hydroxyalkyl, C2-C18 hydroxyalkenyl, C1-C18 aminoalkyl, C2-C18 aminoalkenyl, C6-C12 aminoaryl, C5-C18 cycloalkyl, C5-C18 cycloalkenyl, C1-C18 aminoalkyl alcohol, C1-C18 alkylaminoalkyl alcohol, C2-C18 aminoalkenyl alcohol and C6-C12 aminoarylalcohol. In another embodiment, R1and R2and / or R1* and R2* can be connected to form a ring that has 3 to 10 ring atoms, wherein the ring atoms (except the N of the amine) are selected from C, N, O and S. Preferred amine catalysts are compounds of the above structural formula, wherein R1, R2, R3, R1*, and R2* independently selected from H, C1-C18 alkyl, C1-C18 hydroxyalkyl, CICIS alkylene-C6-C12 aryl and C5-C18 cycloalkyl or compounds wherein R1and R2and / or R1* and R2* are connected to form a ring. Compounds wherein R1, R2, R3, R1*, and R2* are independently selected from H, C1-C18 alkyl, and C1-C18 hydroxyalkyl are especially preferred.

[0212] L is selected from C1-C12 alkylene, C1-C6 alkylene-O-C1-C6 alkylene, C1-C6 alkylene-NH-C1-C6 alkylene, C1-C6 alkylene-N(C1-C6 Alkyl)-C1-C6 alkylene, and -C(=NH)-. L is preferably selected from C1-C12 alkylene. Gaseous amines are amines that can be evaporated by flowing through and / or evaporating through a carrier gas (usually air or an inert gas). Depending on the boiling point and vapor pressure of the amine, this can take place from about +10 °C to about +120 °C. As a rule, the vaporizable amines have a boiling point of less than about 95 °C (1013 mbar). These include, for example, trimethylamine, triethylamine, dimethylethylamine, dimethylpropylamine and dimethylisopropylamine or mixtures thereof.

[0213] In a preferred embodiment, the amines used are N,N,N'-trimethylaminoethylethanolamine, dimethylethanolamine, dimethylisopropylamine, tetramethylguanidine, diazabicyclooctane, diazabicycloundecane or mixtures thereof.

[0214] Furthermore, blocked amines can be used. These have the advantage of a "switching temperature" and only start the reaction at a certain temperature. Formic acid, for example, can be used as a blocking agent.

[0215] Such blocked amines are known, for example, from WO 2011 / 095440 and include the commercially available products Toyocat DB 30, Toyocat DB 40, Toyocat DB 41, Toyocat DB 60 and Toyocat DB 70 from Tosoh Corporation, Tokyo, which in terms of technical application differ in the degree of their thermal latency.

[0216] Hardening can also be carried out exclusively with metal catalysts.

[0217] Organic or inorganic salts of the elements bismuth, iron and zinc are generally suitable as metal catalysts, preferably in combination with organic carboxylates. The following examples are suitable metal catalysts: zinc neodecanoate, iron(ll) chloride, iron(lll) chloride, zinc chloride, and bismuth octoate. Preferably, no tin-containing catalyst is used.For the targeted formation of polyisocyanurate structures, trimerization catalysts, usually potassium carboxylates, such as potassium acetate or potassium octoate, can be added.

[0218] In order to achieve certain hardening properties, two or more catalysts can also be mixed, whereby they can belong to different classes of compounds. Different hardening processes can also be combined. One or more catalysts can additionally be added to the first component and / or the second component and / or in the multi-component polyurethane foam composition to increase the activity, and those catalysts may belong to different classes of compounds.

[0219] Catalysts which are liquid or solid at the operating temperature can be mixed with solvents, e.g. to influence the reaction rate in this way. This can be done to convert amines which are solid at the operating temperature into a liquid state.

[0220] The exact amount of the catalyst depends on the type of catalyst and can be appropriately selected by the person skilled in the art. The amount of catalyst required for hardening depends on the reactivity of the multi-component polyurethane foam composition, the desired hardening time and the operating temperature. In the case of an amine catalyst, generally from about 0.0001% by weight to about 0.2% by weight are used, preferably from about 0.0002 to about 0.15% by weight and especially preferably from about 0.0003 to about 0.12% by weight, based on the total amount of multi-component polyurethane foam composition used.

[0221] If the reaction rate is not relevant, the multi-component polyurethane foam composition can also be applied and hardened without the addition of a catalyst.

[0222] Since the reaction between the phenolic resin of the benzyl ether type, the optional polyol, and the isocyanate compound progresses relatively fast, the hardening conditions are not critical. Hardening can, for example, take place in a temperature range of about -40 °C to about +130 °C and / or at a relative humidity of up to about 98%. The hardening of the multi-component polyurethane foam composition is also possible both under reduced and increased pressure loads.

[0223] Method for producing a

[0224]

[0225] foam

[0226] A polyurethane foam can be produced from the multi-component polyurethane foam composition. Optionally, the multi-component polyurethane foam composition can be used to coat a surface of a substrate.The first component, the second component and, if applicable, the third component of the multicomponent polyurethane foam composition as well as optional additives (which are not already present in the first, second or third component, including silicone surfactants and hardeners) are mixed. Preferably, all components except the second component are mixed and then the second component is mixed in. The mixture is then placed in a mold that houses the expanding foam or the mixture is applied to the surface of the substrate. A foam is formed upon mixing the components.

[0227] When the multi-component polyurethane foam composition comprises water, CO2 is produced in situ from water and the isocyanate upon mixing the components of the multi-component polyurethane foam composition. The CO2 forms bubbles within the reaction mixture, whereby a foam is formed.

[0228] In an embodiment, The multi-component polyurethane foam composition can comprise one or more (halogen)hydrocarbon-containing blowing agents. Upon mixing the components, the isocyanate reacts with the phenolic resin (and possibly with water, if present) to form polyurethane. The reaction is exothermic and generates heat. The heat of the reaction causes the (halogen)hydrocarbon blowing agent to vaporize. The vaporized blowing agent forms bubbles within the reaction mixture, whereby a foam is formed.

[0229] In either case, no separate blowing step is needed as the foam forms upon mixing the components of the multi-component polyurethane foam composition.

[0230] Homogeneous mixing can be carried out, for example, by means of a suitable mixing apparatus or manually. The time between mixing the first and second components (and possibly other components), the blowing agent and optional additives and the introduction into a mold or application to the substrate depends on the selection of the first and second components and, above all, their reactivity. It is generally from about 30 seconds to about 2 hours, preferably about 40 seconds to about 1.5 hours.

[0231] As mentioned above, blowing agents are divided into CO2 produced in situ, which is formed from water and the isocyanate component, and (halogen)hydrocarbon-containing blowing agents. The water can be included in the first component and / or added as part of the third component during the mixing process. Preferably, the water is first mixed with the first component before the second component is added.The substrate is not particularly limited. Examples of substrates include metals, ceramics, fabrics, nonwoven materials, wood, glass, artificial stone, natural stones, e.g. soil, rocks, granite, limestone, and plastic. In one embodiment, the substrate includes metals, fabrics, nonwoven materials, wood, glass, and plastic. In a preferred embodiment, the substrate includes metal.

[0232] The viscosity of the multi-component polyurethane foam composition is not particularly limited and can be in the range of about 50 mPa s to about 50 Pa s, preferably from about 60 mPa s to about 40 Pa s. Viscosity can be measured with a CAP-2000 rotational viscometer (measurement conditions: 25 °C, spindle and revolutions are selected such that the utilization is between about 40 and about 60%). This means that the viscosity of the first component and the second component of the multi-component polyurethane foam composition should preferably be in the specified ranges. Furthermore, it is preferred that the mixture of the first component and the second component of the multi-component polyurethane foam composition, optionally water, and the optional additives, without the addition of the (halogen)hydrocarbon-containing blowing agent, fall in the above-mentioned ranges immediately after the mixing process and before foaming. Depending on the reactivity of the components, the viscosity of the mixture is measured within about 5 minutes, preferably within about 1 minute after the mixing process.

[0233] After application or placement into a mold, the mixture can be hardened. Possible curing agents are mentioned above.

[0234] The hardened composition according to the present invention has a foam structure. The density of the hardened foamed composition (measured at 20 °C) is preferably at least about 10 kg / m3, more preferably at least about 20 kg / m3, and especially preferably at least about 30 kg / m3, and preferably at a maximum of about 75 kg / m3, more preferably at a maximum of about 70 kg / m3, especially preferably at a maximum of about 60 kg / m3. The density of the hardened foamed composition (measured at 20 °C) is preferably at least about 10 kg / m3to a maximum of about 75 kg / m3, more preferably at least about 20 kg / m3to a maximum of about 75 kg / m3, and especially preferably at least about 30 kg / m3to a maximum of about 60 kg / m3. Density can be measured by water displacement.

[0235] Use

[0236] The multi-component polyurethane foam composition according to the present invention can be used in a variety of applications, especially for sound insulation, heat insulation, or as rust protection. Examples of possible applications include cavity sealing (especially for motorvehicles), as an insulating foam in sandwich panels, for pipe insulation, in refrigerators, for house insulation, as spray insulation in mines or as impact sound insulation.

[0237] The multi-component polyurethane foam composition according to the present invention is also suitable as a surface coating. In particular, it can be used as a protective layer to protect substrates for example against mechanical influences and / or oxidation. In a particularly preferred embodiment, it can be used as a surface coating on metals, e.g. to protect them against corrosion.

[0238] In the above uses, the components of the multi-component polyurethane foam composition are mixed so that a polyurethane foam is formed.

[0239] The phenolic resins of the benzyl ether type described in the present application, wherein a) the phenolic resin comprises free phenol and free hydroxybenzyl alcohol, wherein at least about 1.2 parts by weight of free hydroxybenzyl alcohol per 1 part by weight of free phenol are comprised in the phenolic resin, and / or

[0240] b) the phenolic resin comprises free phenol and free saligenin (o-hydroxybenzyl alcohol), wherein at least about 1.1 parts by weight of free saligenin (o-hydroxybenzyl alcohol) per 1 part by weight of free phenol are comprised in the phenolic resin,

[0241] can be used for producing a polyurethane foam. The embodiments described above in the section "Phenolic resin of the benzyl ether type" also apply to the present use of the phenolic resin of the benzyl ether type for producing a polyurethane foam.

[0242] EXAMPLES

[0243] Chemicals used

[0244] Phenol 99 % Supplier Sigma Aldrich

[0245] o-Cresol 99 % Supplier Sigma Aldrich

[0246] Paraformaldehyde 91 % Supplier Sigma Aldrich

[0247] n-Butanol Supplier Sigma Aldrich

[0248] Lupranate M 20 S Supplier BASF Polyurethans GmbH

[0249] Technical mixture of MDI and polymeric MDI Dimethylethanolamine Supplier Sigma Aldrich

[0250] Niax Silicon L 580 Supplier Momentive, silicone surfactant

[0251] n-Pentane Supplier Sigma Aldrich

[0252] Propylene carbonate tech. Supplier BASF SESaligenin Supplier Sigma Aldrich

[0253] (2-Hydroxybenzyl alcohol)

[0254] Zink acetate di hydrate Supplier Sigma Aldrich

[0255] Palmer 1500-1 Supplier Palmer International, mixture of cardanol and cardol

[0256] Preparation of the phenolic resins of the benzyl ether type

[0257] Comparative Phenolic Resin 1

[0258] A benzyl ether resin was prepared in accordance with Example 21 of US 04448951 A1. Molar weight (Mn) 259 g / mol, molar weight (Mw) 489 g / mol,

[0259] Free phenol content: 13.1% by weight

[0260] Free saligenin content: 13.1% by weight

[0261] Ratio free phenol : free saligenin = 1 : 1

[0262] Free water content: 0.16 %

[0263] Free n-butanol content: 4.9%

[0264] Comparative Phenolic Resin 2

[0265] A benzyl ether resin was prepared in accordance with Example 1 of JP2006152218A. Molar weight (Mn) 220 g / mol, molar weight (Mw) 404 g / mol,

[0266] Free phenol content: 25.6% by weight

[0267] Free saligenin content: 6.1% by weight

[0268] Ratio free phenol : free saligenin = 1 : 0.21

[0269] Free water content: 0.20% by weight

[0270] Comparative Phenolic Resin 3

[0271] A benzyl ether resin was prepared in accordance with Example 2 of JP2006152218A. Molar weight (Mn) 209 g / mol, molar weight (Mw) 295 g / mol,

[0272] Free phenol content: 11.7% by weight

[0273] Free saligenin content: 0.2% by weight

[0274] Ratio free phenol : free saligenin = 1 : 0.015

[0275] Free water content: 0.15% by weightInventive Phenolic Resin 1

[0276] A phenolic resin was prepared in accordance with Example 21 of US 04448951 A1. However, the given mass of phenol was divided 1:1 by weight into phenol and o-cresol.

[0277] Molar weight (Mn) 395g / mol, molar weight (Mw) 810g / mol,

[0278] Free phenol content: 6.5% by weight

[0279] Free saligenin content: 7.6% by weight

[0280] Ratio free phenol : free saligenin = 1 : 1.17

[0281] Free water content: 0.18 %

[0282] Free n-butanol content: 3.9%

[0283] Inventive Phenolic Resin 2

[0284] A phenolic resin was prepared in accordance with Example 21 of US 04448951 A1. However, the given mass of phenol was divided 1:1 by weight into phenol and o-cresol. When 120 °C was reached under distillation, 4% by weight of Palmer 15001 was added.

[0285] Molar weight (Mn) 420 g / mol, molar weight (Mw) 936 g / mol,

[0286] Free phenol content: 5.8% by weight

[0287] Free saligenin content: 8.4% by weight

[0288] Ratio free phenol : free saligenin = 1 : 1.45

[0289] Free water content: 0.19 %

[0290] Free n-butanol content: 3.7%

[0291] Inventive Phenolic Resin 3

[0292] Benzyl ether resin (o-cresol / phenol / cardanol copolymer), characterized by the following analytical parameters:

[0293] Molar weight (Mn) 525 g / mol, molar weight (Mw) 1400 g / mol,

[0294] Free phenol content: 1.8% by weight

[0295] Free saligenin content: 3.8% by weight

[0296] Ratio free phenol : free saligenin = 1 : 2.1

[0297] Free water content: 0.11% by weight

[0298] Inventive Phenolic Resin 4 (synthesis example)

[0299] 648.4 g phenol (99%), 352.6 g paraformaldehyde (91%) and 0.6 g zinc acetate dihydrate were placed in a reaction vessel equipped with an agitator, reflux condenser and thermometer. While stirring, the temperature was raised evenly to 105 to 115 °C within 60 minutes and maintained until a refractive index (25 °C) of 1.5590 was reached. Then 50 g of cardanol was added, the cooler was switched to atmospheric distillation and the temperature was brought to 120 to 125 °Cwithin an hour. At this temperature, distillation was continued until a refractive index (25 °C) of 1.5940 was reached. Then a vacuum was applied and distillation was continued at a reduced pressure until a refractive index (25 °C) of approx. 1.6020 was reached. Subsequently, 8 parts by weight of n-butanol and 2 parts by weight of water were added for every 90 parts by weight of the resulting resin, and the mixture was kept at 100-112 °C for 60 minutes under reflux. Then, the unconverted butanol was largely removed under vacuum. The resin had a refractive index (25 °C) of about 1.5980.

[0300] Molar weight (Mn) 480 g / mol, molar weight (Mw) 1102 g / mol,

[0301] Free phenol content: 3.8% by weight

[0302] Free saligenin content: 6.7% by weight

[0303] Ratio free phenol : free saligenin = 1 : 1.76

[0304] Free water content: 0.17% by weight

[0305] Free n-butanol content: 2.6%

[0306] Preparation of the foam bodies

[0307] Step 1 :

[0308] Preparation of the phenolic resin solution (first component)

[0309] A homogeneous pre-solution of the phenolic resin of the benzyl ether resin type in the specified amount of propylene carbonate was prepared.

[0310] Step 2:

[0311] The first component was presented in a paper cup and the isocyanate component (second component) was homogeneously added while stirring with a toothed disc.

[0312] Step 3:

[0313] Subsequently, the other ingredients of the formulation were added one after the other in the order shown in Tables 1 to 3. (Unless otherwise stated, the quantities in the tables are in percent by weight (wt.%). After a minute of maximum stirring, 40 g of the obtained mass was filled into a round silicone mold measuring d=5 cm, h=5 cm. After 24 hours at room temperature, the foam was removed from the mold and the foam structure was visually assessed.

[0314] Assessment:

[0315] Pore size - a centric longitudinal section was used to assess the pore size at the cut surface. The smaller the pores, the more advantageous.

[0316] • : fine pores

[0317] o: coarse poresPore surface - the pore surface was assessed on the cut surface obtained by a longitudinal section through the center point. The rounder and more even (not burst or run into each other) the pores are, the more advantageous.

[0318] • : closed

[0319] o: mostly open

[0320] Foam height: Foam that rises above the height of the silicone mold (higher than 5 cm). The higher, the more advantageous.

[0321] Blowholes: Large cavities that are not pores and can form, for example, by a strong exothermic reaction in the center of the molded body. Blowholes are undesirable because the affected area is reject material.

[0322] Molded body (inside to outside): Assessment of the outside areas adjacent to the mold to the inner area. Mold contacts often appear as a smooth, non-foamed layer (similar to a cheese rind). If this is assessed as "homogeneous", both the inner areas and the outside contact (with the mold) are homogeneously foamed.

[0323] O: homogeneous

[0324] X: heterogenous

[0325] Homogeneity of the emulsion before hardening: Under stirring by means of a toothed disc, all the formulation components of the multi-component polyurethane foam composition were added and the obtained mixture / emulsion was visually assessed after the stirring process was completed. If slight drops or streaks were observed, it is described as heterogeneous.

[0326] O: homogeneous

[0327] X: heterogenousTable 1 : Formulations of the tested foams foamed with water

[0328] " " " "

[0329]

[0330] Table 2: Formulations of the tested foams foamed with water and n-pentane at different silicon surfactant contents

[0331]

[0332] Table 3: Formulations of the tested foams foamed with water and n-pentane at different water contents

[0333]

[0334] The test results prove that the phenolic resins according to the invention in the formulation shown herein show advantages in terms of pore size, pore surface, foam height, blowholes, and homogeneity of the molded bodies. Based on these properties, a higher compatibility with blowing agents can be derived. This also results in the observed more homogeneous mixture before hardening. The results also show that the amount of silicone surfactant can be significantly reduced to achieve the same properties as in the known prior art. In addition, the novel phenolic resins have an increased phenol to saligenin ratio.

Claims

New PCT applicationbased on DE 102024004417.5ASK Chemicals GmbHVossius Ref.: AJ1865 PCTCLAIMS1. A multi-component polyurethane foam composition comprising:(i) a first component, comprising one or more phenolic resins of the benzyl ether type, whereina) the first component comprises free phenol and free hydroxybenzyl alcohol, wherein at least about 1.2 parts by weight of free hydroxybenzyl alcohol per 1 part by weight of free phenol are comprised in the first component; and / orb) the first component comprises free phenol and free saligenin (o-hydroxybenzyl alcohol), wherein at least about 1.1 parts by weight of free saligenin (o-hydroxybenzyl alcohol) per 1 part by weight of free phenol are comprised in the first component;(ii) a second component, comprising an isocyanate formulation consisting of one or more isocyanate compounds, wherein at least one isocyanate compound has at least 2 isocyanate groups per molecule; and(iii) optionally, a third component, comprising one or more (halogen)hydrocarbon- containing blowing agents and / or water,wherein, if the multi-component polyurethane foam composition does not include a third component, then the first component comprises at least 0.95% by weight, preferably at least 1.0% by weight, and especially preferably at least 2.0% by weight of water.

2. The multi-component polyurethane foam composition according to claim 1, wherein the weight ratio of free phenol to free hydroxybenzyl alcohol in the first component is• 1 : 1.2 to 1 : 10,• preferably 1 : 1.2 to 1 : 8, and• more preferably 1 : 1.3 to 1 : 6, and• especially preferably 1 : 1.5 to 1 : 4,and / orwherein the weight ratio of free phenol to free saligenin in the first component is• 1 : 1.1 to 1 : 8,• preferably 1 : 1.1 to 1 : 6, and• more preferably 1 : 1.2 to 1 : 4,especially preferably 1 : 1.4 to 1 : 2.5.

3. The multi-component polyurethane foam composition according to claim 1 or 2, wherein the multi-component polyurethane foam composition comprises water in a total amount of about 0.3% by weight to about 10% by weight, preferably about 0.5% by weight to about 7% by weight, more preferably about 1.0% by weight to about 6% by weight, based on the multicomponent polyurethane foam composition.

4. The multi-component polyurethane foam composition according to any of claims 1 to 3, wherein the water content of the first component is 0.2 to 30% by weight, more preferably 0.4 to 25% by weight, and especially preferably 0.5 to 20% by weight.

5. The multi-component polyurethane foam composition according to any of claims 1 to 4, wherein the multi-component polyurethane foam composition comprises one or more (halogen)hydrocarbon-containing blowing agents in a total amount of about 0.5% by weight to about 25% by weight, preferably about 1% by weight to about 20% by weight, more preferably about 2% by weight to about 10% by weight, based on the multi-component polyurethane foam composition.

6. The multi-component polyurethane foam composition according to any of claims 1 to 5, wherein the (halogen)hydrocarbon-containing blowing agent is selected from n-pentane, isopentane, cyclopentane, hexane, chloropropane, and hydrofluoroolefins, or mixtures thereof.

7. The multi-component polyurethane foam composition according to any of claims 1 to 6, wherein the first component comprises at most about 12.0% by weight of free phenol, preferably at most about 8.0% by weight of free phenol, more preferably at most about 5.0% by weight, especially preferably at most about 2.0% by weight of free phenol, and / or wherein the multi-component polyurethane foam composition, based on the weight of the first component, comprises free saligenin (o-hydroxybenzyl alcohol) in an amount of about 1.0 to about 21.0% by weight, or about 2.0 to about 18.0% by weight, and / or free hydroxybenzyl alcohol in an amount of about 2.0 to about 30.0% by weight, preferably about 2.5 to about 28.0% by weight.

8. The multi-component polyurethane foam composition according to any of claims 1 to 7, wherein the multi-component polyurethane foam composition, based on the total weight of the multi-component polyurethane foam composition, comprises:• about 8 to about 70% by weight, preferably about 10 to about 62% by weight of phenolic resin of the benzyl ether type, and / or• about 13 to about 90% by weight, preferably about 17 to about 80% by weight of isocyanate formulation.

9. The multi-component polyurethane foam composition according to any of claims 1 to 8, wherein the weight ratio of the first to the second component ranges from about 1 : 1.2 to about 1 : 5, preferably about 1 : 1.4 to about 1 : 4.5, more preferably about 1 : 1.5 to about 1 : 4, and / orwherein the molar ratio of the isocyanate-reactive groups to the isocyanate groups ranges from about 1 : 1.2 to about 1 : 4.5, preferably about 1 : 1.4 to about 1 : 4, more preferably about 1 : 1.5 to about 1 : 3.7.

10. The multi-component polyurethane foam composition according to any of claims 1 to 9, wherein the density of the hardened foamed composition is at least about 10 kg / m3, preferably at least about 20 kg / m3and more preferably at least about 30 kg / m3, and is at most about 75 kg / m3, preferably at most about 70 kg / m3, more preferably at most about 60 kg / m3.

11. A method for producing a polyurethane foam, wherein the first component, the second component and, optionally, the third component of the multi-component polyurethane foam composition as well as optional additives according to any of claims 1 to 10 are mixed into a mixture,wherein the mixture is optionally placed into a mold or the mixture is applied to the surface of a substrate, and / orthe polyurethane foam is hardened.

12. A polyurethane foam obtainable by the method of claim 11.

13. Use of the multi-component polyurethane foam composition according to any of claims 1 to 10 as a cavity sealant (in particular for motor vehicles), as an insulating foam in sandwich panels, for pipe insulation, in refrigerators, for house insulation, as spray insulation in minesor as impact sound insulation, and / or for sound insulation, heat insulation, or for rust protection, and / or for coating the surface of a substrate.

14. Use of a phenolic resin of the benzyl ether type to produce a polyurethane foam, wherein a) the phenolic resin comprises free phenol and free hydroxybenzyl alcohol, wherein at least about 1.2 parts by weight of free hydroxybenzyl alcohol per 1 part by weight of free phenol are comprised in the phenolic resin; and / orb) the phenolic resin comprises free phenol and free saligenin (o-hydroxybenzyl alcohol), wherein at least about 1.1 parts by weight of free saligenin (o-hydroxybenzyl alcohol) per 1 part by weight of free phenol are comprised in the phenolic resin.

15. The use according to claim 13 or 14 to improve the homogeneity of the pore distribution in the polyurethane foam.

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