Hydrolysis resistance of polyurethane foams

Abstract

The present invention relates to a composition for production of a polyurethane foam, containing a polyalkylene oxide-modified aryl sulfonate as additive, and to the use of the aryl sulfonate in the production of a polyurethane foam.

Description

[0001] HYDROLYSIS RESISTANCE OF POLYURETHANE FOAMS

[0002] TECHNICAL FIELD

[0003]

[0001] The present invention relates to a composition for production of a polyurethane foam, containing a polyalkylene oxide-modified aryl sulfonate as additive, and to the use of the aryl sulfonate in the production of a polyurethane foam.

[0004] BACKGROUND

[0005]

[0002] Mouldable polyurethane foams are commonly used in automotive applications, for example seat cushions, headrests, dashboard, headliner and steering wheels. As a result of the requirement to use a minimum level of volatile organic compounds (VOCs), amine catalysts are used, which are incorporable into the polyurethane foam either in high molecular weight form or in isocyanate-reactive form. While these reactive or low-emission amine catalysts make only a very slight contribution to emissions in the conventional automotive industry test, VDA 278, the use thereof has an adverse effect on the ageing resistance of PU foams under hot and moist conditions. It is therefore an important technical problem to develop additives that can be used, for example, together with low- emission amine catalysts as a component in PU systems or PU foams, and, through the use thereof, to increase the resistance of the PU foams to hydrolytic ageing (humid ageing).

[0006]

[0003] Some of the known additives for improving ageing properties under hot and moist conditions have the disadvantage that they can be mixed only relatively shortly before the foaming process with the other formulation constituents, especially catalysts and water, since they otherwise greatly reduce the gel catalysis and blowing catalysis of the respective PU system over a period of a few hours up to a few days.

[0007]

[0004] EP 1 834 974 A3 describes the use of aromatic diesters for improving physical foaming properties after humid ageing. However, the effect of the diesters is comparatively weak; in particular, they result in only a very slight improvement in ageing resistance under hot and moist conditions of TDI foams.

[0008]

[0005] US20190100638A1 uses halohydrins (compounds having at least one halogen function (e.g. chlorine, bromine) and at least one OH function (for example 6-chlorohexan-1-ol)) for improvement of physical foam properties after humid ageing.

[0009]

[0006] US 2022 / 0033603 A1 describes the use of structurally diverse hydrochlorocarbon compounds for improving the foam properties of PU foams after humid ageing. However, emissions of hydrochlorocarbons are undesirable since they can be toxic.

[0010]

[0007] WO 2022034151 A1 discloses that sulfonic esters added as additive lead to an improvement in the hydrolysis (and heat) stability of the properties of polyurethane foams. PU foams that are subjected to high temperatures at high humidity have much poorer material properties as a result of humid ageing. The material properties of PU foams comprising sulfonic esters are affected to a less significant degree (damaged) by humid ageing. However, a crucial disadvantage of the sulfonic esters described in WO 2022034151 A1 is the low stability thereof in PU systems, such that, in PU system premixes composed of polyols, amine catalysts, water, sulfonic esters according to WO 2022034151 A1 and optional further constituents, there is a distinct decrease in catalytic action of the respective amine catalyst or of the respective amine catalyst mixture over a period of a few hours to a few days. The emissions burden resulting from the compound described in WO 2022034151 A1 is also too high.

[0011]

[0008] The aim of the present invention was therefore that of developing additives that improve the stability of the foams with respect to humid ageing and have high stability as a component in PU systems, and even after ageing of the respective PU system have only a very slight effect, if any, on the catalytic activity thereof and the associated foam rise characteristics. The additives should likewise lead to only very low foam emissions, if any, in the VDA 278 emissions test which is standard in the automotive industry.

[0012]

[0009] Surprisingly, aryl sulfonates according to the present invention have particularly good storage stability as an additive to PU systems blended in advance of foaming, and result in improved storage stability of the foams to humid ageing and low foam emissions according to VDA 278.

[0013] SUMMARY

[0014]

[0010] The present invention relates to a composition for production of a polyurethane foam, comprising: (a) a polyol, (b) an amine catalyst, (c) blowing agent, preferably water, (d) aryl sulfonate as per compound (I) where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,

[0015] R5is hydrogen, 2,6-di-tert-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula

[0016] (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii), where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),

[0017] Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + b + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0018]

[0011] The present invention further relates to a method of producing a polyurethane foam, comprising (A) providing the composition according to the present invention, (B) mixing the composition from step (A) with a compound having isocyanate-functional groups, and (C) producing the polyurethane foam from the mixture obtained in step (B).

[0012] In addition, the invention relates to the use of an aryl sulfonate according to the present invention in the production of a polyurethane foam.

[0019] DETAILED DESCRIPTION

[0020]

[0013] The word “contains” is not supposed to exclude further constituents, process steps etc. Moreover, the word “contains” - in conjunction with individual features, for example of the composition - may be further restricted or replaced by the expression “consisting of’.

[0021]

[0014] Statements of range, for example 1 to 10, shall also include the numerical values that are not disclosed explicitly within the stated range. For example, 1 to 10 also includes the numbers within that range, for example 2, 3, 4, 5, 6, 7, 8 and 9. The lower limits and upper limits of stated ranges of the respective features may be combined with lower limits and upper limits of the individually preferred ranges or optional ranges.

[0022]

[0015] Unless stated otherwise, percentages are reported in per cent by weight, based on the total weight of the respective composition.

[0023]

[0016] An amount stated in “pphp” (“parts per hundred polyol”) means parts by weight per 100 parts by weight of polyol (total polyol) in the composition. For example, 1 .0 pphp of a substance A means 1 .0 g of substance A per 100 g of polyol in the composition.

[0024]

[0017] Terms described in the singular also include the plural form. For example, “polyol” means that one or more polyols covered by the term “polyol” may be present.

[0025]

[0018] The present invention relates to a composition for production of a polyurethane foam, comprising: (a) a polyol, (b) an amine catalyst, (c) blowing agent, (d) aryl sulfonate (inventive aryl sulfonate).

[0026]

[0019] The aryl sulfonate (d) comprises a single aryl sulfonate, or else mixtures of aryl sulfonates.

[0027]

[0020] The composition according to the invention for production of a polyurethane foam may likewise be referred to as a PU system (polyurethane system), PU system premix (polyurethane system premix) or PU foam mix (polyurethane foam mix). In particular, it is a mouldable polyurethane foam. In particular, the composition is a premix for production of a polyurethane foam.

[0028]

[0021] The aryl sulfonate or aryl sulfonate according to the invention is one (or more) aryl sulfonates where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,

[0029] R5is hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii), where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),

[0030] Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + b + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0031]

[0022] When no separate details for the abovementioned indices, substituents and / or radicals (for instance “a”, “b”, “c”, “R1”, “R2” etc.) are given in formulae / radicals / compounds, the details are correspondingly applicable for the underlying formulae, for example the underlying formulae: formula (I2), formula (i), formula (ii) etc.

[0032]

[0023] The dotted line in the case of formula (i), for example, is intended to show the point at which the structure is bonded. For example, for formula (I) and R5= formula (i), this would give the following formula (11):

[0033]

[0024] In formula (11), two R1and two R2are depicted, and the person skilled in the art is able to select R1and R2independently. This is correspondingly true of the remaining Rxradicals, such as R2, R3, R4, R6, R7, R8and R9. However, it is preferable that all the respective Rx(R1, R3, R4, R6, R7, R8and R9) have the same radicals.

[0034]

[0025] It is accordingly preferable for the formulae according to the invention that each R1is hydrogen, methyl or ethyl, especially preferably hydrogen, each R2is hydrogen, methyl or ethyl, especially preferably methyl, each R3is hydrogen, phenyl, or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is hydrogen, phenyl, or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R5is hydrogen, 2,6-di-tert-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n-dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii), R6is hydrogen, phenyl, or alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is hydrogen, phenyl, or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is hydrogen, phenyl, or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is hydrogen, 2 ,6-di-tert- butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, or a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n-dodecyl, or a radical of formula (i), especially preferably hydrogen, or a radical of formula (i).

[0035]

[0026] What is meant by the definitions that each R3is independently hydrogen, phenyl, or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, more preferably methyl, and each R4is independently hydrogen, phenyl, or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, more preferably methyl, is that, in each repeat unit with the index “a”, the repeat units may have a different substituent. This is the case, for example, in the polyether tosylate 3 (additive 7) according to the examples. This is correspondingly also true of the repeat units with the indices “d” and “e”.

[0036]

[0027] In principle, there should be at least four repeat units (a + b + c + d + e) in the aryl sulfonate according to the invention. When the radical of formula (ii) is absent in the aryl sulfonate according to the invention, d and e are 0, and hence a + b + c + 0 + 0 = a + b + c. As described above, when R5is not the radical of formula (ii), the sum total of a + b + c should be 4 to 20, preferably 4 to 15, more preferably 4 to 12, and, when R5is the radical of formula (ii), the sum total of a + b + c + d + e should be 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0037]

[0028] The catalytic effect of the respective amine catalyst or the respective amine catalyst mixture in a composition was improved by the aryl sulfonate according to the invention in the course of ageing over a period of a few hours to a few days.

[0038]

[0029] Surprisingly, particularly aryl sulfonates that have a sulfonated propylene oxide end group, e.g. -[CH2-C(CH3)H-O]-SO3-CeH5CH3, have particularly good storage stability as an additive to PU systems blended in advance of foaming. PU systems that are blended in advance of foaming are especially PU systems that still do not include a compound having isocyanate-functional groups.

[0039]

[0030] Moreover, the aryl sulfonates according to the invention bring about a crucial improvement over low molecular weight sulfonic esters in respect of the physical foam properties of PU foams after humid ageing. Furthermore, aryl sulfonates according to the invention are nonvolatile, and therefore use thereof leads to only very low foam emissions, if any, in the VDA 278 emissions test which is standard in the automotive industry.

[0040]

[0031] More preferably, the aryl sulfonates according to the invention are used as per the examples in the composition according to the invention for production of a polyurethane foam. These illustrative aryl sulfonates may be used in the amounts according to the invention.

[0041]

[0032] Preference is given to the aryl sulfonate (b) as per compound (I2): where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, R5is hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii), where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),

[0042] Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0043]

[0033] The present invention likewise encompasses a method of producing a polyurethane foam, comprising (A) providing the composition according to the invention, (B) mixing the composition from step (A) with a compound having isocyanate-functional groups, and (C) producing the polyurethane foam from the mixture obtained in step (B).

[0044]

[0034] The composition may be free of any compound having isocyanate-functional groups. This would then be a premix. It is then possible to add a compound having isocyanate-functional groups to the premix for the foam to be produced. According to the invention, the composition may be mixed or prepared as early as 21 days before the addition of the compound having isocyanate-functional groups without significant deterioration in the foam properties (short rise time).

[0045]

[0035] Accordingly, between the (A) providing or preparing of the composition and the (B) mixing of the composition from step (A) with a compound having isocyanate-functional groups, there may be 12 hours to 30 days, preferably 1 day to 21 days, more preferably 1 day to 15 days, especially preferably 1 day to 9 days, most preferably 1 day to 3 days.

[0046]

[0036] The composition according to the invention may be provided as a kit, where a first component is the composition according to the invention and a second component contains a compound having isocyanate-functional groups.

[0047]

[0037] The composition according to the invention may already contain (e) a compound having isocyanate-functional groups. The composition according to the invention may contain (e) a compound having isocyanate-functional groups. This is typically the case shortly before the production of foam.

[0048]

[0038] The compound having isocyanate-functional groups may comprise hexamethylene diisocyanate (HDI), phenylene diisocyanate (PDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and / or isophorone diisocyanate (IPDI), preferably toluene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI), especially preferably toluene diisocyanate (TDI).

[0049]

[0039] The compound having isocyanate-functional groups (isocyanate component) may contain 2,4-TDI, 2,6-TDI or a combination thereof. The isocyanate-functional groups (isocyanate component) may contain crude MDI, for example a mixture of about 60% 4,4’-MDI and / or a stoichiometric amount together with other isomers and analogous higher polyisocyanates. Other suitable isocyanates are the isocyanates according to U.S. Pat. No. 4,394,491 , which are part of this invention.

[0050]

[0040] Moulded TDI foams with amine catalysts (or with reactive and / or nonvolatile amine catalysts), by comparison with moulded MDI foams, are even more sensitive to hydrolytic ageing or humid ageing. The composition according to the invention and method including the inventive aryl sulfonate (b) brings about a distinct improvement in the physical foam properties of TDI foams after humid ageing.

[0051]

[0041] The amount of the compound having isocyanate-functional groups is typically based on an NCO index. The NCO index is the number of isocyanate equivalents divided by the total number of equivalents of active hydrogen (for example of the polyol), multiplied by 100 (based, for example, on an NCO index of [NCO / (OH+NH)]*100). The composition may have an NCO index of 70 to 500, or of 70 to 115. An NCO index of 70 to 115 is typically used when the composition is used for production of flexible foams. The mixing ratio by weight of the composition or premix to the compound having isocyanate-functional groups may be 1 :1 to 3:1 . The composition may contain 10% to 40% by weight of the compound having isocyanate-functional groups, preferably 10% to 35% by weight, especially preferably 20% to 30% by weight, based on the total weight of the composition.

[0042] The composition according to the invention contains a polyol (a). Polyols are organic compounds having at least two hydroxyl groups. The polyol may be any polyol suitable for the production of polyurethane foams. In principle, the polyol reacts with a compound having isocyanate- functional groups to obtain a polyurethane. Suitable polyols can be found in WO 03 / 016373 A1 , WO 01 / 58976 A1 , WO 04060956 A1 , WO 03 / 016372 A1 , and WO 03 / 055930 A1 , and these polyols in the applications cited are part of this invention. Accordingly, the polyol should be a polyol that can react with a compound having isocyanate-functional groups.

[0052]

[0043] Suitable polyols include polyether polyols or copolymers of polyether polyols. The polyol may be polyether polyol, poly(alkylene oxide) polymers, for example poly(ethylene oxide), polypropylene oxide) and / or copolymers having terminal hydroxyl groups derived from polyhydric compounds (e.g. diols and triols). The polyol may have a molecular weight of 4500 to 7000 g / mol and / or from 2000 to 4000 g / mol. Diols and triols, which can likewise be assigned to the group of the polyols, may be ethylene glycol, propylene glycol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylolpropane, other suitable polyols of low molecular weight, or a combination thereof. The polyol may be a polyhydroxyterminated acetal resin, hydroxy-terminated amine, hydroxy-terminated polyamine, or a combination of these. The polyol may be a polyalkylene carbonate-based polyol, a phosphate-based polyol, or a combination of these.

[0053]

[0044] Suitable polyols can additionally be found in the examples.

[0054]

[0045] The polyol may contain copolymer polyols. Copolymer polyols, based on weight, may account for up to about 20% of the total polyol content. The copolymer polyols improve the polyurethane foam formed by the composition in that they increase the deformation resistance of the polyurethane foam and hence improve the load-bearing properties of a polyurethane foam formed by the composition. The copolymer polyol may be a graft polyol, a polyurea-modified polyol or a combination of these, or comprises one of these.

[0055]

[0046] The graft polyol is any suitable graft polyol. The graft polyol may be produced by copolymerization of vinyl monomers (e.g. styrene and acrylonitrile) with a suitable starting polyol. The starting polyol may be a glycerol-initiated triol end-capped with ethylene oxide (for example with 80% to 85% primary hydroxyl groups). The graft polyol here comprises a copolymer grafted onto the starting polyol, homopolymers of the vinyl monomers, and the starting polyol (in unchanged form). The graft polymer may contain the styrene or the acrylonitrile in a concentration of about 5 to 45 per cent by weight.

[0056]

[0047] The polyurea-modified polyol is formed by the reaction of a diamine and a diisocyanate in the presence of the starting polyol. The polyurea-modified polyol here contains a polyurea dispersion. The polyurea-modified polyol may be a polyisocyanate polyaddition polyol (PIPA), which is formed, for example, in situ from a reaction between the compound having isocyanate-functional groups and an alkanolamine.

[0057]

[0048] The polyol may be present in an amount of 50% to 98% by weight, preferably 70% to 97% by weight, more preferably 80% to 96% by weight, especially preferably 85% to 95% by weight, based on the total weight of the composition.

[0049] The blowing agent (c) may be any suitable blowing agent. Blowing agents are compounds that react with isocyanate, for example, and form a gas. Blowing agents may be carbon dioxide, hydrochlorofluorocarbons, hydrogenated hydrofluorocarbons, hydrogenated hydrochlorofluorocarbons, fluoroolefins, chlorofluoroolefins, hydrofluorocarbons, hydrochlorofluoroolefins, acetone, low-boiling hydrocarbons (e.g. cyclopentane, isopentane, n- pentane or a combination thereof), water or a combination thereof. It is particularly preferable that the blowing agent (c) is water. Thus, component (c) would be water. The blowing agent may be present in the composition in an amount of 0.02% to 10% by weight, preferably 0.1 % to 8% by weight, more preferably 1 % to 7% by weight, especially preferably 1 .5% to 5% by weight, based on the total weight of the composition. Water may be present in the composition in an amount of 0.02% to 10% by weight, preferably 0.1 % to 8% by weight, more preferably 1 % to 7% by weight, especially preferably 1 .5% to 5% by weight, based on the total weight of the composition.

[0058]

[0050] The composition may additionally contain an additive selected from a cell stabilizer, a crosslinking agent, a chain extender, a pigment, a filler, a flame retardant, a urethane-gel auxiliary catalyst, and a blowing catalyst or combinations thereof.

[0059]

[0051] The composition may additionally contain a cell stabilizer. Cell stabilizers contain silicone surfactants, anionic surfactants or a combination of these. The cell stabilizer may be a silicon surfactant, for example polyalkylsiloxane, polyoxyalkylene polyol-modified dimethylpolysiloxane, alkylene glycol-modified dimethylpolysiloxane, or a combination of these. The cell stabilizer preferably does not contain an acyl group. The silicone surfactant may contain an acyl group. The cell stabilizer may be an anionic surfactant, for example a salt of a fatty acid, a salt of a sulfuric ester, a salt of a phosphoric ester, a salt of a sulfonic acid or a combination of these. The composition may contain a cell stabilizer in an amount of 0.1 pphp to 20 pphp, 0.1 pphp to 10 pphp, or 0.1 pphp to 5 pphp.

[0060]

[0052] The composition may contain a crosslinking agent. Crosslinking agents may be low molecular weight compounds containing at least two radicals, such as hydroxyl groups, primary amino groups, secondary amino groups, other active hydrogen-containing groups that are reactive with an isocyanate group, or a combination of these.

[0061]

[0053] The crosslinking agent may be a polyhydric alcohol (e.g. a trihydric alcohol, such as glycerol or trimethylolpropane), a polyamine or a combination of these. A polyamine may be diethyltoluenediamine, chlorodiaminobenzene, diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, 1 ,6-hexanediamine or a combination of these. In one embodiment in which the crosslinking agent is a diamine, the crosslinking agent contains twelve or fewer carbon atoms, seven carbon atoms or fewer than seven carbon atoms. The mixing of the crosslinking agent(s), for example a low molecular weight crosslinker, with the polyol component can increase hardness and promote faster demoulding. The amount of crosslinking agent in the composition is typically from 0.10 pphp to 20 pphp.

[0062]

[0054] The composition may contain chain extenders. Chain extenders may be compounds including those having a functional hydroxyl or amino group, such as glycols, amines, diols or a combination of these. The chain extender may be ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1 ,4-butanediol, 1 ,3-butanediol, 1 ,5-pentanediol, neopentyl glycol, 1 ,6-hexanediol, 1 ,10-decanediol, 1 ,12-dodecanediol, ethoxylated hydroquinone, 1 ,4-cyclohexanediol, N- methylethanolamine, N-methylisopropanolamine, 4-aminocyclohexanol, 1 ,2-diaminoethane, 2,4- toluenediamine or a combination of these. The amount of the chain extenders in the composition is typically from 0.10 pphp to 20 pphp.

[0063]

[0055] The composition may contain pigments. Pigments may include organic pigments, inorganic pigments or a combination of these. The pigments enable colouring (for example for adjustment to a shade), concealment (for example for concealment of yellowing), or a combination of these. The pigment may be an azo / diazo dye, a phthalocyanine, dioxazine, carbon black or a combination of these. The pigment may be titanium dioxide, iron oxide, chromium oxide or a combination of these. The amount of the pigments in the composition is typically from 0.01 pphp to 20 pphp.

[0064]

[0056] The composition may contain a filler. Fillers increase the density and load-bearing capacity of polyurethane foams. The filler may be barium sulfate, calcium carbonate or a combination of these. The amount of the filler in the composition may typically be from 0.01 pphp to 20 pphp.

[0065]

[0057] The composition may contain a flame retardant. Flame retardants reduce the flammability of polyurethane foams. The flame retardant may be a chlorinated phosphate ester, a chlorinated paraffin, a melamine powder or a combination of these. The flame retardant may be present in the composition in an amount of 1 pphp to 20 pphp, of 1 pphp to 10 pphp, or of 1 pphp to 5 pphp.

[0066]

[0058] The composition may additionally contain a metal catalyst. The metal catalyst is preferably an organometallic metal salt, organic metal salt, inorganic metal salt and / or organometallic compound, where the metal is Sn, Bi, Zn, Al and / or K, preferably Sn, Zn and / or Bi. Accordingly, the composition may contain Sn, Bi, Zn, Al and / or K, preferably Sn, Zn and / or Bi. It is particularly preferable that the composition contains an organotin compound, for example dimethyltin dineodecanoate.

[0067]

[0059] The composition may additionally contain a blowing catalyst, preferably 2-[N- (dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropylbis(aminoethyl) ether and / or bis(dimethylamino)ethyl ether.

[0068]

[0060] The amine catalyst (b) may be an isocyanate-reactive amine catalyst and / or a non- isocyanate-reactive amine catalyst. For example, triethylenediamine is a non-isocyanate-reactive amine catalyst. For example, 1 ,4-diazabicyclo[2.2.2]octane-2-methanol is an isocyanate-reactive amine catalyst. The amine catalyst (b) is preferably a tertiary amine catalyst. It is particularly preferable that the amine catalyst is a reactive and / or nonvolatile amine catalyst.

[0069]

[0061] The amine catalyst (b) may be selected from the group consisting of triethylenediamine, 1 ,4- diazabicyclo[2.2.2]octane-2-methanol, diethanolamine, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N- methyl-1 ,3-propanediamine, 2-[[2-(2-(dimethylamino)ethoxy)ethyl]methylamino]ethanol, 1 ,1 '-[(3- {bis[3-(dimethylamino)propyl]amino}propyl)imino]dipropan-2-ol, [3-(dimethylamino)propyl]urea, 1 ,3- bis[3-(dimethylamino)propyl]urea, amine catalysts of the general structure (1 a) and / or amine catalysts of the general structure (1 b): where each Y is independently -NRVIIIRIXor -ORIX,

[0070] R1is a linear, cyclic, aliphatic or aromatic hydrocarbon having 1-8 carbon atoms, optionally functionalized with an -OH group or hydrogen, R" is a linear, cyclic, aliphatic or aromatic hydrocarbon having 1-8 carbon atoms, optionally functionalized with an -OH group or hydrogen,

[0071] X is oxygen, nitrogen, hydroxyl, amines of the structure -NR111- or -NRIHRIVor urea groups of the structure -NRVCONRVI- or -NRVIICONRVIRV", each RIII IXis independently a linear, cyclic, aliphatic or aromatic hydrocarbon having 1-8 carbon atoms, optionally functionalized with an -OH group, an -NH- or -NH2 group or hydrogen, m = 0 to 4, preferably 2 or 3, n = 2 to 6, preferably 2 or 3, i = 0 to 3, preferably 0-2,

[0072] Z N - Rx

[0073] (lb) where Rxis hydrogen, or a linear, branched or cyclic aliphatic or aromatic hydrocarbon which has 1- 18 carbon atoms and is optionally substituted by a hydroxyl group and / or optionally substituted by an -NH2 group,

[0074] Z is oxygen, -NRX- or -CH2.

[0075]

[0062] The amine catalyst (b) is preferably selected from a group consisting of diethanolamine, N,N- bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine N,N-dimethyl-N',N'-2-hydroxy(propyl)-1 ,3-propylenediamine, dimethylaminopropylamine, (N,N- dimethylaminoethoxy)ethanol, methylhydroxyethylpiperazine, bis(N,N-dimethyl-3- aminopropyl)amine, N,N-dimethylaminopropylurea, diethylaminopropylurea, N,N'-bis(3- dimethylaminopropyl)urea, N,N'-bis(3-diethylaminopropyl)urea; bis(dimethylamino)-2-propanol, 6- dimethylamido-1 -hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole and N-(2- hydroxyethyl)imidazole. Particular preference is given to 6-dimethylamido-1 -hexanol, N-(3- aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole and / or N-(2-hydroxyethyl)imidazole.

[0076]

[0063] The molecular weight of the aryl sulfonate (d) is preferably 300 g / mol to 20 000 g / mol, preferably 340 g / mol to 10 000 g / mol, more preferably 400 g / mol to 5000 g / mol, further preferably 450 g / mol to 2000 g / mol, especially preferably 500 g / mol to 1000 g / mol.

[0064] Preferred aryl sulfonates are shown below with reference to particularly preferred formulae, such as compound (11) etc. The compound (I) may be selected from the group consisting of compound (11), compound (I2), compound (I3), compound (I4), compound (I5), compound (I6), compound (I7), compound (I8), compound (I9), compound (110), compound (111), compound (112), compound (113), compound (114), compound (115), compound (116), compound (117), compound (118), compound (119), compound (I20), compound (121), compound (I22), compound (I23) or combinations thereof.

[0077]

[0065] Compound (11) is as follows:

[0078] Accordingly, compound (11) is a specificized compound by comparison with compound (I) where R5is formula (i). Since R5is the radical having the formula (i) and R5is not the radical of formula (ii), the sum of a + b + c must be 4 to 20, preferably 4 to 15, especially preferably 4 to 12. As already mentioned, the two R1and the two R2may be the same or respectively different substituents. They are preferably the same substituents. This is correspondingly true of the further compounds. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds.

[0079]

[0066] Compound (I2) is as follows:

[0080] In compound (I2), the unit with the index b is absent and hence 0 (by comparison with compound (I)). The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. If R5is not the radical of formula (ii), a + b + c = 4 to 20 (i.e. a + 0 + c = 4 to 20 and hence a + c = 4 to 20), preferably 4 to 15, especially preferably 4 to 12. If R5is the radical of formula (ii), the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20 (where b = 0). This is correspondingly true of the remaining compounds. In the case of compound (I2), the sum of a + c may be 4 to 20, preferably 3 to 15, especially preferably 4 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12. In particular, c may be 1 to 20, preferably 2 to 20, more preferably 2 to 15, especially preferably 2 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12, and c may be 1 to 20, preferably 2 to 20, more preferably 2 to 15, especially preferably 2 to 12.

[0081]

[0067] Compound (I3) is as follows:

[0082] In compound (I3), the unit with the index b is absent and hence 0. R5is likewise formula (i) (by comparison with compound (I)). The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In the case of compound (I3), the sum of a + c is 4 to 20, preferably 3 to 15, especially preferably 4 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12. In particular, c may be 1 to 20, preferably 2 to 20, more preferably 2 to 15, especially preferably 2 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12, and c may be 1 to 20, preferably 2 to 20, more preferably 2 to 15, especially preferably 2 to 12.

[0083]

[0068] Compound (I4) is as follows: (I4). In compound (I4), R5is formula (ii) (by comparison with compound (I)). The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds.

[0084]

[0069] Compound (I5) is as follows:

[0085] (I5).

[0086] In compound (I5), R5is formula (ii) and both R9are formula (i) (by comparison with compound (I)). The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds.

[0087]

[0070] Compound (I6) is as follows:

[0088] In compound (16), the units with the indices b and c are absent and hence each 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In compound (16), a is 4 to 20, preferably 4 to 15, especially preferably 4 to 12.

[0089]

[0071] Compound (I7) is as follows:

[0090] In compound (I7), the units with the indices b and c are absent and hence each 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In compound (I7), a is 4 to 20, preferably 4 to 15, especially preferably 4 to 12.

[0091]

[0072] Compound (I8) is as follows:

[0092] In compound (I8), the units with the indices b and c are absent and hence each 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In compound (I8), a is 4 to 20, preferably 4 to 15, especially preferably 4 to 12.

[0093]

[0073] Compound (I9) is as follows:

[0094] The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds.

[0095]

[0074] Compound (110) is as follows:

[0096] In compound (110), the unit with the index c is absent and hence 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In the case of compound (110), the sum of a + b should be 4 to 20, preferably 3 to 15, especially preferably 4 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12. In particular, b may be 1 to 20, preferably 1 to 15, more preferably 1 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12, and b may be 1 to 20, preferably 1 to 15, more preferably 1 to 12.

[0097]

[0075] In a particularly preferred embodiment of compound (110), b is 1 to 20, preferably 1 to 15, more preferably 1 to 12, and a = 0.

[0098]

[0076] Compound (111) is as follows:

[0099] The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds.

[0100]

[0078] Compound (113) is as follows:

[0101] In compound (113), the unit with the index b is absent and hence 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In the case of compound (113), the sum of a + c may be 4 to 20, preferably 3 to 15, especially preferably 4 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12. In particular, c may be 1 to 20, preferably 2 to 20, more preferably 2 to 15, especially preferably 2 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12, and c may be 1 to 20, preferably 2 to 20, more preferably 2 to 15, especially preferably 2 to 12.

[0102]

[0079] Compound (114) is as follows:

[0103] In compound (114), the unit with the index b is absent and hence 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In the case of compound (114), the sum of a + c is 4 to 20, preferably 3 to 15, especially preferably 4 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12. In particular, c may be 1 to 20, preferably 2 to 20, more preferably 2 to 15, especially preferably 2 to 12. In particular, a may be 2 to 20, more preferably 2 to 15, especially preferably 2 to 12, and c may be 1 to 20, preferably 2 to 20, more preferably 2 to 15, especially preferably 2 to 12.

[0104]

[0080] Compound (115) is as follows: The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. It is preferable that one R9is a hydrogen and one R9the radical having the formula (i).

[0105]

[0081] Compound (116) is as follows:

[0106] The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds.

[0107]

[0082] Compound (117) is as follows:

[0108] In compound (117), the units with the indices b and c are absent and hence each 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In compound (117), a may be 4 to 20, preferably 4 to 15, especially preferably 4 to 12.

[0109]

[0083] Compound (118) is as follows:

[0110] In compound (118), the units with the indices b and c are absent and hence each 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In compound (118), a may be 4 to 20, preferably 4 to 15, especially preferably 4 to 12.

[0111]

[0084] Compound (119) is as follows:

[0112] The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds.

[0113]

[0085] Compound (120) is as follows:

[0114] In compound (120), the units with the indices b and c are absent and hence each 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In compound (120), a may be 4 to 20, preferably 4 to 15, especially preferably 4 to 12.

[0115]

[0086] Compound (121) is as follows:

[0116] In compound (121), the units with the indices b and c are absent and hence each 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In compound (121), a is 4 to 20, preferably 4 to 15, especially preferably 4 to 12.

[0117]

[0087] Compound (I22) is as follows:

[0118] In compound (I22), the units with the indices b and c are absent and hence each 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In compound (I22), the R3radical for a portion of the repeat unit with the index a is a hydrogen (see right-hand repeat unit with the index a in compound (I22)). The R3radical in the repeat unit with the index a in compound (I22) may in each case be selected according to the description for the compound (I), i.e. each R3is independently hydrogen, phenyl, or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, more preferably methyl.

[0119] The index a should be 2 to 20, more preferably 4 to 15, especially preferably 4 to 12. An illustrative compound is polyether tosylate 3 (additive 7) according to the examples.

[0120]

[0088] Compound (I23) is as follows:

[0121] In compound (I23), the units with the indices b and c are absent and hence each 0. The description of all radicals, indices and substituents with regard to compound (I) is correspondingly applicable to these and all other specificized compounds. In compound (I23), the R3radical for a portion of the repeat units with the index a is a hydrogen (see right-hand repeat unit with the index a in compound (I22)). In the other portion of the repeat unit with the index a, R3is a methyl radical. The index a should be 2 to 20, more preferably 4 to 15, especially preferably 4 to 12. An illustrative compound is polyether tosylate 3 (additive 7) according to the examples.

[0122]

[0089] It is preferable that the formula (i) is the formula (i1):

[0123] This is true of compound (I) and of all other compounds as mentioned above.

[0124]

[0090] It is further preferable that each R1is methyl, and each R2is hydrogen. This is true of compound (I) and of all other compounds as mentioned above.

[0125]

[0091] The formula (ii) may be selected from the group consisting of formula (ii1), formula (ii2), formula (ii3), formula (ii4) or combinations thereof:

[0092] The aryl sulfonate (d) is preferably an aryl sulfonate selected from the group consisting of tetraethylene glycol monotosylate, pentaethylene glycol monotosylate, hexaethylene glycol monotosylate, heptaethylene glycol monotosylate, octaethylene glycol monotosylate, tetrapropylene glycol monotosylate, pentapropylene glycol monotosylate, hexapropylene glycol monotosylate, heptapropylene glycol monotosylate, octapropylene glycol monotosylate, nonapropylene glycol monotosylate, decapropylene glycol monotosylate, undecapropylene glycol monotosylate, dodecapropylene glycol monotosylate, tridecapropylene glycol monotosylate, tetradecapropylene glycol monotosylate, tetraethylene glycol ditosylate, pentaethylene glycol ditosylate, hexaethylene glycol ditosylate, heptaethylene glycol ditosylate, octaethylene glycol ditosylate, tetrapropylene glycol ditosylate, pentapropylene glycol ditosylate, hexapropylene glycol ditosylate, heptapropylene glycol ditosylate, octapropylene glycol ditosylate, nonapropylene glycol ditosylate, decapropylene glycol ditosylate, undecapropylene glycol ditosylate, dodecapropylene glycol ditosylate, tridecapropylene glycol ditosylate, tetradecapropylene glycol ditosylate or a combination of these. The abbreviation ‘tosylate’ is used as a synonym for ‘4-methylphenylsulfonate’.

[0093] The composition may contain (a) polyol in an amount of 50% to 98% by weight, preferably 70% to 97% by weight, more preferably 80% to 96% by weight, especially preferably 85% to 95% by weight, based on the total weight of the composition.

[0126]

[0094] The composition may contain (b) amine catalyst in an amount of 0.01 % to 5% by weight, preferably 0.05% to 3.5% by weight, more preferably 0.08% to 2.5% by weight, especially preferably 0.1 % to 1 .5% by weight, based on the total weight of the composition.

[0127]

[0095] The composition may contain (c) water in an amount of 0.02% to 10% by weight, preferably 0.1 % to 8% by weight, more preferably 1 % to 7% by weight, especially preferably 1.5% to 5% by weight, based on the total weight of the composition.

[0128]

[0096] The composition may contain (d) aryl sulfonate in an amount of 0.01 % to 7% by weight, preferably 0.1 % to 6% by weight, more preferably 0.3% to 5% by weight, especially preferably 0.5% to 4% by weight, based on the total weight of the composition.

[0129]

[0097] It is preferable that the composition contains (b) amine catalyst in an amount of 0.01 % to 5% by weight, preferably 0.05% to 3.5% by weight, further preferably 0.08% to 2.5% by weight, especially preferably 0.1 % to 1 .5% by weight, based on the total weight of the composition, and (d) aryl sulfonate in an amount of 0.01 % to 7% by weight, preferably 0.1 % to 6% by weight, more preferably 0.3% to 5% by weight, especially preferably 0.5% to 4% by weight, based on the total weight of the composition.

[0130]

[0098] It is particularly preferable that the composition contains (d) aryl sulfonate in an amount of 0.5% to 7% by weight, preferably 1 % to 6% by weight, more preferably 1.5% to 5% by weight, especially preferably 1 .9% to 3% by weight, based on the total weight of the composition.

[0131]

[0099] The aryl sulfonates (inventive aryl sulfonates) of formula (I) are used in the production of a polyurethane foam: where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,

[0132] R5is hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii), where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),

[0133] Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + b + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0134]

[0100] The invention is described hereinafter by aspects.

[0101] Aspect 1 . A composition for production of a polyurethane foam, comprising: (a) a polyol, (b) where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,

[0135] R5is hydrogen, 2,6-di-tert-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii), where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),

[0136] Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + b + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0137]

[0102] Aspect 2. A composition for production of a polyurethane foam, comprising: (a) a polyol, (b) an amine catalyst, (c) blowing agent, preferably water, (d) aryl sulfonate as per compound (I) where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, the sum of a + b + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, R5is hydrogen, 2,6-di-tert-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula

[0138] (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i)

[0139]

[0103] Aspect 3. A composition for production of a polyurethane foam, comprising: (a) a polyol, (b) where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),

[0140] Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0141]

[0104] Aspect 4. A composition for production of a polyurethane foam, comprising: (a) a polyol, (b) an amine catalyst, (c) water, (d) aryl sulfonate as per compound (I) where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,

[0142] R5is hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula

[0143] (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii), where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),

[0144] Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + b + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0145]

[0105] Aspect 5. The composition according to any of the preceding aspects, wherein the aryl sulfonate (b) is aryl sulfonate as per compound (I2): where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,

[0146] R5is hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii), where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-ter -butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),

[0147] Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0148]

[0106] Aspect 6. The composition according to any of the preceding aspects, wherein the blowing agent is water.

[0149]

[0107] Aspect 7. The composition according to any of the preceding aspects, wherein the composition further contains (e) a compound having isocyanate-functional groups or the composition does not contain (e) a compound having isocyanate-functional groups.

[0150]

[0108] Aspect 8. The composition according to any of the preceding aspects, wherein the compound having isocyanate-functional groups comprises hexamethylene diisocyanate (HDI), phenylene diisocyanate (PDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and / or isophorone diisocyanate (IPDI), preferably toluene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI), especially preferably toluene diisocyanate (TDI).

[0151]

[0109] Aspect 9. The composition according to any of the preceding aspects, wherein the amine catalyst (b) is an isocyanate-reactive amine catalyst and / or a non-isocyanate-reactive amine catalyst.

[0152]

[0110] Aspect 10. The composition according to any of the preceding aspects, wherein amine catalyst (b) is a tertiary amine catalyst.

[0153]

[0111] Aspect 11. The composition according to any of the preceding aspects, wherein the amine catalyst (b) is selected from the group consisting of triethylenediamine, 1 ,4- diazabicyclo[2.2.2]octane-2-methanol, diethanolamine, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N- methyl-1 ,3-propanediamine, 2-[[2-(2-(dimethylamino)ethoxy)ethyl]methylamino]ethanol, 1 ,1 '-[(3- {bis[3-(dimethylamino)propyl]amino}propyl)imino]dipropan-2-ol, [3-(dimethylamino)propyl]urea, 1 ,3- bis[3-(dimethylamino)propyl]urea, amine catalysts of the general structure (1 a) and / or amine catalysts of the general struct where each Y is independently -NRVIIIRIXor -ORIX, R1is a linear, cyclic, aliphatic or aromatic hydrocarbon having 1-8 carbon atoms, optionally functionalized with an -OH group or hydrogen,

[0154] R" is a linear, cyclic, aliphatic or aromatic hydrocarbon having 1-8 carbon atoms, optionally functionalized with an -OH group or hydrogen,

[0155] X is oxygen, nitrogen, hydroxyl, amines of the structure -NRIH- or -NRIHRIVor urea groups of the structure -NRVCONRVI- or -NRVIICONRVIRV", each RIII IXis independently a linear, cyclic, aliphatic or aromatic hydrocarbon having 1-8 carbon atoms, optionally functionalized with an -OH group, an -NH- or -NH2 group or hydrogen, m = 0 to 4, preferably 2 or 3, n = 2 to 6, preferably 2 or 3, i = 0 to 3, preferably 0-2, where Rxis hydrogen, or a linear, branched or cyclic aliphatic or aromatic hydrocarbon which has 1- 18 carbon atoms and is optionally substituted by a hydroxyl group and / or optionally substituted by an -NH2 group, Z is oxygen, -NRX- or -CH2.

[0156]

[0112] Aspect 12. The composition according to any of the preceding aspects, wherein amine catalyst (b) is selected from a group consisting of diethanolamine, N,N-bis(3-dimethylaminopropyl)- N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'- trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine N,N- dimethyl-N',N'-2-hydroxy(propyl)-1 ,3-propylenediamine, dimethylaminopropylamine, (N,N- dimethylaminoethoxy)ethanol, methylhydroxyethylpiperazine, bis(N,N-dimethyl-3- aminopropyl)amine, N,N-dimethylaminopropylurea, diethylaminopropylurea, N,N'-bis(3- dimethylaminopropyl)urea, N,N'-bis(3-diethylaminopropyl)urea; bis(dimethylamino)-2-propanol, 6- dimethylamido-1 -hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole and N-(2- hydroxyethyl)imidazole.

[0157]

[0113] Aspect 13. The composition according to any of the preceding aspects, wherein the composition further contains a blowing catalyst, preferably 2-[N-(dimethylaminoethoxyethyl)-N- methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropylbis(aminoethyl) ether and / or bis(dimethylamino)ethyl ether.

[0158]

[0114] Aspect 14. The composition according to any of the preceding aspects, wherein the composition further contains a metal catalyst, the metal catalyst preferably being an organometallic metal salt, organic metal salt, inorganic metal salt and / or organometallic compound, where the metal is Sn, Bi, Zn, Al or K, preferably Sn, Zn and / or Bi.

[0115] Aspect 15. The composition according to any of the preceding aspects, wherein the composition further includes an additive selected from a chain extender, a pigment, a filler, a flame retardant, a urethane-gel auxiliary catalyst, and a blowing catalyst.

[0159]

[0116] Aspect 16. The composition according to any of the preceding aspects, wherein the molecular weight of the aryl sulfonate (d) is 300 g / mol to 20 000 g / mol, preferably 340 g / mol to 10 000 g / mol, especially preferably 400 g / mol to 5000 g / mol, more preferably 450 g / mol to 2000 g / mol, especially preferably 500 g / mol to 1000 g / mol.

[0160]

[0117] Aspect 17. The composition according to any of the preceding aspects, wherein compound (I) is selected from the group consisting of compound (11), compound (I2), compound (I3), compound (I4), compound (I5), compound (I6), compound (I7), compound (I8) or combinations thereof:

[0161]

[0162]

[0118] Aspect 18. The composition according to any of the preceding aspects, wherein compound (I) is selected from the group consisting of compound (I9), compound (110), compound (111), compound (112), compound (113), compound (114), compound (115), compound (116), compound (117), compound (118) or combinations thereof:

[0163]

[0119] Aspect 19. The composition according to any of the preceding aspects, wherein compound

[0164] (I) is selected from the group consisting of compound (119), compound (I20), compound (121), compound (I22), compound (I23) or combinations thereof:

[0165]

[0120] Aspect 20. The composition according to any of the preceding aspects, wherein the formula (i) is the formula (i1):

[0166]

[0121] Aspect 21. The composition according to any of the preceding aspects, wherein each R1is methyl, and each R2is hydrogen.

[0167]

[0122] Aspect 22. The composition according to any of the preceding aspects, wherein the radical offormula (ii) is selected fromthe group consisting ofthe radical offormula (ii1), the radical of formula (ii2), the radical of formula (ii3), the radical of formula (ii4) or combinations thereof:

[0123] Aspect 23. The composition according to any of the preceding aspects, wherein the composition contains: (a) polyol in an amount of 50% to 98% by weight, preferably 70% to 97% by weight, more preferably 80% to 96% by weight, especially preferably 85% to 95% by weight, based on the total weight of the composition, and / or (b) amine catalyst in an amount of 0.01 % to 5% by weight, preferably 0.05% to 3.5% by weight, more preferably 0.08% to 2.5% by weight, especially preferably 0.1 % to 1 .5% by weight, based on the total weight of the composition, and / or (c) water in an amount of 0.02% to 10% by weight, preferably 0.1 % to 8% by weight, more preferably 1 % to 7% by weight, especially preferably 1 .5% to 5% by weight, based on the total weight of the composition, and / or (d) aryl sulfonates in an amount of 0.01 % to 7% by weight, preferably 0.1 % to 6% by weight, more preferably 0.3% to 5% by weight, especially preferably 0.5% to 4% by weight, based on the total weight of the composition.

[0168]

[0124] Aspect 24. The composition according to any of the preceding aspects, wherein one R9in the radical of formula (ii) is a hydrogen and one R9in the radical of formula (ii) is a radical of formula (i).

[0125] Aspect 25. A method of producing a polyurethane foam, comprising (A) providing the composition according to any of the preceding aspects, (B) mixing the composition from step (A) with a compound having isocyanate-functional groups, and (C) producing the polyurethane foam from the mixture obtained in step (B).

[0169]

[0126] Aspect 26. Use of an aryl sulfonate of formula (I) in the production of a polyurethane foam: where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,

[0170] R5is hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii), where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),

[0171] Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + b + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

[0172] EXAMPLES

[0173]

[0127] The examples which follow serve to illustrate particular elements of the invention and are not intended to restrict the scope of the appended claims. However, individual parts of the examples may be used for further delimitation.

[0174] Various additives are mixed hereinafter into a composition for production of a polyurethane foam, and the properties of the foam produced are measured. Additive 1 is a long-chain chloroparaffin C24- C28 and is used to produce noninventive compositions. Additive 2 is methyl tosylate (Sigma- Aldrich®) and is used to produce noninventive compositions. Additive 3 is n-octyl tosylate (Tokyo Chemical Industry, TCI) and is used to produce noninventive compositions. Additives 2 and 3 are short-chain monomeric tosylates according to the prior art. Additive 4 is tetraethylene glycol bistosylate (abcr GmbH) and is used to produce inventive compositions. The production of additives 5 to 11 is described hereinafter.

[0175]

[0128] General description for production of the additives In advance of the syntheses of the aryl sulfonates according to the invention, their parent polyether alcohols (polyoxyalkylenes) were either acquired commercially (e.g. PTHF250 from BASF) or prepared by established methods that are described briefly hereinafter. The prior art includes various documents in which alcohols, carboxylic acids or amines are used as starter compounds for the alkoxylation reaction to give polyether alcohols (polyoxyalkylenes). A good overview of polyoxyalkylenes and processes for preparing polyoxyalkylenes is given by "N. Schonfeldt, Surface Active Ethylene Oxide Adducts, Pergamon Press, 1969".

[0176] The polyoxyalkylenes used as starting materials in association with the synthesis of the polyethersulfonic acid according to the invention are preferably colourless to yellow-orange liquids that are of low viscosity at room temperature (preferably up to about 1000 mPas), which may be clear or opaque.

[0177]

[0129] The polyether alcohols used in the context of this invention, if they were not acquired commercially, were prepared by the following method:

[0178] In the first step, a starter compound is reacted using a catalyst with epoxides, for example ethylene oxide, propylene oxide, butylene oxide or any mixtures of these epoxides. Catalysts used for the alkoxylation reaction are the alkaline catalysts known to those skilled in the art, such as potassium hydroxide, potassium hydroxide solution, sodium methoxide or potassium methoxide, or double metal cyanide compounds. Starter compound and catalyst are initially charged in the reactor at the start of the process prior to the metered addition of alkylene oxide, it being necessary to adjust the amount of catalyst so as to give sufficient catalytic activity for the process. The reaction temperature in the first step is preferably 80 to 220°C, more preferably 100 to 180°C. The pressure in the first step is preferably 0.5 bar to 20 bar, preferably 1 .0 bar to 12 bar (absolute).

[0179]

[0130] The epoxy monomers may be used in pure or mixed form, such that homopolymers or random copolymers are obtained. After the metered addition of a first monomer or a monomer mixture, further monomer may be metered in, such that block structures are obtained. It is also possible to effect continuous metered addition of a further epoxide over time into an epoxide already present in the reaction mixture in order to bring about an increasing concentration gradient of the continuously added epoxide. The correlations between metered addition and product structure are known to those skilled in the art.

[0180]

[0131] The end of the epoxide addition is typically followed by a period of further reaction to allow the reaction to proceed to completion. The further reaction can be conducted, for example, by continued reaction under reaction conditions (i.e. maintenance, for example, of the temperature and the pressure) without addition of reactants. Preferably, the further reaction is effected with mixing of the reaction mixture, especially with stirring.

[0181]

[0132] In an optional second step, residual monomers are removed in a vacuum distillation and, if required, the reaction product is neutralized with an acid such as lactic acid, acetic acid, propionic acid or phosphoric acid, and the salts formed are optionally removed by filtration.

[0182]

[0133] Reactors used for the alkoxylation in the first process step may in principle be any suitable reactor types that allow control over the reaction and its exothermicity. The first process step can be effected continuously, semi-continuously or else batchwise, in a manner known in chemical engineering.

[0134] For the polyether alcohols used here, the basis used for subsequent reactions is typically the number-average molar masses ascertained via determination of the hydroxyl number.

[0183] The preparation of the sulfonates according to the invention was in accordance with “Yoshida, Y.; Sakakura, Y.; Aso, N.; Okada, S.; Tanabe, Y.: Tetrahedron 1999, 55, 2183-2192”.

[0184]

[0135] For the obtaining of the poly ether toluenesulfonates, the following polyether precursors were prepared using the general synthesis description given above:

[0185] • polyethylene glycol) monomethyl ether having a number-average molar mass of 539 g / mol

[0186] • polypropylene glycol) monobutyl ether having a number-average molar mass of 700 g / mol

[0187] • poly(ethylene glycol)-b-poly(propylene glycol) monobutyl ether having a number-average molar mass of 660 g / mol

[0188] • polypropylene glycol) having a number-average molar mass of 485 g / mol

[0189] • bis-propoxylated polytetrahydrofuran having a number-average molar mass of 347 g / mol

[0190] • glycerol-based polypropylene glycol) having a number-average molar mass of 668 g / mol

[0191] • polyputylene oxide) monobutyl ether having a number-average molar mass of 731 g / mol

[0192]

[0136] Preparation of additive 5 - polyether tosylate 1

[0193] A 1 I four-neck round-bottom flask with precision glass stirrer, thermometer, jacketed coil condenser and dropping funnel with pressure equalization under a nitrogen atmosphere was charged with 170.9 g (0.32 mol, 1 eq) of polypthylene glycol) monomethyl ether having a number-average molar mass of 539 g / mol and 32.0 g (0.32 mol, 1 eq) of triethylamine. 3.1 g (0.03 mol, 0.1 eq) of trimethylammonium chloride was added while stirring. Subsequently, 50.3 g of p-toluenesulfonyl chloride (TsCI; 0.26 mol, 0.8 eq) dissolved in 250 ml of dichloromethane was added dropwise via a dropping funnel over the course of 60 min such that the temperature did not rise above 35°C. The reaction mixture was stirred at room temperature for 18 h. Then 100 ml of water was added, and the reaction mixture was transferred to a separating funnel. The phases were separated, and the organic phase was washed twice with 60 ml of 6 N HCI and four times with 200 ml of water. It was dried with magnesium sulfate, and the solvent was removed on a rotary evaporator at 45°C and 10 mbar. 147 g (72%) of a clear yellow liquid was obtained as product. The product was characterized by1H and13C NMR spectroscopy.

[0194] Polyether tosylate 1

[0195]

[0137] Preparation of additive 6 - polyether tosylate 2

[0196] A 2 I four-neck round-bottom flask with precision glass stirrer, thermometer, jacketed coil condenser and dropping funnel with pressure equalization under a nitrogen atmosphere was charged with 240.9 g (0.34 mol, 1 .0 eq) of polypropylene glycol) monobutyl ether having a number-average molar mass of 700 g / mol and 34.8 g (0.34 mol, 1.0 eq) of triethylamine. 3.3 g (0.03 mol, 0.1 eq) of trimethylammonium chloride was added while stirring. Subsequently, 59.1 g of p-toluenesulfonyl chloride (TsCI; 0.31 mol, 0.9 eq) dissolved in 200 ml of dichloromethane was added dropwise via a dropping funnel over the course of 35 min such that the temperature did not rise above 35°C. The reaction mixture was stirred at room temperature until complete conversion of the TsCI was established by TLC monitoring. Then 150 ml of water was added, and the reaction mixture was transferred to a separating funnel. The phases were separated, and the organic phase was washed four times with 120 ml of 6 N HCI and four times with 250 ml of saturated sodium chloride solution. It was dried with magnesium sulfate, and the solvent was removed on a rotary evaporator at 45°C and 10 mbar. 218.5 g (76%) of a clear orange-brown liquid was obtained as product. The product was characterized by1H and13C NMR spectroscopy.

[0197]

[0138] Preparation of additive 7 - polyether tosylate 3

[0198] A 2 I four-neck round-bottom flask with precision glass stirrer, thermometer, jacketed coil condenser and dropping funnel with pressure equalization under a nitrogen atmosphere was charged with 200 g (0.3 mol, 1 eq) of poly(ethylene glycol)-b-poly(propylene glycol) monobutyl ether having a numberaverage molar mass of 660 g / mol and 30.3 g (0.3 mol, 1 eq) oftriethylamine. 2.8 g (0.03 mol, 0.1 eq) of trimethylammonium chloride was added while stirring. Subsequently, 40.4 g of p-toluenesulfonyl chloride (TsCI; 0.21 mol, 0.7 eq) dissolved in 400 ml of dichloromethane was added dropwise via a dropping funnel over the course of 2 h such that the temperature did not rise above 35°C. The reaction mixture was stirred at room temperature for 4 h. Then 150 ml of water was added, and the reaction mixture was transferred to a separating funnel. The phases were separated, and the organic phase was washed twice with 60 ml of 6 N HCI and four times with 150 ml of water. It was dried with magnesium sulfate, and the solvent was removed on a rotary evaporator at 45°C and 10 mbar. 154 g (69%) of a clear yellow liquid was obtained as product. The product was characterized by1H and13C NMR spectroscopy.

[0199]

[0139] Preparation of additive 8 - polyether tosylate 4

[0200] A 1 I four-neck round-bottom flask with precision glass stirrer, thermometer, jacketed coil condenser and dropping funnel with pressure equalization under a nitrogen atmosphere was charged with 87.9 g (0.18 mol, 1 eq) of polypropylene glycol) having a number-average molar mass of 485 g / mol and 27.5 g (0.27 mol, 1 .5 eq) oftriethylamine. 1 .7 g (0.02 mol, 0.1 eq) of trimethylammonium chloride was added while stirring. Subsequently, 34.6 g of p-toluenesulfonyl chloride (TsCI; 0.18 mol, 1 eq) dissolved in 200 ml of dichloromethane was added dropwise via a dropping funnel over the course of 30 min such that the temperature did not rise above 35°C. The reaction mixture was stirred at room temperature until complete conversion of the TsCI was established by TLC monitoring. Then 100 ml of water was added, and the reaction mixture was transferred to a separating funnel. The phases were separated, and the organic phase was washed three times with 60 ml of 6 N HCI and four times with 100 ml of saturated sodium chloride solution. It was dried with magnesium sulfate, and the solvent was removed on a rotary evaporator at 45°C and 10 mbar. 92 g (80%) of a clear yellow-orange liquid was obtained as product. The product was characterized by1H and13C NMR spectroscopy. c + a = 8

[0201] Polyether tosylate 4

[0202]

[0140] Preparation of additive 9 - polyether tosylate 5

[0203] A 2 I four-neck round-bottom flask with precision glass stirrer, thermometer, jacketed coil condenser and dropping funnel with pressure equalization under a nitrogen atmosphere was charged with 145.5 g (0.30 mol, 1 eq) of polypropylene glycol) having a number-average molar mass of 485 g / mol and 59.7 g (0.59 mol, 2 eq) of triethylamine. 2.9 g (0.03 mol, 0.1 eq) of trimethylammonium chloride was added while stirring. Subsequently, 102.9 g of p-toluenesulfonyl chloride (TsCI; 0.54 mol, 1 .8 eq) dissolved in 300 ml of dichloromethane was added dropwise via a dropping funnel over the course of 2 h such that the temperature did not rise above 35°C. The reaction mixture was stirred at room temperature until complete conversion of the TsCI was established by TLC monitoring. Then 150 ml of water was added, and the reaction mixture was transferred to a separating funnel. The phases were separated, and the organic phase was washed three times with 120 ml of 6 N HCI and four times with 200 ml of saturated sodium chloride solution. It was dried with magnesium sulfate, and the solvent was removed on a rotary evaporator at 45°C and 10 mbar. 195 g (88%) of a clear yellow- orange liquid was obtained as product. The product was characterized by1H and13C NMR spectroscopy.

[0204] Polyether tosylate 5

[0205]

[0141] Preparation of additive 10 - polyether tosylate 6 A 2 I four-neck round-bottom flask with precision glass stirrer, thermometer, jacketed coil condenser and dropping funnel with pressure equalization under a nitrogen atmosphere was charged with 121.6 g (0.35 mol, 1 eq) of bis-propoxylated polytetrahydrofuran having a number-average molar mass of 347 g / mol and 70.1 g (0.69 mol, 2 eq) of triethylamine. 3.3 g (0.03 mol, 0.1 eq) of trimethylammonium chloride was added while stirring. Subsequently, 120.1 g of p-toluenesulfonyl chloride (TsCI; 0.63 mol, 1.8 eq) dissolved in 400 ml of dichloromethane was added dropwise via a dropping funnel over the course of 2 h such that the temperature did not rise above 35°C. The reaction mixture was stirred at room temperature until complete conversion of the TsCI was established by TLC monitoring. Then 150 ml of water was added, and the reaction mixture was transferred to a separating funnel. The phases were separated, and the organic phase was washed three times with 100 ml of 6 N HCI and four times with 200 ml of saturated sodium chloride solution. It was dried with magnesium sulfate, and the solvent was removed on a rotary evaporator at 45°C and 10 mbar. 150 g (72%) of a clear yellow-brown liquid was obtained as product. The product was characterized by1H and13C NMR spectroscopy.

[0206] Polyether tosylate 6

[0207]

[0142] Preparation of additive 11 - polyether tosylate 7

[0208] A 2 I four-neck round-bottom flask with precision glass stirrer, thermometer, jacketed coil condenser and dropping funnel with pressure equalization under a nitrogen atmosphere was charged with 210 g (0.31 mol, 1.0 eq) of glycerol-based polypropylene glycol having a number-average molar mass of 668 g / mol and 62.0 g (0.61 mol, 2.0 eq) of triethylamine. 3.8 g (0.04 mol, 0.1 eq) of trimethylammonium chloride was added while stirring. Subsequently, 89.9 g of p-toluenesulfonyl chloride (TsCI; 0.47 mol, 1.5 eq) dissolved in 250 ml of dichloromethane was added dropwise via a dropping funnel over the course of 20 min such that the temperature did not rise above 35°C. The reaction mixture was stirred at room temperature until complete conversion of the TsCI was established by TLC monitoring. Then 150 ml of water was added, and the reaction mixture was transferred to a separating funnel. The phases were separated, and the organic phase was washed three times with 100 ml of 6 N HCI and four times with 200 ml of saturated sodium chloride solution. It was dried with magnesium sulfate, and the solvent was removed on a rotary evaporator at 45°C and 10 mbar. 194 g (79%) of a clear pale yellow liquid was obtained as product. The product was characterized by1H and13C NMR spectroscopy.

[0209] Polyether tosylate 7

[0210]

[0143] Preparation of additive 12 - polyether tosylate 8

[0211] A 2 I four-neck round-bottom flask with precision glass stirrer, thermometer, jacketed coil condenser and dropping funnel with pressure equalization under a nitrogen atmosphere was charged with 241.2 g (0.33 mol, 1 eq) of poly(butylene oxide) monobutyl ether having a number-average molar mass of 731 g / mol and 33.1 g (0.33 mol, 1 eq) of triethylamine. 3.2 g (0.03 mol, 0.1 eq) of trimethylammonium chloride was added while stirring. Subsequently, 56.6 g of p-toluenesulfonyl chloride (TsCI; 0.30 mol, 0.9 eq) dissolved in 200 ml of dichloromethane was added dropwise via a dropping funnel over the course of 30 min such that the temperature did not rise above 35°C. The reaction mixture was stirred at room temperature until complete conversion of the TsCI was established by TLC monitoring. Then 100 ml of water was added, and the reaction mixture was transferred to a separating funnel. The phases were separated, and the organic phase was washed four times with 100 ml of 6 N HCI and four times with 200 ml of saturated sodium chloride solution. It was dried with magnesium sulfate, and the solvent was removed on a rotary evaporator at 45°C and 10 mbar. 211 g (75%) of a brown liquid was obtained as product. The product was characterized by1H and13C NMR spectroscopy.

[0212]

[0144] General production of the moulded polyurethane foams for testing of additives to improve properties after humid ageing or for determination of volatile components by thermodesorption analysis

[0213] The polyurethane foams were produced as moulded foams in the laboratory according to Formulations 1 , 2, 3 and 4. The foams were produced according to the details that follow at 22°C and an air pressure of 762 mmHg. The foams were produced using a heatable aluminium mould of dimensions 40 x 40 x 10 cm. The mould temperature was in each case 50 ± 2°C (Formulations 1 , 2 and 4) or 60 ± 2°C (Formulation 3). Before the foam was produced, the mould was treated with a solvent-based release agent.

[0214]

[0145] Table 1 : Formulation 1 : MDI, mould temperature 50°C, demoulding time 4 minutes

[0146] Table 2: Formulation 2, MDI, mould temperature 50°C, demoulding time 4 minutes

[0215]

[0147] Table 3: Formulation 3, TDI, mould temperature 60°C, demoulding time 5 minutes

[0216]

[0148] Table 4: Formulation 4, MDI, mould temperature 50°C, demoulding time 4.5 minutes

[0217]

[0149] Compounds used:

[0218] *1Arcol® 1374, polyether triol, Covestro AG

[0219] *2Voranol® CP 1421 Polyol, cell opener, The Dow Chemical Company

[0220] *3DABCO® DEOA 85 (diethanolamine 85% in water, crosslinker from Evonik® Industries AG)

[0221] *4water (demineralized, chemical blowing agent)

[0222] *5DABCO® NE 300, amine catalyst (blowing catalyst from Evonik® Industries AG, isocyanate-reactive blowing catalyst)

[0223] *6DABCO® NE 1600, amine catalyst (gel catalyst from Evonik® Industries AG, isocyanate-reactive gel catalyst, contains tin compounds)

[0224] *7TEGOSTAB® B 8734 LF 2 (foam stabilizer from Evonik® Industries AG)

[0225] *8Suprasec® 2447, MDI from Huntsman

[0226] *9DABCO® NE 1550 amine catalyst (gel catalyst from Evonik® Industries AG, isocyanate-reactive gel catalyst)

[0227] *10DABCO® DEOA 85 (diethanolamine 85% in water, crosslinker from Evonik® Industries AG)

[0228] *11Hyperlite® 1629, polyether triol, Covestro AG

[0229] *12Hyperlite® 1650, polyether triol SAN-filled, Covestro AG

[0230] *13TEGOSTAB® B 8761 LF 2 (foam stabilizer from Evonik®)

[0231] *14glycerol (crosslinker)

[0232] *15DESMODUR T80 index 90 (TDI from Covestro®)

[0233] *16DABCO® DMEA, amine catalyst (blowing catalyst from Evonik®)

[0234] *17TEGOAMIN® ZE 1 , amine catalyst (gel catalyst from Evonik®)

[0150] The moulded polyurethane foams according to Formulations 1 and 2 (MDI formulations) were each produced using 600 g of the polyol Arcol® 1374; for foams according to Formulation 4 (likewise MDI), 700 g of Arcol® 1374 was used. For production of the moulded polyurethane foams according to Formulation 3 (TDI formulation), 420 g of the polyol Hyperlite® 1629 and 180 g of the polyol Hyperlite® 1650 were used. The other formulation constituents were adjusted accordingly. For example, 1.0 part (1.0 pphp) of a component meant 1 .0 g of that substance per 100 g of polyol (Formulations 1 , 2 and 4: polyol is Arcol® 1374; Formulation 3: polyol is Hyperlite® 1629). For example, Formulation 1 contains 0.71 g of the crosslinker DABCO® DEOA 85 to 100 g of Arcol® 1374. The corresponding foam was produced by combining the polyols with the additive together with all the other formulation components apart from the diisocyanate, and mixing with a paddle stirrer at 1000 revolutions per minute for one minute to give a premix.

[0235]

[0151] Subsequently, within a few seconds, 337 g of methylene diphenyl diisocyanate (Formulations 1 , 2), 405 g of methylene diphenyl diisocyanate (Formulation 4) or 201 g of toluene diisocyanate (Formulation 3, isomer ratio of 2,4-toluene diisocyanate:2,6-toluene diisocyanate = 80:20) was added to the respective abovementioned premix, and the mixture was stirred at 2500 revolutions per minute for 7 seconds. The polymerizing and foaming reaction mixture was transferred into the aluminium mould within a few seconds, and the mould was closed until demoulding. After 4 minutes (Formulations 1 and 2) or after 5 minutes (Formulation 3) or after 4.5 minutes (Formulation 4), the product was removed as a finished foam pad. The foam body was compressed manually. The foam body was weighed and conditioned at constant temperature and air humidity for at least 168 hours before being cut to size, and further tests were conducted.

[0236]

[0152] Example 1 : Physical properties of the test foams

[0237]

[0153] The foams produced with the amounts of the additives used and the foam properties are mentioned in the tables that follow.

[0238]

[0154] Humid ageing and performance tests of foam properties

[0239]

[0155] a) Humid ageing

[0240] Humid ageing or hydrolysis ageing of the test specimens was conducted in accordance with DIN EN ISO 2440. This involved subjecting the test specimens to steam or 100% relative humidity at 120°C for 15 hours. After humid ageing, the test specimens were dried by placing them in a heated cabinet with air exchange at 70°C for 3 hours. For the sake of simplicity, measurement results for test specimens after humid ageing are labelled HA (humid aged), whereas results for test specimens without humid ageing are labelled amb (ambient).

[0241]

[0156] b) Measurement of compression hardness (compressive stress under compression) Compressive stress was determined both for unaged and for humid-aged foam test specimens of dimensions 7 x 7 x 3 cm under compression to 40% in accordance with DIN EN ISO 3386:2015-10. The respective test specimen of the unaged foam, after measurement of compressive stress, was then subjected to humid ageing and, after drying and conditioning, tested again for compressive stress. The measurements were reported in kilopascals. The decrease in compressive stress of the foam test specimen after humid ageing is also referred to as HALL (Humid Aged Load Loss).

[0242]

[0157] c) Measurement of compression set Five test specimens having dimensions of 5 cm x 5 cm x 2.5 cm were cut out of each of the finished foams. The starting thickness do was measured. Compression set CS (50% / 22 h / 70°C) was measured both for unaged and for humid-aged foam test specimens in accordance with DIN EN ISO 1856:2020-11 . For this purpose, the test specimens were compressed to half their thickness (i.e. to 12.5 mm) and then placed into an oven at 70 ± 1 °C for 22 hours. The decompression time before remeasurement of the thickness dr (after expansion) was 30 minutes. The results are reported in per cent according to the following formula: CS = (do-dr) / do x 100% (do = original thickness, dr = thickness after expansion). Compression set of the respective test specimens after humid ageing is also referred to as HACS (Humid Aged Compression Set).

[0158] d) Measurement of tensile strength and elongation at break

[0243] Tensile strength (at break) and elongation at break were determined in accordance with DIN EN ISO 1798:2008-04. Measured values for tensile strength are reported in kilopascals (kPa) and measured values for elongation at break in per cent (%).

[0244]

[0159] Table 5: Physical properties of the test foams according to Formulation 1 before and after humid ageing, amb = ambient - before humid ageing, HA = after humid ageing, 15 h, 120°C,

[0245] 100% relative humidity, amounts of the various additives given in pphp (see tables for Formulations 1 to 3).

[0246] CE = comparative example

[0247]

[0160] Table 5 continued:

[0248]

[0161] Table 5 shows the results for the measurements of the physical properties of the MDI foams with the inventive additives 4, 5, 7, 8, 9, 10, 11 and 12 by comparison with a foam without humid ageing additive (foam 1) and foams comprising noninventive additives 1 , 2 and 3 (foams 2, 3, 4 and 5). In the case of MDI foams, humid ageing generally results in deterioration in compression hardness (CLD) and compression set. The purpose of using humid ageing additives in MDI foams is to counteract the deterioration (increase) in compression set and avoid a significant decrease in compression hardness. For foam 1 without humid ageing additive, compression set after humid ageing is 31.5%. With the noninventive additive 1 (foam 2), an improvement to 23.7% is achieved. However, foam 2 has an undesirably high decrease in compression hardness of 46.5%. With noninventive additives 2 and 3, there is likewise a distinct improvement in compression set after humid ageing, but additives 2 and 3 have crucial drawbacks such as a major contribution to foam emissions and low stability in polyurethane systems, which will be illustrated in more detail later on. The use of the inventive additives surprisingly achieves very good values for compression set, which are in some cases below 25% and to some degree even below 21 %. The reduction in tensile strength at break after humid ageing is minimized by the use of the inventive additives by comparison with foam 1 .

[0249]

[0162] Table 6. Physical properties of the test foams according to Formulation 2 before and after humid ageing, amb = ambient - before humid ageing, HA = after humid ageing, 15 h, 120°C, 100% relative humidity, amounts of the various additives given in pphp.

[0250] CE = comparative example

[0251]

[0163] Table 6 shows the results of the measurements of the physical properties of the MDI foams according to Formulation 2 with inventive additives 5, 6 and 9 by comparison with a foam without humid ageing additive and a foam with noninventive additive 2. Formulation 2 differs from Formulation 1 in that DABCO® NE 1550 is used here as a purely aminic reactive gel catalyst. Just like the noninventive additive 2, the use of the inventive additives 5, 6 and 9 achieves a distinct improvement in compression set after humid ageing compared to the foam without additive (foam 19). All the additives mentioned likewise increase tensile strength at break after humid ageing.

[0252]

[0164] Table 7. Physical properties of the test foams according to Formulation 3 before and after humid ageing, amb = ambient - before humid ageing, HA = after humid ageing, 15 h, 120°C,

[0253] 100% relative humidity, amounts of the various additives given in pphp.

[0254] CE = comparative example

[0255]

[0165] Table 7 shows the results of the measurements of the physical properties of the TDI foams according to Formulation 3 with inventive additives 5, 9 and 1 1 by comparison with a foam without humid ageing additive and by comparison with noninventive additive 3. The TDI foams according to Formulation 3, by contrast with the MDI foams of Formulations 1 and 2, are generally even more sensitive to humid ageing, which is shown by the example of foam 26 (without additive). Unlike in the case of MDI foams, compression set is not critically lowered by humid ageing in the case of the TDI foams according to Formulation 3. The focus hereinafter will therefore lie particularly on the effect of the additives according to the invention on the change in compression hardness, tensile strength and elongation at break after humid ageing. The compression hardness of foam 26 (without humid ageing additive) declines crucially by 67.7% after humid ageing. Tensile strength and elongation at break is not measurable in the test specimens of foam 26 since they tear directly when pulled apart. Overall, the effect of the humid ageing in the case of foam 26 is thus a distinct deterioration in material properties. When the inventive additives 5, 9 and 11 are used, the decrease in compression hardness after humid ageing can always be limited to less than 43%, which testifies to an improvement in the mechanical integrity ofthe foams. In the case of foams 30, 31 and 32, excellent values for decreases in compression hardness of less than 25% are actually observed. The effect of the use of the additives is likewise a substantial improvement in tensile strength and elongation at break. It is also apparent when additives 5 and 11 are used that an increased use amount of the corresponding additive leads to a further increase in tensile strength.

[0256]

[0166] Example 2: Test method for determining the effect of additives on the rise time of polyurethane foam (test on free-risen foam)

[0257] For the determination of rise times, a mixture according to Formulation 2 was produced with all components apart from the methylene diphenyl diisocyanate (see above), and additionally admixed with 1 pphp of the appropriate additive. 108 g of the mixtures, after a storage time of 1 , 3, 6, 9 or 21 days, was stirred up at 1000 revolutions per minute for one minute, and then 56.2 g of methylene diphenyl diisocyanate (Suprasec 2447) was added. After the methylene diphenyl diisocyanate had been added, the already polymerizing mixtures were stirred at 2500 revolutions per minute for 7 seconds and introduced into an open, nearly cylindrical paper cup with a circular base of 168 cm2. A height measurement system (instrument type: FOAMAT® 285, measurement principle: ultrasound) was then used to determine the rise time required for the foam to reach 98% of its respective maximum height. The rise time of the freshly mixed system according to Formulation 2 without additive was about 87 + / - 2 seconds. When the foam rise process had still not ended after 5 minutes, a rise time of > 300 seconds was reported.

[0258]

[0167] Table 8. Effect of humid ageing additives on the rise time of polyurethane foam system (Formulation 2) after ageing for up to 21 days The rise time corresponds to the time measured until attainment of 98% of the maximum foam height and is shown in seconds (s). When the rise process had not yet ended after 5 minutes or 300 seconds, a rise time of > 300 seconds was reported; X = not measured.

[0259]

[0168] Table 8 shows the rise time of an MDI polyurethane foam system according to Formulation 2 which is required before the respective foam reaches 98% of its final height. For the foam system without additive, rise times of 87-90 seconds were measured from the measurement immediately after the mixing up to the foaming after a storage time of the system of 21 days. The small variance of 3 seconds shows that the reactivity of the system is unchanged or almost unchanged over the period of 21 days or three weeks.

[0260]

[0169] Use of the noninventive additive 1 results in only minimal changes in rise time of less than five seconds over the measurement period. The use of the noninventive additive 2 (methyl tosylate), by contrast, directly after blending of the system without further ageing, leads directly to an extension to 102 seconds and hence to a distinct delay in rise characteristics. After ageing of the system with additive 2 for one day, it was foamed again. This time there was an extreme delay in rise characteristics, such that the foam rise process was still not complete even after 300 seconds. The test system with the noninventive additive 3 immediately after blending has no delay compared to the formulation without additive. After 21 days, however, an increased rise time of 1 10 seconds is measured. When the inventive polyether tosylates 1 , 3, 5, 6, 7 and 8 are used, a slight increase in rise time after 21 days is observed only in the case of polyether tosylates 1 and 6. Polyether tosylates 3, 5, 7 and 8 surprisingly have only a negligibly small influence, if any, on rise time after ageing for up to 21 days. Thus, these polyether tosylates provide high system stability (negligible effect on rise time after ageing) with a very good improvement in physical properties after humid ageing.

[0261]

[0170] Example 3: Thermodesorption analysis for foams according to VDA 278

[0262]

[0171] By thermodesorption analysis according to VDA 278, foams (according to Formulation 4) both with additives according to the prior art and the additives according to the invention were examined. The emissions assigned to an additive were determined by measurement of the VOC or FOG value of the respective foam and subtraction of the blank value that was measured in the analysis of a foam without additive. Example: VOC (additive in foam 33) = VOC (foam 33) - VOC (reference foam without additive). Table 9 lists the additives used and the results of the measurements.

[0172] The materials are characterized with regard to the type and the amount of the organic substances outgassable therefrom. To this end, two semi-quantitative empirical values are determined to enable estimation of the emission of volatile organic compounds (VOC value), and the proportion of condensable substances (FOG value). Individual substances from the emission are also determined. In the analysis, the samples are thermally extracted and the emissions are separated by gas chromatography and detected by mass spectrometry. The overall concentrations thus obtained for the VOC fraction are calculated in toluene equivalents and provide the VOC value as a result; the FOG fraction is given in hexadecane equivalents and provides the FOG value.

[0263]

[0173] The analysis method serves to determine emissions from non-metallic materials used for moulded parts in motor vehicles; they also include foams. In thermodesorption analysis (TDA), small amounts of material are heated up in a desorption tube in a defined manner and the volatile substances emitted in the course of heating are cryofocused by means of an inert gas stream in a cold trap of a temperature-programmable evaporator. After the heating phase has ended, the cold trap is rapidly heated to 280°C. This evaporates the focused substances. They are subsequently separated in the gas chromatography separation column and detected by mass spectrometry. Calibration with reference substances permits a semi-quantitative estimate of the emission, expressed in “pg / g”. The quantitative reference substances used are toluene for the VOC analysis (VOC value) and n-hexadecane for the FOG value. Signal peaks can be assigned to substances using their mass spectra and retention indices. Source: VDA 278 / 10.2011 , www.vda.de

[0264]

[0174] The amount of benzaldehyde determined is based on toluene equivalents (mg / g). Test specimen analysis: sample preparation, sampling and specimen dimensions

[0265]

[0175] After the foams have been demoulded, they are stored at 21 °C and about 50% relative humidity for 24 hours. Samples of the moulding are then taken at suitable and representative sites distributed uniformly across the width of the (cooled) moulding. The foams are then wrapped in aluminium foil and sealed in a polyethylene bag. The amount of the foam samples introduced into the desorption tube is 10-15 mg in each case. Test procedure: VOC / FOG thermodesorption:

[0266]

[0176] The sealed samples are sent for direct determination immediately after receipt. The samples are weighed on an analytical balance to an accuracy of 0.1 mg before commencement of the analysis and the corresponding amount of foam is placed centrally in the desorption tube. A helium stream is passed over the sample and the latter is heated to 90°C for 30 minutes. All volatile substances are collected in a cold trap cooled with liquid nitrogen. After 30 minutes the cold trap is heated to 280°C. The evaporating substances are separated from one another using the described gas chromatography column and then analysed by mass spectrometry.

[0267]

[0177] GC-MS instrument parameters The following instrument is used for the analysis: Gerstel, D- 45473 Muhlheim an der Ruhr, Eberhard-Gerstel-Platz 1 , TDS-3 I KAS-4, Tenax® desorption tubes, Agilent Technologies 7890A (GC) I 5975C (MS), column: HP Ultra2 (50 m, 0.32 mm, 0.52 mm), carrier gas: helium.

[0268]

[0178] Table 9: Additive-related foam emissions by thermodesorption analysis according to

[0269] VDA 278 Amount of additive given in pphp, amount of VOC and FOG based on the proportion in the mass of foam given in ppm, amounts of the various additives given in pphp.

[0270]

[0179] Additive 1 has very low contributions to foam emissions of only 10 ppm both in the VOC and in the FOG range. Even though foam emissions from additive 1 are low, the emission of toxic hydrochlorocarbon compounds is undesirable.

[0180] In the case of noninventive additives 2 and 3 (short-chain monomeric tosylates), with a use amount of 1 pphp, comparatively high emissions of 90-113 ppm in the VOC range are found. For the inventive polyether tosylates (including additive 4 - tetraethylene glycol bistosylate), with use amounts of 1-2 pphp, only low VOC values below 50 ppm are found, which shows that the polyether tosylates, by comparison with the low molecular weight tosylates, have not only distinctly better system stability (negligible effect on rise time after ageing) and an improvement in physical properties after humid ageing, but also an advantageous VOC and emissions profile. The FOG values of the foams with the polyether tosylates are likewise very low compared to additive 3 - especially for polyether tosylates 2 and 7.

Claims

Claims1 . A composition for production of a polyurethane foam, comprising:(a) a polyol,(b) an amine catalyst,(c) blowing agent, preferably water,(d) aryl sulfonate as per compound (I)where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,R5is hydrogen, 2,6-di-tert-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii),where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + b + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

2. The composition according to Claim 1 , wherein the aryl sulfonate (b) is aryl sulfonate as per compound (I2):where a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen,each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,R5is hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii),where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12,when R5is the radical of formula (ii), the sum of a + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

3. The composition according to any of Claims 1 and 2, wherein the composition further contains (e) a compound having isocyanate-functional groups or the composition does not contain (e) a compound having isocyanate-functional groups.

4. The composition according to any of the preceding claims, wherein the compound having isocyanate-functional groups comprises hexamethylene diisocyanate (HDI), phenylene diisocyanate (PDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and / or isophorone diisocyanate (I PDI), preferably toluene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI), especially preferably toluene diisocyanate (TDI).

5. The composition according to any of the preceding claims, wherein the amine catalyst (b) is selected from the group consisting of triethylenediamine, 1 ,4-diazabicyclo[2.2.2]octane-2- methanol, diethanolamine, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1 ,3-propanediamine, 2- [[2-(2-(dimethylamino)ethoxy)ethyl]methylamino]ethanol, 1 ,1 '-[(3-{bis[3- (dimethylamino)propyl]amino}propyl)imino]dipropan-2-ol, [3-(dimethylamino)propyl]urea, 1 ,3-bis[3- (dimethylamino)propyl]urea, amine catalysts of the general structure (1a) and / or amine catalysts of the general structure (1 b):where each Y is independently -NRVIIIRIXor -ORIX,R1is a linear, cyclic, aliphatic or aromatic hydrocarbon having 1-8 carbon atoms, optionally functionalized with an -OH group or hydrogen,R" is a linear, cyclic, aliphatic or aromatic hydrocarbon having 1-8 carbon atoms, optionally functionalized with an -OH group or hydrogen,X is oxygen, nitrogen, hydroxyl, amines of the structure -NRIH- or -NRIHRIVor urea groups of the structure -NRVCONRVI- or -NRVIICONRVIRV", each RIII IXis independently a linear, cyclic, aliphatic or aromatic hydrocarbon having 1-8 carbon atoms, optionally functionalized with an -OH group, an -NH- or -NH2 group or hydrogen, m = 0 to 4, preferably 2 or 3, n = 2 to 6, preferably 2 or 3, i = 0 to 3, preferably 0-2,where Rxis hydrogen, or a linear, branched or cyclic aliphatic or aromatic hydrocarbon which has 1- 18 carbon atoms and is optionally substituted by a hydroxyl group and / or optionally substituted by an -NH2 group,Z is oxygen, -NRX- or -CH2.

6. The composition according to any of the preceding claims, wherein the composition further contains a blowing catalyst, preferably 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3- aminopropylbis(aminoethyl) ether and / or bis(dimethylamino)ethyl ether.

7. The composition according to any of the preceding claims, wherein the composition further contains a metal catalyst, the metal catalyst preferably being an organometallic metal salt, organic metal salt, inorganic metal salt and / or organometallic compound, where the metal is Sn, Bi, Zn, Al or K, preferably Sn, Zn and / or Bi.

8. The composition according to any of the preceding claims, wherein the molecular weight of the aryl sulfonate (d) is 300 g / mol to 20 000 g / mol, preferably 340 g / mol to 10 000 g / mol, especially preferably 400 g / mol to 5000 g / mol, more preferably 450 g / mol to 2000 g / mol, especially preferably 500 g / mol to 1000 g / mol.

9. The composition according to any of the preceding claims, wherein the compound (I) is selected from the group consisting of compound (11), compound (I2), compound (I3), compound (I4), compound (I5), compound (I6), compound (I7), compound (I8), compound (I9), compound (110), compound (11 1), compound (112), compound (113), compound (114), compound (115), compound (116), compound (117), compound (118), compound (119), compound (I20), compound (121), compound (I22), compound (I23) or combinations thereof:(123).

10. The composition according to any of the preceding claims, wherein the formula (i) is the formula (i1):

11. The composition according to any of the preceding claims, wherein each R1is methyl, and each R2is hydrogen.

12. The composition according to any of the preceding claims, wherein the formula (ii) is selected from the group consisting of formula (ii1), formula (ii2), formula (ii3), formula (ii4) or combinations thereof:

13. The composition according to any of the preceding claims, wherein the composition contains:(a) polyol in an amount of 50% to 98% by weight, preferably 70% to 97% by weight, more preferably 80% to 96% by weight, especially preferably 85% to 95% by weight, based on the total weight of the composition, and / or(b) amine catalyst in an amount of 0.01% to 5% by weight, preferably 0.05% to 3.5% by weight, more preferably 0.08% to 2.5% by weight, especially preferably 0.1% to 1 .5% by weight, based on the total weight of the composition, and / or(c) water in an amount of 0.02% to 10% by weight, preferably 0.1 % to 8% by weight, more preferably 1 % to 7% by weight, especially preferably 1 .5% to 5% by weight, based on the total weight of the composition, and / or(d) aryl sulfonate in an amount of 0.01 % to 7% by weight, preferably 0.1 % to 6% by weight, more preferably 0.3% to 5% by weight, especially preferably 0.5% to 4% by weight, based on the total weight of the composition.

14. A method of producing a polyurethane foam, comprising(A) providing the composition according to any of the preceding claims,(B) mixing the composition from step (A) with a compound having isocyanate- functional groups, and(C) producing the polyurethane foam from the mixture obtained in step (B).

15. Use of an aryl sulfonate of formula (I) in the production of a polyurethane foam:a is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, b is 0 to 20, preferably 0 to 15, more preferably 0 to 12, especially preferably 0, c is 0 to 20, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of a + c is 0 to 20, preferably 3 to 15, especially preferably 4 to 12, each R1is independently hydrogen, methyl or ethyl, especially preferably methyl, each R2is independently hydrogen, methyl or ethyl, especially preferably hydrogen, each R3is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R4is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl,R5is hydrogen, 2,6-di-tert-butyl-4-methylphenyl, alkyl radical C1-C16, -C(O)Me, a radical of formula (i) or a radical of formula (ii), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n-octyl, n- dodecyl, a radical of formula (i) or a radical of formula (ii), especially preferably hydrogen, a radical of formula (i) or a radical of formula (ii),where R6is hydrogen, phenyl or an alkyl radical C1-C10, preferably hydrogen, methyl or ethyl, each R7is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R8is independently hydrogen, phenyl or an alkyl radical C1-C16, preferably hydrogen, methyl or ethyl, especially preferably methyl, each R9is independently hydrogen, 2,6-di-terf-butyl-4-methylphenyl, alkyl radical C1-C16, - C(O)Me, a radical of formula (i), preferably hydrogen, methyl, ethyl, isopropyl, n-butyl, n- octyl, n-dodecyl, a radical of formula (i), especially preferably hydrogen or a radical of formula (i),Y is oxygen or -CH2-O-, d is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, e is 0 to 25, preferably 1 to 20, more preferably 2 to 15, especially preferably 2 to 12, the sum of d + e is 0 to 20, preferably 1 to 15, especially preferably 4 to 12, when R5is not the radical of formula (ii), the sum of a + b + c is 4 to 20, preferably 4 to 15, especially preferably 4 to 12, when R5is the radical of formula (ii), the sum of a + b + c + d + e is 4 to 40, preferably 4 to 30, more preferably 5 to 25, especially preferably 6 to 20.

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