PROCESS FOR PRODUCING A POLYURETHANE FOAM, PROCESS FOR REDUCING ALDEHYDE EMISSIONS FROM A POLYURETHANE FOAM, AND POLYURETHANE FOAM

Abstract

PROCESS FOR PRODUCING A POLYURETHANE FOAM, PROCESS FOR REDUCING ALDEHYDE EMISSIONS, POLYURETHANE FOAM, AND POLYETHER-POLYOL. Polyurethane foams are produced by curing a reaction mixture containing an aromatic polyisocyanate, at least one isocyanate-reactive material having an average functionality of at least 2 and an equivalent weight of at least 200 per isocyanate-reactive group, at least one blowing agent, at least one surfactant and at least one catalyst, a certain β-diketone compound and at least one water-soluble amino-functional polymer. The foams thus produced emit low levels of aldehydes.

Description

"PROCESS FOR PRODUCING A POLYURETHANE FOAM, PROCESS FOR REDUCING ALDEHYDE EMISSIONS FROM A POLYURETHANE FOAM AND POLYURETHANE FOAM"

[0001] This invention relates to polyether-polyols and polyurethanes having low aldehyde content and to methods for producing such polyurethanes.

[0002] Polyurethane foams are used in many applications in offices, homes, and vehicles. They are used, for example, in appliance applications and as padding for bedding and furniture. In cars and trucks, polyurethanes are used as seat padding, in headrests, in control panels and instrument panels, in armrests, in headliners, as noise, vibration and harshness attenuation features, as acoustic attenuation features, and other applications.

[0003] These polyurethanes often emit varying levels of aldehydes, such as formaldehyde, acetaldehyde, and propionaldehyde. Due to the cellular structure of these foams, the aldehydes contained within the foam easily escape into the atmosphere. This can present odor and exposure problems, especially when people or animals are exposed to the material within an enclosed space. Vehicle manufacturers are imposing stricter limits on emissions from materials used in passenger cabins of cars, trucks, buses, trains, and aircraft.

[0004] Sequestrants are sometimes used to reduce aldehyde emissions from various types of materials. In the field of polyurethane, for example, there is WO 2006 / 111492, which describes the addition of antioxidants and hindered amine light stabilizers (HALS) to polyols to reduce aldehydes. WO 2009 / 114329 describes the treatment of polyols with certain types of amino alcohols and the treatment of polyisocyanates with certain nitroalkanes in order to reduce aldehydes in polyols and polyisocyanates, respectively, and in polyurethanes made from these materials. JP 2005-154599 describes the addition of boron. Petition 870250047619, dated 06 / 06 / 2025, p. 9 / 41 2 / 28 Alkaline metal hydride is added to a polyurethane formulation for this purpose. US Patent No. 5,506,329 describes the use of certain aldimine oxazolidine compounds to sequester formaldehyde from preparations containing polyisocyanate and describes nitroalkanes and amino alcohols as formaldehyde scavengers in textile and plywood applications. Document EP 1428847A describes the use of various polyamine compounds to sequester formaldehyde.

[0005] These approaches provide limited benefits, in part because the aldehydes present in polyurethane foam are not always introduced from the raw materials used to produce the foam. Formaldehyde and acetaldehyde in particular can form during the curing stage or when the foam is later subjected to UV light, high temperatures, or other conditions.

[0006] Document WO 2018 / 148898 describes the use of amino alcohols along with certain antioxidants to reduce aldehyde emissions from polyurethane foam. This combination provides some improvement, but a greater reduction in aldehyde emissions is desired.

[0007] Certain acetoacetamide compounds are described as aldehyde scavengers for polyurethane foam in U.S. Patent No. 10,196,493 and in U.S. Published Patent Application No. 2019-0119460. Certain cyclic β-diketones are described as aldehyde scavengers in document PCT / CN19 / 103566.

[0008] A method for effectively and economically reducing aldehyde emissions is desired. Preferably, this method does not result in a significant alteration in the properties or performance of polyurethane.

[0009] This invention is a process for producing a polyurethane foam comprising forming a reaction mixture containing an aromatic polyisocyanate, at least one isocyanate-reactive material having an average functionality of at least 2 and an equivalent weight of at least 200 grams per mole of isocyanate-reactive groups, at least one blowing agent, at least one surfactant and at least one catalyst, and curing the Petition 870250047619, dated 06 / 06 / 2025, page 10 / 41 3 / 28 reaction mixture to form a polyurethane foam, wherein the curing is carried out in the presence of (i) at least one β-diketone compound, wherein the β-diketone compound is a compound represented by structure I: Oo IIII .C..0. R1X R2 / \HH(I) wherein R1 and R2 are independently selected from hydrogen, NH2, -NH-R3-N(R4)2, -OR4 and -R4, wherein each R3 and R4 is independently an unsubstituted hydrocarbon or a hydrocarbon substituted with one or more of O, N, S, P or halogen, provided that R1 and R2 together can form a divalent radical, and additionally provided that at least one of R1 and R2 is not hydrogen, and (ii) at least one water-soluble amino-functional polymer having a number average molecular weight of at least 300 and at least 3 primary and / or secondary amino groups per molecule.

[0010] The invention is also a process for reducing aldehyde emissions from a polyurethane foam comprising: a) combining (i) at least one β-diketone compound which is a compound represented by structure I: O o II II R1 xc R2 / \ H H wherein R1 and R2 are independently selected from hydrogen, NH2, -NH-R3-N(R4)2, -OR4 and -R4, wherein each R3 and R4 is independently an unsubstituted hydrocarbon or a hydrocarbon substituted with one or more of O, N, S, P or halogen, provided that R1 and R2 together can form a divalent radical and additionally provided that at least one of R1 and R2 is not hydrogen, and (ii) at least one water-soluble amino-functional polymer having a number-average molecular weight of at least 300 and at least 3 amino groups Petition 870250047619, dated 06 / 06 / 2025, page 11 / 41 4 / 28 primary and / or secondary per molecule, with at least one isocyanate-reactive material having an average functionality of at least 2 and an equivalent weight of at least 200 grams per mole of isocyanate-reactive groups to form a mixture and then b) combine the mixture from step a) with at least one organic polyisocyanate and cure the resulting reaction mixture in the presence of at least one blowing agent, at least one surfactant and at least one catalyst to form a polyurethane foam.

[0011] The invention is also a polyurethane foam made in any of the processes mentioned above.

[0012] The invention is also a process for reducing aldehyde emissions from a polyether-polyol, comprising combining 0.01 to 5 parts by weight of at least one β-diketone compound and 0.01 to 5 parts by weight of at least one water-soluble amino-functional polymer having a number-average molecular weight of at least 300 and at least 3 primary and / or secondary amino groups per molecule with 100 parts by weight of the polyether-polyol, wherein the β-diketone compound is represented by structure I: O o II II R1 XC R2 / \ H H wherein R1 and R2 are independently selected from hydrogen, NH2, -NH-R3-N(R4)2, -OR4 and -R4, wherein each R3 and R4 is independently an unsubstituted hydrocarbon or a hydrocarbon substituted by one or more of O, N, S, P or halogen, provided that R1 and R2 together can form a divalent radical and additionally provided that at least one of R1 and R2 is not hydrogen.

[0013] The invention is also a polyether-polyol having a hydroxyl equivalent weight of at least 200 grams per hydroxyl group equivalent, which polyether-polyol contains 0.01 to 5 parts by weight of at least one β-diketone compound and 0.01 to 5 parts by weight of at least one water-soluble amino-functional polymer having a number average molecular weight of at least 300 Petition 870250047619, dated 06 / 06 / 2025, page 12 / 41 5 / 28 and at least 3 primary and / or secondary amino groups per molecule with 100 parts by weight of the polyether-polyol, wherein the β-diketone compound is represented by structure I: Oo IIII .C..0. R1X ^R2 / \ H H wherein R1 and R2 are independently selected from hydrogen, NH2, -NH-R3-N(R4)2, -OR4 and -R4, wherein each R3 and R4 is independently an unsubstituted hydrocarbon or a hydrocarbon substituted by one or more of O, N, S, P or halogen, provided that R1 and R2 together can form a divalent radical and additionally provided that at least one of R1 and R2 is not hydrogen.

[0014] It has been observed that the presence of both the β-diketone compound and the water-soluble amino-functional polymer reduces the aldehyde content emitted by polyurethane foam and polyether-polyol. The performance of the combination is far superior to the expected performance of the β-diketone compound alone and the amino-functional polymer alone. In some embodiments, the β-diketone compound has the added advantage of being reactive to isocyanate groups. As such, it reacts during the curing step to be incorporated into the polyurethane polymer structure. This further reduces emissions of organic compounds. At least some of the structure I β-diketone compounds are resistant to hydrolysis, which reduces the generation and possible emission of volatile hydrolysis byproducts.

[0015] In structure I, each R3 and R4 can independently be aromatic, aliphatic, alicyclic, or any combination thereof. R3 and R4 can be independently substituted by O, N, S, P, or halogen atoms. Oxygen-containing substituents can be, for example, carbonyl, hydroxyl, ester, carbonate, or ether groups. Each R4 preferably has up to 50 carbon atoms, more preferably up to 10 carbon atoms, up to 6 carbon atoms, or up to 4 carbon atoms. R3, when present, preferably has... Petition 870250047619, dated 06 / 06 / 2025, page 13 / 41 6 / 28 up to 10, up to 6, up to 4 or up to 2 carbon atoms. In a specific embodiment, each R4 may independently be alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl and the like (including any isomers of any of the aforementioned); cyclohexyl; alkyl-substituted cyclohexyl; phenyl and alkyl-substituted phenyl, in each case preferably having up to 10, especially up to 6 carbon atoms.

[0016] In some embodiments R1 and R2 together form a divalent radical, and, in this case, the β-diketone compound is a cyclic compound in which a -C(O)-CH2-C(O)- moiety forms part of a ring structure together with the divalent radical formed by R1 and R2.

[0017] The β-diketone compound preferably has a molecular weight of up to 290 g / mol, more preferably up to 250 g / mol.

[0018] In some embodiments, the β-diketone compound is an acetoacetate ester or an acetoacetate amide characterized by having one or more acetoacetate ester or acetoacetate amide groups having structure II: Oo III .c. —XC R / \ H H (||) with R5 being a substituted or unsubstituted C1-C6 alkyl group or a substituted or unsubstituted aryl group, preferably a C1 or C2 alkyl group, and X is -O- in the case of an ester and -NH- in the case of an amide. R5 is most preferably methyl. The acetoacetate ester or acetoacetate amide may have two or more such acetoacetate ester or acetoacetate amide groups. Among the suitable acetoacetate esters and acetoacetate amides are those represented by structure II: (III) Petition 870250047619, dated 06 / 06 / 2025, p. 14 / 41 7 / 28 wherein A is a linking group, n is at least 1, and R5 and X are as described with respect to structure II. A may be, for example, an unsubstituted or substituted linear or branched C1-C30 alkyl, aryl, arylalkyl, or alkyl group, and the substituents may optionally be or include one or more of O, N, S, P, or halogen. Oxygen-containing substituents may be, for example, carbonyl, hydroxyl, ester, carbonate, or ether groups. n may be, for example, 1 to 100, 1 to 20, 1 to 10, or 1 to 4. n is preferably at least 2 when X is oxygen.

[0019] Useful acetoacetate compounds include those described in documents JP 2005-06754A, JP 2005-179423A and in US publication no. 2016 / 0304686.

[0020] In some embodiments, X in structure III is oxygen, n is at least 2, and A is the residue of a polyalcohol after the removal of one or more -OH groups. The acetoacetate compound in such a case is an acetoacetate ester or polyester of an alcohol that has the form A(OH)x, where x is equal to or greater than n. Examples of acetoacetate esters include mono- and polyacetoacetate esters of polyols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, trimethylolethane, trimethoxymethane, erythritol, pentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, mannitol, glucose, fructose, sucrose, 1,2,3,4,5,6-hexahydroxyhexane, and the like.

[0021] Specific acetoacetate ester compounds include, for example, trimethylolpropane mono-, di- or triacetoacetate ester, trimethylolethane mono-, di- or triacetoacetate ester, trimethoxymethane mono-, di- or triacetoacetate ester; ethylene glycol mono- or diacetoacetate ester; 1,2-propylene glycol mono- or diacetoacetate ester, 1,3-propylene glycol mono- or diacetoacetate ester, pentaerythritol mono-, di-, tri- or tetra-acetoacetate ester, glycerin mono-, di-, triacetoacetate ester, diethylene glycol mono- or diacetoacetate ester, dipropylene glycol mono- or diacetoacetate ester, triethylene glycol mono- or diacetoacetate ester, ester of Petition 870250047619, dated 06 / 06 / 2025, page 15 / 41 8 / 28 erythritol mono, di, tri or tetraacetoacetate, ester of mono, di, tri, tetra, penta or hexaacetoacetate of n-hexane, ester of mono, di, tri, tetra, penta or hexaacetoacetate of sorbitol and ester of mono or diacetoacetate of 1,4-butanediol.

[0022] In some embodiments, X in structure III is -NH-, n is one or more, and A is the residue of an amine or polyamine after the removal of one or more NH2 groups. The acetoacetate compound in such a case is an acetoacetate amide or polyamide of an amine having the form A(NH2)x, where x is equal to or greater than n. An example of such an amide compound is H (AcAcNPh).

[0023] In specific embodiments, the β-diketone compound is a 3-oxopropanamide compound represented by structure IV: (IV), wherein R8 is hydrogen or a hydrocarbon group, R6 is hydrogen, hydrocarbon, hydroxyalkyl or aminoalkyl, R7 is hydroxyalkyl or aminoalkyl and n is at least 1. In some embodiments, R6 is hydrogen or an aminoalkyl or hydroxyalkyl group having up to 6, preferably 2 to 4, carbon atoms. R6 is most preferably hydrogen. R7 is preferably hydroxyalkyl having up to 6, especially 2 to 4, carbon atoms. R7 is most preferably 2-hydroxyethyl (-CH2-CH2-OH) or 2-hydroxypropyl (-CH2CH(CH3)-OH). n is preferably from 1 to 6, most preferably from 1 to 4. In specific embodiments, n may be 1, 2, 3 or 4. n is most preferably 1.

[0024] In some embodiments, R8 is phenyl or alkyl having up to 6 carbon atoms, R6 is hydrogen, R7 is 2-hydroxyethyl or 2-hydroxypropyl and is 1. A particularly preferred 3-oxopropanamide is N-(2-hydroxyethyl)-3-oxobutanamide, Petition 870250047619, dated 06 / 06 / 2025, page 16 / 41 9 / 28 which corresponds to structure IV in which R8 is methyl, R6 is hydrogen, R7 is 2-hydroxyethyl and is 1.

[0025] In still other embodiments, the β-diketone compound is a cyclic compound characterized by having at least one: moiety as part of a ring. The ring may contain, for example, 4, 5, or 6 ring atoms. The ring atoms (in addition to the atoms of the 1,3-diketone structure that form part of the ring) may be, for example, carbon, nitrogen, and / or oxygen atoms.

[0026] Among the suitable cyclic β-diketone compounds are those represented by the structure (V) where X, Y, Z are independently carbonyl, -C(R9R10)-, -NR11-, -O- or a chemical bond. Each R9 and R10 are independently H, a substituted or unsubstituted linear or branched alkyl or alkylene group having from 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a halogen, -CO2CH3, or -CN, provided that any two or more of R9 and R10 may be intra- or intermolecularly connected and each R11 is independently H, a substituted or unsubstituted linear or branched alkyl or alkylene group having from 1 to 10 carbon atoms or a substituted or unsubstituted phenyl group. Substituents on the R9, R10 and R11 groups may optionally include N, O, S, P and / or halogen atoms.

[0027] Other suitable cyclic β-diketones are represented by structure VI: Petition 870250047619, dated 06 / 06 / 2025, p. 17 / 41 10 / 28 HL O OK / CHG / O R12 R12(VI) wherein Z is carbonyl, -C(R13R14)-, -NR15-, -O- or a chemical bond, each R12, R13 and R14 is independently H, a linear or branched substituted or unsubstituted alkyl or alkylene group having from 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, a halogen, -CO2CH3, or -CN, provided that any two or more of R12, R13 and R14 may be intra- or intermolecularly connected and each R15 is independently H, a linear or branched substituted or unsubstituted alkyl or alkylene group having from 1 to 10 carbon atoms or a substituted or unsubstituted phenyl group.

[0028] R12, R13, R14 and R15, when substituted by heteroatoms, are preferably substituted by only nitrogen and / or oxygen atoms. The oxygen substituents may be, for example, ether, carboxyl or hydroxyl oxygens. The nitrogen substituents may be primary or secondary amino, imido or starch nitrogens.

[0029] As specific β-dicetonas cíclicas incluem, for example, ciclo-hexano1,3,5-triona, 1,3-ciclo-hexanodiona, pyrazolidina-3,5-diona, 1,2-dimethylpyrazolidina3,5-diona, 1-methylpyrazolidina-3,5-diona, 1,1-dimethyl-cyclopentan-2,4-diona, 1-ethylcyclo-hexan-2,4-diona, 1,1-diethyl-cyclo-hexan-3,5-diona, 6-methyl-pyran-2,4-diona, 6ethyl-pyran-2,4-diona, 6-isopropyl-pyran-2,4-diona, 6-(n)-butyl-pyran-2,4-diona, 6isobutyl-pyran-2,4-diona, 6-pentyl-pyran-2,4-diona, 6-isopentyl-pyran-2,4-diona, 6,7di-hidrociclopenta[b]pyran-2,4(3H,5H)-diona, 5,6,7,8-tetra-hidro-croman-2,4-diona, croman-2,4-diona, 6-trans-propenyl-di-hidro-piran-2,4-diona, 1-oxaespiro-[5,5]undecan-2,4-diona, 2,2-dipropyl-[1,3]-dioxan-4,6-diona, 2-phenyl-[1,3]-dioxan-4,6diona, 6,10-dioxa-espiro-[4,5]-decan-7,9-diona, 1,5-dioxa-espiro-[5,5]-undecan2,4-diona, 1-methyl-2,4,6-trioxo-hexa-hidro-pyrimidine, 1-ethyl-2,4,6-trioxo-hexa-hidro-pyrimidine, 1-phenyl-2,4,6-trioxo-hexa-hidro-pyrimidine, s-indaceno-1,3,5,7(2H,6H)tetraona, furan-2,4(3H,5H)-diona, 3,3'-(hexano-1,1 -di-yl)bis(1 -methylpyrimidine, Petition 870250047619, 06 / 06 / 2025, pág. 18 / 41 11 / 28 2,4,6(1 H,3H,5H)-triona), 2,2-dimethyl-1,3-dioxane-4,6-diona, furan-2,4(3H,5H)diona, pyrimidine-2,4,6(1H,3H,5H)-triona and 1,3-dimethylpyrimidine-2,4,6(1H, 3H,5H)triona.

[0030] The water-soluble amino-functional polymer has a number-average molecular weight of at least 300 g / mol. The molecular weight may be at least 500 g / mol and may be up to, for example, 1,000,000 g / mol, up to 500,000 g / mol, up to 250,000 g / mol, up to 100,000 g / mol, up to 25,000 g / mol, up to 10,000 g / mol, up to 5,000 g / mol or up to 2,000 g / mol. The water-soluble amino-functional polymer has at least 3 primary and / or secondary amino groups per molecule. It may contain at least 5, at least 10, at least 20 or at least 50 primary and / or secondary amino groups and may contain up to 20,000 primary and / or secondary amino groups. The equivalent weight per amino group can be, for example, at least 40 or at least 50, and can be, for example, up to 500, up to 300 or up to 250.

[0031] Useful water-soluble amino-functional polymers include vinylamine homopolymers and copolymers, crosslinked polyamidoamines, ethyleneimine-grafted crosslinked polyamidoamines, polyethyleneimines, alkoxylated polyethyleneimines, crosslinked polyethyleneimines, amidated polyethyleneimines, alkylated polyethyleneimines, amine-epichlorohydrin polycondensates, water-soluble polyadducts produced from multifunctional epoxides and multifunctional amines, alkoxylated polyamines, polyallylamines, and condensates of lysine, ornithine, or arginine, or mixtures of any two or more of the same. Suitable water-soluble amino-functional polymers are described, for example, in document EP 1-428-847 A.

[0032] A preferred water-soluble amino-functional polymer is a polyethyleneimine. Polyethyleneimines can be produced by polymerization of ethyleneimine in aqueous solution in the presence of a catalyst.

[0033] To produce foam according to the invention, at least one polyisocyanate is reacted with at least one isocyanate-reactive compound having a functionality of at least 2 and an equivalent weight of at least 200 Petition 870250047619, dated 06 / 06 / 2025, page 19 / 41 12 / 28 grams per mole of isocyanate reactive groups. Other ingredients may be present as discussed later in this document. The reaction is carried out in the presence of a β-diketone compound of structure I and the water-soluble amino-functional polymer.

[0034] A suitable amount of β-diketone compound is 0.01 to 5 ppc (i.e., 0.01 to 5 parts by weight per 100 parts by weight of isocyanate-reactive compound(s) having (have) at least two isocyanate-reactive groups per molecule and an equivalent weight of at least 200 per isocyanate-reactive group). A preferred minimum amount is at least 0.1 or at least 0.2 ppc and a preferred maximum amount is up to 2.5, up to 1.5, up to 1, up to 0.75 or up to 0.5 ppc.

[0035] A suitable amount of water-soluble amino-functional polymer is 0.01 to 2 ppc (i.e., 0.01 to 2 parts by weight per 100 parts by weight of isocyanate-reactive compound(s) having (have) at least two isocyanate-reactive groups per molecule and an equivalent weight of at least 200 per isocyanate-reactive group). A preferred minimum amount is at least 0.025 or at least 0.04 ppc and a preferred maximum amount is up to 1, up to 0.5, up to 0.25 or up to 0.10 ppc.

[0036] The β-diketone compound and the water-soluble amino-functional polymer can be supplied as a mixture with any one or more of the various ingredients of the formulation used to produce the foam. Alternatively, each of them can be added to the reaction as a separate component or a separate stream without being previously combined with any of the other ingredients.

[0037] Preferably, however, the β-diketone compound and the water-soluble amino-functional polymer are mixed with the isocyanate-reactive compound(s) having (have) at least two isocyanate-reactive groups per molecule and an equivalent weight of at least 200 grams per mole of isocyanate-reactive groups, prior to the formation of the polyurethane foam. The isocyanate-reactive compound(s) preferably include at least Petition 870250047619, dated 06 / 06 / 2025, page 20 / 41 13 / 28 a polyether-polyol. The resulting mixture can be kept at approximately room temperature or at a higher temperature (but below the boiling point of the β-diketone compound and below the temperature at which the polyol degrades) for a period of at least 30 minutes before producing foam. Such a mixture can be kept under these conditions for any arbitrarily longer time, such as up to a month, up to a week, or up to a day.

[0038] The foam formulation includes at least one isocyanate-reactive compound having a functionality of at least 2 and an equivalent weight of at least 200 grams per mole of isocyanate-reactive groups. Functionality refers to the average number of isocyanate-reactive groups per molecule. The functionality may be up to 8 or more, but is preferably 2 to 4. The isocyanate-reactive groups may be, for example, hydroxyl, primary amino and / or secondary amino groups, but hydroxyl groups are preferred. The equivalent weight may be up to 6,000 or more, but is preferably 500 to 3,500 and more preferably 1,000 to 2,500. This isocyanate-reactive compound may be, for example, a polyether-polyol, a polyester-polyol, a hydroxyl-terminated butadiene polymer or copolymer, a hydroxyl-containing acrylate polymer, and the like.A preferred type of isocyanate-reactive compound is a polyether-polyol, especially a propylene oxide polymer or a propylene oxide-ethylene oxide copolymer. A propylene oxide-ethylene oxide copolymer may be a block copolymer having terminal poly(oxyethylene) blocks and in which at least 50% of the hydroxyl groups are primary. Another suitable propylene oxide-ethylene oxide copolymer may be a random or pseudorandom copolymer, which may also contain terminal poly(oxyethylene) blocks and in which at least 50% of the hydroxyl groups are primary.

[0039] Polyester-polyols that are useful as the isocyanate reactive compound include reaction products of polyols, preferably diols, with polycarboxylic acids or their anhydrides, preferably dicarboxylic acids or Petition 870250047619, dated 06 / 06 / 2025, page 21 / 41 14 / 28 Dicarboxylic acid anhydrides. Polycarboxylic acids or anhydrides can be aliphatic, cycloaliphatic, aromatic, and / or heterocyclic and can be substituted, for example, with halogen atoms. Polycarboxylic acids can be unsaturated. Examples of these polycarboxylic acids include succinic acid, adipic acid, terephthalic acid, isophthalic acid, trimellitic anhydride, phthalic anhydride, maleic acid, maleic acid anhydride, and fumaric acid.The polyols used in the production of polyester-polyols preferably have an equivalent weight of 150 or less and include ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol, 1,4-butanediol and 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, cyclohexanedimethanol, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methylglucoside, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, dibutyl glycol and the like. Polycaprolactone-polyols, such as those sold by The Dow Chemical Company under the trade name Tone, are also useful.

[0040] Mixtures of two or more isocyanate-reactive compounds having a functionality of at least 2 and an equivalent weight of at least 200 per isocyanate-reactive group may be used if desired.

[0041] The isocyanate-reactive compound(s) may contain dispersed polymer particles. These so-called polyol polymers contain, for example, vinyl polymer particles such as styrene, acrylonitrile or styreneacrylonitrile, particles of a polyurea polymer or polymers of a polyurethane-urea polymer, in each case dispersed in a continuous polyol phase.

[0042] In addition, the aforementioned isocyanate-reactive compounds may be used in mixtures with one or more crosslinking agents and / or chain-extending agents. For the purposes of this descriptive report, crosslinking agents are compounds that have at least three isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 200 grams per mole of isocyanate-reactive groups. Petition 870250047619, dated 06 / 06 / 2025, page 22 / 41 15 / 28 Chain extension agents for the purposes of this invention have exactly two isocyanate-reactive groups per molecule and have an equivalent weight per isocyanate-reactive group of less than 200 grams per mole of isocyanate-reactive groups. In each case, the isocyanate-reactive groups are preferably hydroxyl, primary amino, or secondary amino groups. The crosslinking agents and chain extension agents preferably have equivalent weights of up to 150 and, more preferably, up to 125.

[0043] Examples of crosslinking agents include glycerin, trimethylolpropane, trimethylolethane, diethanolamine, triethanolamine, triisopropanolamine, alkoxylates of any of the aforementioned having equivalent weights up to 199, and the like. Examples of chain extending agents include alkylene glycols (e.g., ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and the like), glycol ethers (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like), ethylenediamine, toluenediamine, diethyltoluenediamine and the like, and also alkoxylates of any of the aforementioned having equivalent weights up to 199 and the like.

[0044] Crosslinking agents and / or chain extension agents are typically present in small amounts (if at all). A preferred amount is 0 to 5 ppc of crosslinking agents and / or chain extension agents. A more preferred amount is 0.05 to 3 ppc and a still more preferred amount is 0.1 to 2.5 ppc of one or more crosslinking agents.

[0045] Examples of suitable polyisocyanates include, for example, m-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate (TDI), the various isomers of diphenylmethane diisocyanate (MDI diphenylmethanediisocyanate), so-called polymeric MDI products (which are a mixture of polymethylene-polyphenylene polyisocyanates in monomeric MDI), carbodiimide-modified MDI products (such as so-called liquid MDI products which have an equivalent weight of Petition 870250047619, dated 06 / 06 / 2025, page 23 / 41 16 / 28 isocyanate na faixa de 135 a 170), 1,6-di-isocyanato de hexamethylene, 1,4-diisocyanato de tetramethylene, 1,4-di-isocyanato de ciclo-hexano, di-isocyanato de hexa-hidrotolueno, MDI hidrogenado (H12MDI), di-isocyanato de isoforona, 1,5-diisocyanato de naftileno, 2,4-di-isocyanato de metoxifenila, 4,4'-di-isocyanato de bifenileno, di-isocyanato de 3,3'-dimetóxi-4,4'-bifenila, 4,4'-di-isocyanato de 3,3'dimetildifenilmethane, di-isocyanato de 4,4',4”-trifenilmethane, poli-isocyanatos de hydrogenated polymethylene-polyphenyl, 2,4,6-tri-isocyanate of tolueno and 2,2',5,5'tetraisocyanate of 4,4'-dimethyldiphenylmethane. All of the above mentioned items that are modified to include the groups urethane, urea, uretonimine, biuret, halophonate and / or carbodimide can be used.

[0046] Preferred isocyanates include TDI, MDI and / or polymeric MDI, as well as derivatives of MDI and / or polymeric MDI containing urethane, urea, uretonimine, biuret, allophanate and / or carbodiimide groups. A particularly preferred isocyanate is a mixture of TDI and MDI.

[0047] The amount of polyisocyanate supplied to the foam formulation is expressed as the isocyanate index, which is 100 times the ratio of isocyanate groups to isocyanate-reactive groups in the foam formulation. The isocyanate index is typically around 60 to 150. A preferred isocyanate index is 60 to 125 and a more preferred isocyanate index is 65 to 115. In some embodiments, the isocyanate index is 70 to 115 or 75 to 115. Water is considered to have two isocyanate-reactive groups.

[0048] The blowing agent may be a chemical (exothermic) type, a physical (endothermic) type, or a mixture of at least one of each type. Chemical types typically react or decompose to produce carbon dioxide gas or nitrogen gas under the conditions of the foaming reaction. Water and various carbamate compounds are examples of suitable chemical blowing agents. Physical types include carbon dioxide, various low-boiling-point hydrocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, ethers, and the like. Water is the most preferred blowing agent, either by itself or in combination with one or more other blowing agents. Petition 870250047619, dated 06 / 06 / 2025, page 24 / 41 17 / 28 physical expansion.

[0049] Blowing agents are present in sufficient quantities to provide the desired foam density. When water is the blowing agent, a suitable quantity is generally 1.0 to 7 ppc, preferably 2 to 6 ppc.

[0050] Suitable surfactants are materials that help stabilize the cells of the foam-forming reaction mixture until the materials have been cured. A wide variety of silicone-based surfactants, such as are commonly used in the manufacture of polyurethane foams, can be used in the production of foams with polymer polyols or dispersions of this invention. Examples of such silicone-based surfactants are commercially available under the trade names Tegostab™ (Evonik Corporation), Niax™ (Momentive), and Dabco™ (Evonik Corporation).

[0051] Surfactants are typically present in amounts up to 5 ppc, more typically 0.1 to 2 ppc and preferably 0.25 to 1.5 ppc.

[0052] Suitable catalysts include those described in U.S. Patent No. 4,390,645. Representative catalysts include: (a) tertiary amines, such as trimethylamine, triethylamine, N-methylmorpholine, Netylmorpholine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N,N',N'tetramethyl-1,4-butanediamine, N,N-dimethylpiperazine, 1,4-diazobicyclo-2,2,2-octane, bis(dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, 4,4'-(oxy-2,1-ethanediyl)bismorpholine, tri(dimethylaminopropyl)amine, pentamethyldiethylenetriamine and triethylenediamine and the like; as well as so-called low-emissivity tertiary amine-based catalysts containing one or more isocyanate-reactive groups, such as dimethylaminopropylamine and the like; (b) tertiary phosphines, such as trialkylphosphines and dialkylbenzylphosphines; (c) Chelates of various metals, such as those that can be obtained from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate and the like with metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co and Ni; Petition 870250047619, dated 06 / 06 / 2025, p. 25 / 41 18 / 28 (d) acidic metallic salts of strong acids, such as ferric chloride, stannic chloride, stannous chloride, antimony trichloride, bismuth nitrate and bismuth chloride; (e) strong bases, such as hydroxides, alkoxides and phenoxides of alkali metals and alkaline earth metals; (f) alcoholates and phenolates of various metals, such as Ti(OR)4, Sn(OR)4 and Al(OR)3, where R is alkyl or aryl, and the reaction products of alcoholates with carboxylic acids, beta-diketones and 2-(N,N-dialkylamino)alcohols; (g) salts of organic acids with a variety of metals, such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni and Cu, including, for example, sodium acetate, stannous octoate, stannous oleate, lead octoate, metallic drying agents such as manganese and cobalt naphthenate; and (h) organometallic derivatives of tetravalent tin, trivalent and pentavalent As, Sb and Bi, and metallic carbonyls of iron and cobalt.

[0053] Catalysts are typically present in small amounts, such as up to 3 ppc and usually up to 2 ppc. A preferred amount of catalyst is 0.05 to 2 ppc.

[0054] Foam can be produced in the presence of additional compounds that reduce aldehyde and / or other emissions in the resulting foam. Among these are amino alcohol compounds, which are characterized by having at least one primary or secondary amino group and at least one hydroxyl group, each attached to an aliphatic carbon atom, and alkyl hydroxylamine compounds that include an -NH-OH group in which the nitrogen atom is attached to an aliphatic carbon atom.

[0055] Amino alcohol compounds are known and include, for example, those described in US Publications Nos. 2009 / 0227758 and 2010 / 0124524, each of which is incorporated herein in its entirety.

[0056] In some embodiments, the amino alcohol or alkylhydroxylamine compound is a compound represented by structure VII: R17H R1^--l / R19R16(VII) Petition 870250047619, dated 06 / 06 / 2025, p. 26 / 41 19 / 28 or a salt of such a compound, wherein R17, R18 and R19 are each independently H, alkyl optionally substituted with phenyl or NR20R21, wherein R20 and R21 are independently H, C16C6 alkyl, phenyl, or hydroxyalkyl optionally independently substituted with phenyl or NR20R21; R16 is H, hydroxyl, phenyl, alkyl optionally substituted with phenyl or NR20R20, or hydroxyalkyl optionally independently substituted with phenyl or NR20R21, provided that when none of R17, R18 and R19 is hydroxyalkyl, then R16 is hydroxyl or hydroxyalkyl optionally independently substituted with phenyl or another NR20R21.

[0057] The amino alcohol or alkylhydroxylamine preferably has a molecular weight not greater than 500 grams / mol.

[0058] Specific examples of suitable amino alcohols are 2-amino-1-butanol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, 2-amino-1-methyl-1,3-propanediol, 1,1,1-tris(hydroxymethyl)methylamine, ethanolamine, diethanolamine, N-methylethanolamine, N-butylethanolamine, monoisopropanolamine, 2-amino-2(hydroxymethyl)propane-1,3-diol, di-isopropanolamine, mono-sec-butanolamine, disec-butanolamine, or salts thereof. These amino alcohols are available from a variety of commercial sources, including ANGUS Chemical Company (Buffalo Grove, Ill., USA), The Dow Chemical Company (Midland, Mich., USA), or can be readily prepared by techniques well known in the art. Amino alcohols can be used in the form of salts. Suitable salts include hydrochloride, acetate, formate, oxalate, citrate, carbonate, sulfate, and phosphate salts.

[0059] Specific examples of alkyl-hydroxylamines include N-isopropylhydroxylamine, N-ethylhydroxylamine, N-methylhydroxylamine, N-(n-butyl)hydroxylamine, N-(sec-butyl)hydroxylamine and the like.

[0060] Foam can be produced in the presence of at least one antioxidant. Examples of suitable antioxidants include phenolic compounds, amine antioxidants, thiosynergists such as dilauryl thiodipropionate or Petition 870250047619, dated 06 / 06 / 2025, page 27 / 41 20 / 28 distearyl thiodipropionate, phosphites and phosphonites, benzofuranones and indolinones, as disclosed in U.S. Patent No. 4,325,863; U.S. Patent No. 4,338,244; U.S. Patent No. 5,175,312; U.S. Patent No. 5,216,052; U.S. Patent No. 5,252,643; DEA-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102; Tocopherols, hydroxylated thiodiphenyl ethers, O,N and S-benzyl compounds, hydroxybenzylated malonates, triazine compounds, benzylphosphonates, acylaminophenols, amides of ε-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, ascorbic acid (vitamin C), 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, substituted and unsubstituted benzoic acid esters, acrylates, nickel compounds, oxamides, 2-(2-hydroxyphenyl)-1,3,5-triazines, hydroxylamines, nitrones, β-thiodipropionic acid esters, as described, for example, in USP document no. 6,881,774, incorporated herein by reference.

[0061] The antioxidant(s), when used, is / are present in an effective amount, such as up to about 10 ppc. A preferred range is 0.1 to 5 ppc and a more preferred range is 0.2 to 1.5 ppc.

[0062] In some embodiments, a HALS (hindered amine photostabilizer) compound is present. Suitable HALS compounds include bis(1-octyloxy)-2,2,5,5-tetramethyl-4-piperidinyl sebacate (BASF's Tinuvin™ 123), bis-(1,2,2,6-pentamethyl-4-piperidinyl) n-butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate (BASF's Tinuvin™ 144), dimethyl succinate polymer with 4-hydroxy-2-2,6,6-tetramethyl-1-piperidineethanol (BASF's Tinuvin™ 622), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (BASF's Tinuvin™ 765), and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate. (Tinuvin™ 770 from BASF) and similar products.

[0063] The HALS compound, when used, is present in an effective amount, such as up to about 10 ppc. A preferred range is 0.1 to 5 ppc and a more preferred range is 0.1 to 2.5 ppc.

[0064] Other ingredients may be present during the foaming stage, including, for example, fillers, colorants, masking agents. Petition 870250047619, dated 06 / 06 / 2025, page 28 / 41 21 / 28 odor, flame retardants, biocides, antistatic agents, thixotropic agents and cell openers.

[0065] Polyurethane foam is produced according to this invention by forming a reaction mixture containing the various ingredients and curing the reaction mixture. Free-growth processes, such as continuous block foam production methods (slabstock), can be used. Alternatively, molding methods can be used. Such processes are well known. Generally, no alternation of conventional processing operations is required to produce polyurethane foam according to this invention (other than the inclusion of the β-diketone compound of structure I and the water-soluble amino-functional polymer).

[0066] The various ingredients may be introduced individually or in various subcombinations into a mixing head or other mixing device where they are mixed and distributed into a region (such as a trough or other open container, or a closed mold) where they are cured. It is often convenient, especially when producing molded foam, to form a formulated polyol component containing the isocyanate-reactive compound(s), including crosslinking agents and / or chain extension agents as may be used, the structure I β-diketone compound, the water-soluble amino-functional polymer, other additives (if present) and optionally the catalyst(s), surfactant(s) and blowing agent(s). This formulated polyol component is then contacted with the polyisocyanate (and also with any other ingredients not present in the formulated polyol component) to produce the foam.

[0067] Some or all of the various components may be heated before they are mixed to form the reaction mixture. In other cases, the components are mixed at room temperature (such as between 15 and 40 °C). Heat may be applied to the reaction mixture after all the ingredients have been mixed, but this is usually unnecessary.

[0068] The product of the curing reaction is a flexible polyurethane foam. A Petition 870250047619, dated 06 / 06 / 2025, p. 29 / 41 22 / 28 foam density can be from 20 to 200 kg / m3. For most seating and bedding applications, a preferred density is 24 to 80 kg / m3. The foam may have a resilience of at least 50% in the ASTM 3574-H ball rebound test. The foam produced according to this invention is useful, for example, in padding applications such as bedding and household, office or vehicular seating, and also in other vehicular applications such as headrests, control panels, instrument panels, armrests, headliners, noise, vibration and harshness (NVH) attenuation foam and acoustic foam.

[0069] Polyurethane foams produced according to the invention are characterized by having reduced emissions of aldehydes, in particular one or more of formaldehyde, acetaldehyde, acrolein and propionaldehyde, compared to the case in which the 3e-diketone compound of structure I and the water-soluble amino-functional polymer are absent. A suitable method for measuring the emissions of formaldehyde, acetaldehyde, acrolein and propionaldehyde is as follows: The polyurethane foam sample is crushed to open the cells. The crushed foam is cut into cubic samples of 10 cm χ 10 cm χ 14 cm, which are immediately hermetically packaged in aluminum foil or polyethylene film and kept in this manner for 5 days at about 25 °C.

[0070] Aldehyde concentrations are measured according to the Toyota TSM0508G test method. In this Toyota method, the foam sample is removed from the metal foil or film and then placed in individual 10 l Tedlar gas bags (Delin Co., Ltd., China) that have been previously purged three times with nitrogen gas. The bag containing the foam sample is filled with 7 l of nitrogen, sealed, and heated to 65 °C for two hours. The plastic bag containing the foams is removed from the oven. The gas in the bag is pumped through a 350 mg dinitrophenylhydrazine cartridge to capture the carbonyl compounds. The captured carbonyl compounds are analyzed for formaldehyde, acetaldehyde, acrolein, and propionaldehyde by liquid chromatography, with the results expressed in terms of weight of the respective aldehyde per cubic meter. Petition 870250047619, dated 06 / 06 / 2025, pages 30 / 41 23 / 28 of gas in the gas bag. Details for a specific method of performing the Toyota test method are described in the following examples.

[0071] The amounts of formaldehyde, acetaldehyde, acrolein, and propionaldehyde emitted as determined in this method are all typically reduced by at least 10% compared with an otherwise similar foam produced in the absence of the β-diketone compound and the water-soluble amino-functional polymer. An advantage of this invention is that significant reductions are observed in the amounts emitted of some or even all of these aldehyde compounds. Reductions in emitted formaldehyde can exceed 70% or 75%; reductions in acetaldehyde can exceed 40% or exceed 50%; reductions in acrolein can exceed 70%, exceed 80%, or even exceed 90%.

[0072] In some embodiments, the amount of formaldehyde emitted is not greater than 100 pg / m3, not greater than 75 pg / m3, or not greater than 50 pg / m3, as measured according to the Toyota method. In some embodiments, the amount of acetaldehyde emitted is not greater than 100 pg / m3, as measured according to the Toyota method. In some embodiments, the amount of acrolein emitted is not greater than 100 pg / m3 or not greater than 60 pg / m3, as measured according to the Toyota method. In some embodiments, the amount of propionaldehyde emitted is not greater than 350 pg / m3 or not greater than 250 pg / m3, as measured according to the Toyota method.

[0073] The following examples are provided to illustrate the invention, but are not intended to limit the scope of the invention. All parts and percentages are by weight unless otherwise stated. Example 1 and comparative samples A to C

[0074] General foaming method, Comparative sample A: A formulated polyol is produced by combining 40 parts of a nominally trifunctional polyether-polyol having a hydroxyl number of 29.5, 52.6 parts of a 1,700 equivalent weight polyether-polyol initiated from a mixture of sucrose and glycerin, 0.8 part of glycerin, 1.6 part of a mixture Petition 870250047619, dated 06 / 06 / 2025, pages 31 / 41 24 / 28 part urethane catalyst, 0.5 part organosilicone-based foam stabilizing surfactant, and 4.2 parts water. Polyurethane foams are produced from the formulated polyol by combining the formulated polyol with an isocyanate-terminated prepolymer in a weight ratio of 1.67:1, pouring the resulting reaction mixture into a cup and allowing the reaction mixture to grow and cure to form a polyurethane foam. After the foam has cured sufficiently to be dimensionally stable, it is removed from the cup and, except for Comparative Samples B and C, 10 cm x 10 cm x 14 cm samples, weighing approximately 38 to 41 grams, are cut. For Comparative Samples B and C, 30-gram samples are cut. The foam cubes are each immediately wrapped in aluminum foil to form an airtight package for 7 days.

[0075] Comparative Samples B and C are produced using the general foaming method. In Comparative Sample B, a polyethyleneimine (PEI) of PM 600 (0.05% based on the weight of formulated polyol, 0.054% based on isocyanate-reactive materials of equivalent weight of 200 g / mol or greater) is added to the formulated polyol before foaming. In Comparative Sample B, N-(2-hydroxyethyl)acetoacetamide (N-AAEM) (0.1% based on the weight of formulated polyol, 0.108% based on isocyanate-reactive materials of equivalent weight of 200 g / mol or greater) is added to the formulated polyol before foaming.

[0076] Example 1 is produced using the general foaming method. In Example 1, both PM 600 PEI (0.05% based on the weight of formulated polyol, 0.054% based on isocyanate-reactive materials of equivalent weight of 200 g / mol or greater) and N-AAEM (0.1% based on the weight of formulated polyol, 0.108% based on isocyanate-reactive materials of equivalent weight of 200 g / mol or greater) are added to the formulated polyol before foaming.

[0077] The aldehydes emitted from the foam samples are analyzed by the following Toyota gas bag method. The cube foam samples are, Petition 870250047619, dated 06 / 06 / 2025, pages 32 / 41 25 / 28 in each case, removed from the metal foil and placed in a 10 l Tedlar gas bag that had been washed with pure nitrogen three times and emptied. An empty gas bag is used as a blank. After the foam sample is placed in the gas bag, the gas bag is filled with approximately 7 l of nitrogen gas and heated in an oven for 2 hours at 65 °C. The nitrogen gas in the gas bag is then pumped out by an air pump and analyzed for formaldehyde, acetaldehyde, acrolein, and propionaldehyde.

[0078] The gas from each bag is passed through a dinitrophenylhydrazine (DNPH) cartridge (CNWBOND DNPH-Silica cartridge, 350 mg, cat. no. SEEQ144102, Anple Co., Ltd.) at a sampling rate of 330 ml / min. Aldehydes emitted from the foam into the gas are absorbed by the cartridge to form DNPH derivatives. The DNPH cartridge is eluted with 3 g of acetonitrile, and the resulting acetonitrile solution is analyzed by HPLC to quantify the carbonyls in the sample, as follows.

[0079] A standard solution containing 15 pg / ml each of formaldehyde, acetaldehyde, acrolein, and propionaldehyde (in each case in the form of DNPH derivatives) (carbonyl-DNPH mixture TO11A, cat. no. 48149-U, Supelco Co., Ltd) is diluted with acetonitrile. A vial containing 2 ml of the diluted solution (containing 0.794 ppm each of formaldehyde, acetaldehyde, acrolein, and propionaldehyde) is refrigerated at -4 °C. The refrigerated solution is injected into the HPLC system and analyzed for formaldehyde, acetaldehyde, acrolein, and propionaldehyde derivatives. The response factor is calculated from the elution peak area for each derivative, according to the formula: Response factor i = Peak area i 0.794 where Response factor i = Response factor of derivative i; Peak area i = Peak area of ​​derivative i in the standard solution and 0.794 = the concentration of each derivative in the standard solution.

[0080] The quantities of formaldehyde, acetaldehyde, acrolein, and propionaldehyde emitted by each foam sample are then determined. In each case, the Petition 870250047619, dated 06 / 06 / 2025, pages 33 / 41 A 26 / 28 acetonitrile solution obtained by eluting the DNPH column is injected into the HPLC system, and the elution peak area is determined for each derivative. The concentration of the aldehyde-DNPH derivative in the sample solution is calculated based on the formula as follows: Concentration of i = Peak area i Response factor i where: Concentration of i = Concentration of aldehyde-DNPH derivative in the sample solution, Peak area i = Peak area of ​​derivative i in the sample solution and Response factor i = Response factor of derivative i, determined from the standard solutions as described above. The HPLC conditions are as follows: Instrument: Agilent 1200 HPLC Column: Supelco Ascentis Express C18, 15 cm*4.6 mm, 2.7 µm Mobile Phase: Solvent A: 0.1% H3PO4 in Acetonitrile Solvent B: 0.1% H3PO4 in DI Water Column Oven: 15 °C Detection: DAD detector at 36°C nm Gradient: Time (min) % A % B Flow (ml / min) 0 45 55 1 7 45 55 1 14 50 50 1 20 85 15 1 25 100 0 1 Equilibrium Time: 5 min Injection: 10 pL

[0081] The concentrations of formaldehyde, acetaldehyde, acrolein, and propionaldehyde for each of Example 1 and Comparative Samples A to C are as indicated in Table 1. Petition 870250047619, dated 06 / 06 / 2025, pp. 34 / 41 27 / 28 Table 1 Sample Comp. A* Comp. B* Comp. C* Ex. 1 Additives None 0.054% PEI 0.108% N-AAEM 0.054% PEI + 0.108% N-AAEM Formaldehyde, pg / m3 397 413 101 65 Acetaldehyde, pg / m3 217 374 237 97 Acrolein, pg / m3 1061 937 167 54 Propionaldehyde, pg / m3 362 613 769 315 *This is not an example of that invention.

[0082] As the data in Table 1 show, PEI alone provides no benefit in reducing the levels of any of the aldehydes tested. N-AAEM is effective only in reducing formaldehyde and acrolein. The combination of PEI and N-AAEM results in large reductions in all four aldehydes tested, in each case to levels much lower than those obtained using PEI or N-AAEM alone. These results are quite surprising because PEI alone provides very little benefit; it would not be expected that combining it with N-AAEM would result in any performance better than that of N-AAEM alone. Example 2 and comparative samples D to F

[0083] Comparative Sample D is a repetition of Comparative Sample A.

[0084] Comparative Samples E and F are produced using the general foaming method. In Comparative Sample E, 0.05% of PM 600 polyethyleneimine (PEI) (0.05% based on the weight of formulated polyol, 0.054% based on isocyanate reactive materials of equivalent weight of 200 g / mol or greater) is added to the formulated polyol before foaming. In Comparative Sample F, (acetoacetoxy)ethyl methacrylate (AAEM) (0.1% based on the weight of formulated polyol, 0.108% based on isocyanate reactive materials of equivalent weight of 200 g / mol or greater) is added to the formulated polyol before foaming.

[0085] Example 2 is produced using the general foaming method. In Example 2, both the PEI of PM 600 (0.05% by weight of formulated polyol, 0.054% by weight of isocyanate reactive materials) Petition 870250047619, dated 06 / 06 / 2025, pages 35 / 41 28 / 28 equivalent of 200 g / mol or greater) as well as AAEM (0.1% based on the weight of formulated polyol, 0.108% based on isocyanate reactive materials of equivalent weight of 200 g / mol or greater) are added to the formulated polyol before producing the foam.

[0086] The foams are tested as indicated in the previous examples. The results are shown in Table 2. Table 2 Sample Comp. D* Comp. E* Comp. F* Ex. 1 Additives None 0.054% PEI 0.108% AAEM 0.054% PEI + 0.108% AAEM Formaldehyde, pg / m3 400 306 39 29 Acetaldehyde, pg / m3 189 207 155 90 Acrolein, pg / m3 736 541 158 38 Propionaldehyde, pg / m3 478 495 476 245 *This is not an example of this invention.

[0087] In this set of experiments, PEI alone provides benefits in reducing acrolein content, but not that of any of the other aldehydes. N-AAEM alone moderately reduces formaldehyde, acetaldehyde, and acrolein emissions, but not propionaldehyde emissions. The combination of PEI and N-AAEM results in large reductions in all four aldehydes tested, in each case to much lower levels than those obtained with the use of PEI or N-AAEM alone. Again, these results are quite surprising because IEP alone provides very little benefit.

Claims

1. A process for producing a polyurethane foam, characterized in that it comprises forming a reaction mixture containing an aromatic polyisocyanate, at least one isocyanate-reactive material having an average functionality of at least 2 and an equivalent weight of at least 200 grams per mole of isocyanate-reactive groups, at least one blowing agent, at least one surfactant, and at least one catalyst, and curing the reaction mixture to form the polyurethane foam, wherein the curing step is carried out in the presence of (i) at least one β-diketone compound in an amount of 0.01 to 5 ppc, wherein the β-diketone compound is N-(2-hydroxyethyl)acetoacetamide and (acetoacetoxy)ethyl methacrylate and (ii) at least one water-soluble amino-functional polymer in an amount of 0.01 to 2 ppc, having a number-average molecular weight of at least 300 and at least 3 primary amino groups. and / or secondary by molecule,where the water-soluble aminofunctional polymer is a polyethyleneimine.

2. Process for reducing aldehyde emissions from a polyurethane foam produced by the process as defined in claim 1, characterized in that it comprises: a) combining (i) at least one β-diketone compound in an amount of 0.01 to 5 ppc, wherein the β-diketone compound is N-(2-hydroxyethyl)acetoacetamide and (acetoacetoxy)ethyl methacrylate;and (ii) at least one water-soluble amino-functional polymer in an amount of 0.01 to 2 ppc, having a number-average molecular weight of at least 300 and at least 3 primary and / or secondary amino groups per molecule, wherein the water-soluble amino-functional polymer is a polyethyleneimine, with at least one isocyanate-reactive material having an average functionality of at least 2 and an equivalent weight of at least 200 grams per mole of isocyanate-reactive groups to form a mixture and then (b) combine the mixture from step (a) with at least one organic polyisocyanate and cure the resulting reaction mixture in the presence of at least one blowing agent, at least one surfactant and at least one catalyst to form a polyurethane foam.

3. Polyurethane foam, characterized by being produced by the process as defined in claim 1.