Aldehyde scavenger for polyurethane foams

Abstract

A composition for making a polyurethane foam comprising a polyfunctional isocyanate composition, an isocyanate-reactive composition, and an aldehyde scavenger comprising a borane-amine complex. A method for removing aldehydes from a polyurethane foam, a foam composition, and an article made using the foam composition.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 555,943, filed February 21, 2024. The above application is incorporated herein by reference. Background of the Invention

[0004] Polyurethane (“PU”) foam materials possess excellent cushioning and lightweight properties, are mass-producible, and are economically efficient. Therefore, they are commonly used as cushioning materials in the automotive and furniture industries. PU foam is typically prepared through a high-temperature synthesis process involving the mixing of isocyanate reactive compounds and polyols. However, this process can release volatile organic compounds (“VOCs”) such as formaldehyde and other aldehydes.

[0005] It is generally believed that aldehydes in polyurethane foam are formed by the autoxidation of components containing methyl or other side-chain groups such as methylene, which are present in polyols or amine catalysts, organosilicon surfactants, or similar substances used in polyurethane synthesis. Aldehydes can also be generated during or after the foaming process when the foam is exposed to air. The generated aldehydes include formaldehyde and higher molecular weight compounds such as acetaldehyde and propionaldehyde.

[0006] Aldehydes are generally toxic and can cause neurological disorders and sick building syndrome when present in PU foam. Therefore, there is a demand in the automotive and furniture industries (e.g., bedding) for additives that remove aldehydes from PU foam.

[0007] Several solutions for removing formaldehyde from PU foam are known. For example, US 2018 / 0171064 and US 2008 / 0281013 A1 describe the use of sulfur compounds. EP 2703421 A1 and US 2017 / 0218157 A1 describe the addition of reactive amines as aldehyde scavengers. US 11,555,091 describes the use of alkali metal salts and ammonium salts to remove aldehydes.

[0008] Commercially available products are advertised as being able to remove formaldehyde, such as JEFFADD® AS-53 and JEFFADD® AS-76 (commercially available from Huntsman International LLC).

[0009] Unfortunately, the solutions mentioned above only reduce the formaldehyde level in PU foam. They are not effective enough in removing higher molecular weight aldehydes.

[0010] Purpose of the invention

[0011] Therefore, there is a need for aldehyde scavengers that can be included in PU foam compositions to remove aldehydes (including higher molecular weight aldehydes) without negatively impacting the properties of the PU foam.

[0012] The compositions disclosed herein address problems associated with conventional compositions and methods by providing aldehyde scavengers for use in PU compositions. This disclosure relates to aldehyde scavenger compositions that can be used in the production of low-aldehyde or formaldehyde-free polyurethane foams. This reduced aldehyde emission can be achieved by introducing one or more aldehyde scavengers into a “premixed” formulation used to generate PU foam. Attached Figure Description

[0013] Figure 1 This is a graph showing a comparison of the expansion curves of the PU foam of Example 1 prepared in the presence of 0 pbw and 0.25 pbw borane-triethylamine complexes.

[0014] Figure 2 This is a graph showing the evaluation of aldehyde concentrations when 0 pbw and 0.25 pbw borane triethylamine complexes are added.

[0015] Figure 3 This is a graph showing the evaluation of aldehyde concentrations when 0 pbw and 0.1 pbw borane triethylamine complexes are added.

[0016] Figure 4 The aldehyde content in spiked PU foam is shown in the presence of an aldehyde scavenger.

[0017] Figure 5 The aldehyde content in spiked PU foam is shown in the presence of an aldehyde scavenger.

[0018] Figure 6 The aldehyde evaluation of formaldehyde in a pure tertiary amine catalyst in the presence of a 0.05 pbw borane-amine complex is shown.

[0019] Figure 7 The aldehyde evaluation of acetaldehyde in a pure tertiary amine catalyst in the presence of a 0.05 pbw borane-amine complex is shown.

[0020] Figures 8 to 12 An evaluation of aldehyde emission concentrations is shown when different borane-amine complexes are included at different concentrations. Detailed Implementation

[0021] Unless otherwise defined, all terms (including technical and scientific terms) used in this disclosure shall have the meanings commonly understood by one of ordinary skill in the art to which this disclosure pertains. Further guidance, including terminology definitions, is provided to better understand the teachings of this disclosure.

[0022] It should be noted that the term "comprising," as used in the claims and this disclosure, should not be construed as limiting to the means listed subsequently; it does not exclude other elements or steps. Therefore, it should be interpreted as specifying the presence of the mentioned feature, step, or component, but does not exclude the presence or addition of one or more other features, steps, or components, or groups thereof. Thus, the scope of the expression "a compound comprising components X and Y" should not be limited to compounds consisting solely of components X and Y. This means that, with respect to this disclosure, the only relevant components of the compound are X and Y.

[0023] Throughout this specification, references to "an embodiment" or "an embodiment" are made. Such references indicate that a particular feature described in connection with an embodiment is included in at least one embodiment of this disclosure. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing in various places throughout this specification do not necessarily refer to the same embodiment, although they may refer to the same embodiment. Furthermore, specific features or characteristics may be combined in any suitable manner in one or more embodiments, as will be apparent to those skilled in the art.

[0024] As used herein, the terms "preferred" and "ideally" refer to embodiments that provide certain benefits in certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this disclosure.

[0025] Where substituents are specified by their conventional chemical formula written from left to right, they also cover chemically identical substituents that would be obtained when the structure is written from right to left; for example, -CH2O- is equivalent to -OCH2-.

[0026] As used herein, the terms “optional” or “optionally” mean that an event or situation described below may or may not occur, and the description includes instances where the event or situation occurs and instances where it does not occur.

[0027] Throughout this disclosure, the term “about” as used herein refers to values ​​that include inherent variations in the error of a quantification device, mechanism, or method, or inherent variations present in one or more of the measured objects. For example, but not limitingly, when the term “about” is used, the specified value it refers to may vary by ±10%, or ±9%, or ±8%, or ±7%, or ±6%, or ±5%, or ±4%, or ±3%, or ±2%, or ±1%, or one or more fractions therein.

[0028] As used herein, the phrases “or combinations thereof” and “and combinations thereof” refer to all permutations and combinations of the items listed preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of the following: A, B, C, AB, AC, BC, or ABC, and also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB if the order matters in the particular context. Continuing with this example, it explicitly includes combinations containing one or more repeated items or terms, such as BB, AAA, CC, AABB, AACC, ABCCCC, CBBAAA, CABBB, etc. Those skilled in the art will understand that there is generally no limit to the number of items or terms in any combination unless it is obvious from the context. Similarly, when the phrase “selected from” or “selected from the group consisting of…” is used with the terms “or combinations thereof” and “and combinations thereof,” it refers to all permutations and combinations of the items listed preceding the phrase.

[0029] Unless otherwise stated, the terms “a” or “an” and “the” as used herein include both singular and plural references to the same object, unless the context clearly specifies otherwise. For example, “isocyanate group” as used herein means one or more isocyanate groups.

[0030] As used herein, the terms “aldehyde scavenger” and “aldehyde reducer” refer to compounds that reduce aldehyde emissions from polyurea or polyurethane materials and modified polyurethanes compared to compositions without aldehyde scavengers.

[0031] As used in this article, the term "aromatic" refers to a hydrocarbon radical having 6 to 50 carbon atoms and containing at least one ring (such as a benzene ring) with delocalized π electrons.

[0032] As used in this article, the term "aliphatic" refers to hydrocarbon radicals having 6 to 50 carbon atoms and lacking a delocalized π-electron system.

[0033] As used herein, the term "ambient temperature" refers to the temperature of the surrounding working environment (e.g., the temperature of the area, building, or room where the composition is used), excluding any temperature variations that occur due to the direct application of heat to the composition to promote curing. Ambient temperatures can range from about 10°C to about 30°C, and more specifically from about 15°C to about 25°C.

[0034] As used herein, the “isocyanate index,” “NCO index,” or simply “index” refers to the ratio of NCO groups to isocyanate reactive hydrogen atoms present in the formulation, given as a percentage: [NCO] x 100 / [active hydrogen] (%). In other words, the NCO index represents the percentage of isocyanate actually used in the formulation relative to the amount of isocyanate theoretically required to react with the amount of isocyanate reactive hydrogen used in the formulation. It should be noted that the isocyanate index used herein is considered from the perspective of the actual reaction process involving both isocyanate components and isocyanate reactive components. Any isocyanate groups consumed in the preliminary steps to produce modified polyisocyanates (including such isocyanate derivatives referred to in the art as prepolymers) or any active hydrogen consumed in the preliminary steps (e.g., reacting with isocyanates to produce modified polyols or polyamines) are not considered in the calculation of the isocyanate index. Only free isocyanate groups and free isocyanate reactive hydrogen (including those in water) present in the actual reaction stage are considered.

[0035] The term "hydroxyl value" as used herein refers to the concentration of hydroxyl groups per unit weight of polyol that are capable of reacting with isocyanate groups. The number of hydroxyl groups is reported in mg KOH / g and can be measured according to standard ASTM D 1638.

[0036] The term “average functionality” or “average hydroxyl functionality” for polyols used in this article refers to the number of OH groups per molecule, on average. The average functionality of isocyanates refers to the number of -NCO groups per molecule, on average.

[0037] The mass-average molar mass (Mw) is sometimes referred to as the weight-average molecular weight in this paper. It can be measured using any technique known to a person skilled in the art, such as small-angle laser light scattering.

[0038] Number-average molar mass (Mn) is sometimes referred to as number-average molecular weight in this paper. It can be measured using any technique known to a person skilled in the art, such as osmometry.

[0039] All references cited in this specification are incorporated herein by reference in their entirety. In particular, the teachings of all references specifically mentioned herein are incorporated herein by reference.

[0040] In a first aspect, this disclosure relates to compositions for manufacturing polyurethane foams, said compositions comprising:

[0041] (a) Polyfunctional isocyanates;

[0042] (b) Isocyanate reactive compositions; and

[0043] (c) Aldehyde scavengers containing borane-amine complexes.

[0044] Surprisingly, it was found that including a borananeamine complex in the composition used to prepare polyurethane foam reduced the concentration of aldehydes present in the resulting foam. The borananeamine complex is capable of removing both low-molecular-weight aldehydes (such as formaldehyde) and high-molecular-weight aldehydes (such as acetaldehyde and propionaldehyde) from the foam. It is believed that aldehyde emissions are continuously reduced after foam curing and throughout the foam's service life compared to foam prepared in the absence of an aldehyde scavenger. While not wishing to be limited by any theory or interpretation, it is believed that the aldehyde scavenger of the present invention can interact with or react with aldehydes, thereby converting them into another substance or trapping them within the foam.

[0045] Including borane-amine complexes in compositions used to prepare polyurethane foams does not negatively affect the physical or chemical properties of the resulting polyurethane foams.

[0046] As a result of including the aldehyde scavenger in the composition, polyurethane produced using the compositions of this disclosure does not require post-treatment to remove aldehyde impurities.

[0047] Polyfunctional isocyanates and isocyanate reactive components can be any compounds that react together to form polyurethane foam. Polyurethane is typically prepared by reacting compounds containing isocyanate reactive hydrogens with polyisocyanates. However, this disclosure is not limited to such components.

[0048] In some embodiments, the aldehyde scavenger is essentially composed of a borane-amine complex. In other embodiments, the aldehyde scavenger is composed of a borane-amine complex. That is, in some embodiments, the aldehyde scavenger does not contain other compounds that can act as aldehyde scavengers.

[0049] In some embodiments, the aldehyde scavenger comprises a borane-amine complex and an additional aldehyde scavenger. Any suitable aldehyde scavenger may be included in the composition. For example, the additional aldehyde scavenger may include, but is not limited to, other amine compounds, acidic compounds, compounds containing carbamate and nitrile groups, hydrazine compounds, urea, phosphorus-containing compounds, halogen-containing compounds, and mixtures thereof.

[0050] In some embodiments, the borane-amine complex may be a borane complex of any mono, di, tri, or polyamine having an alkyl or aromatic amine (containing a total of 0 to 100 carbon atoms). Examples include, but are not limited to, ammonia, trimethylamine, triethylamine, trioctylamine, tripropylamine, triisopropylamine, tributylamine, tri-tert-butylamine, triisobutylamine, tricyclohexylamine, tricyclopentylamine, triphenylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, di-tert-butylamine, diisobutylamine, dicyclohexylamine, dicyclopentylamine, diphenylamine, tert-butylamine, isobutylamine, isopropylamine, propylamine, ethylamine, methylamine, diethanolamine, ((2-diethylamino)ethanol), triethanolamine, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentylenediamine, 1,5-hexylenediamine, N,N,N',N'-tetramethyl-1,2-ethylenediamine, N,N N',N'-Tetramethyl-1,3-propylidene diamine, N,N,N',N'-Tetramethyl-1,4-butylidene diamine, N,N,N',N'-Tetramethyl-1,5-pentanediamine, N,N,N',N'-Tetramethyl-1,6-hexanediamine, N,N-dimethylaniline, benzyldimethylamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, N,N,N',N'',N''-pentamethyldipropylenetriamine, bis(2-dimethylaminoethyl) ether, N-methylmorpholine, N-ethylmorpholine, 2,2'-dimorpholinodiethyl ether, 1,3,5-tris(3-(dimethylamino)propyl)-hexahydro-s-triazine, etc. Alternatively or additionally, the borane-amine complex may be selected from one or more polyether amine families, such as commercially available JEFFAMINE® amine products (available from Huntsman International LLC), which consist of monoamines, diamines, and triamines based on PEG, PPG, or polytetramethylene glycol (PTMEG)-based polyether backbone structures, such as the JEFFAMINE® D series (H2N(CH(CH3)CH2O). x CH2CH(CH3)NH2), such as D-230 (Mw 230), D-400 (Mw 400), D-2000 (Mw 2000), and D-4000 (Mw 4000); JEFFAMINE® ED series (H2NCH(CH3)CH2(OCH2CH(CH3))) x (OCH2CH2) y (OCH2CH(CH3)) z NH2), such as ED-600 (Mw 600), ED-900 (Mw 900), ED-2003 (Mw 2000); JEFFAMINE® M series (H3C-(OCH2CH2)). x (OCH2CHR) yNH2), such as M-600 (Mw 600), M-1000 (Mw 1000), M-2005 (Mw 2000), M-2070 (Mw 2000); JEFFAMINE® T series ((H2N(CH(CH3)CH2O)) x CH2)CH2R((CH2) n (OCH2CH(CH3)) y NH2)(CH2(OCH2CH(CH3) z NH2), such as T-403 (R=C2H5, Mw=440) and T-5000 (R=H, Mw=5000); JEFFAMINE® EDR series (H2N(CH2)). x (OCH2CH2O)(CH2) x NH2), such as EDR-148 (Mw 148), EDR-176 (Mw 176); JEFFAMINE® THF series (diamines or triamines based on PTMEG / PPG copolymers), such as THF-100 (Mw 1000), THF-170 (Mw 1700); JEFFAMINE® SD&ST series (secondary amine versions of JEFFAMINE's core products), such as SD-231 (Mw 315), SD-401 (Mw 515), SD-2001 (Mw 2050), ST-404 (Mw 1700), etc. 565); or any amine containing one or more free hydroxyl groups, such as N,N-dimethylethanolamine, N-(3-dimethylaminopropyl)-N,N-diisopropanolamine, N,N,N'-trimethylaminoethyl-ethanolamine, N,N,N'-trimethyl-N'-hydroxyethyl-diaminoethyl ether, 2-(2-dimethylaminoethoxy)ethanol, etc. In one embodiment, the borane-amine complex may be selected from one or more commercially available JEFFCAT® amine products, including but not limited to JEFFCAT® LE-30, ZR-50, Z-80, Z-130, DPA, etc. In at least one embodiment, the borane-amine complex may be selected from one or more ethylenediamine products, including but not limited to ethylenediamine (EDA), tetraethylenepentamine (TEPA), triethylenetetramine (TETA), aminoethylethanolamine (AEEA), aminoethylpiperazine (AEP), etc. In at least one embodiment, any immobilized amine, including but not limited to silica-bonded amines, may be used to generate the borane-amine complex.

[0051] In a preferred embodiment, the borane-amine complex is borane-triethylamine. The borane-triethylamine complex is a liquid at room temperature and is stable in air.

[0052] In some embodiments, the aldehyde scavenger is present in an amount of about 0.05 parts by weight (pbw) to about 5 pbw, preferably about 0.05 to about 1.5 pbw, more preferably about 0.05 to 0.5 pbw. The necessary amount of aldehyde scavenger included in the composition depends on the end use of the foam, the type of PU foam, and any other additives present in the composition. By providing an aldehyde scavenger in the range of 0.1 pbw to 5 pbw, it is generally ensured that all aldehydes are removed from the composition without negatively impacting the chemical and physical properties of any resulting foam. The aldehyde scavenger may also be volatile. Therefore, if the concentration is too high, the volatile organic compound (VOC) content of the foam will be too high. If the concentration of the aldehyde scavenger is too low, it may not be able to remove all the aldehydes present in the PU foam.

[0053] In some embodiments, the composition comprises two or more aldehyde scavengers comprising borane-amine complexes. The second (or additional) borane-amine complex may be selected from the group described above with respect to the first borane-amine complex.

[0054] In some embodiments, the composition may also contain an additional aldehyde scavenger that is not a borane-amine complex. Examples of suitable aldehyde scavengers will be known to those skilled in the art.

[0055] In some embodiments, the polyfunctional isocyanate component comprises a semi-prepolymer or prepolymer formed by the reaction of a polyisocyanate with a polyol.

[0056] According to one embodiment, the polyisocyanate component includes one or more polyisocyanates, such as aliphatic polyisocyanates or aromatic polyisocyanates.

[0057] Examples of aliphatic polyisocyanates include, but are not limited to, hexamethylene diisocyanate (HDI), tetraalkylxylene diisocyanate, cyclohexane diisocyanate, 1,12-dodecane diisocyanate, 1,4-tetramethylene diisocyanate, 1,3- and 1,4-cyclohexane diisocyanates, 1-isocyanate-3,3,5-trimethyl-5-isocyanate-methyl-cyclohexane (isophorone diisocyanate), 4,4′-, 2,2′- and 2,4′-dicyclohexylmethane diisocyanates, and mixtures of the corresponding isomers.

[0058] Examples of aromatic polyisocyanates include, but are not limited to, isophenyl diisocyanate, terephthalic diisocyanate, 4,4′- or 2,4′- or 2,2′-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl diisocyanate (a mixture of MDI and its oligomers known in the art, i.e., “crude” MDI or polymeric MDI having an isocyanate functionality greater than 2), 2,4- and 2,6-toluene diisocyanate (TDI), bianisidine diisocyanate, bitoluene diisocyanate, naphthalene-1,4-diisocyanate, and diphenyl 4,4′-diisocyanate.

[0059] Alternatively, semi-prepolymers or prepolymers formed by reacting polyisocyanates (e.g., MDI, modified MDI, and / or para-MDI) with polyols may also be used as polyisocyanates. The polyol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, or other suitable polyol. These polyols may be used alone or in combination of two or more. Additionally, the polyol may be a copolymer of one or more polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, or other suitable polyols. In one embodiment, the polyol is a copolymer of a polyester polyol and a polycarbonate polyol.

[0060] Examples of polyether polyols include, but are not limited to, polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymers, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and polyether polyols obtained by ring-opening copolymerization of olefin oxides such as ethylene oxide and / or propylene oxide with isocyanate reactive initiators having a functionality of 2 to 8. Isocyanate reactive initiators include, but are not limited to, alcohols, glycols, or high molecular weight polyether polyols.

[0061] Polyester polyols include, but are not limited to, those obtained by reacting a diol with a polybasic acid. Examples of diols include ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol. Examples of polybasic acids include phthalic acid, dimer acids, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid.

[0062] Examples of polycarbonate polyols include, but are not limited to, aliphatic polycarbonate diols, such as those based on alkylene glycols, ether glycols, alicyclic glycols, or mixtures thereof. In some embodiments, the alkylene group used to prepare the polycarbonate polyol may contain 5 to 10 carbon atoms and may be linear, cycloalkylene, or combinations thereof. Non-limiting examples of such alkylene groups include hexene, octene, decene, cyclohexene, and cyclohexyldimethylene. In non-limiting examples, the polycarbonate polyol may be prepared by reacting an alkylene glycol with a dialkyl carbonate such as methyl, ethyl, n-propyl, or n-butyl carbonate or a diaryl carbonate such as diphenyl or dinaphthyl carbonate, or by reacting a hydroxyl-terminated alkylene glycol with phosgene or dichloroformate, in a manner well known to those skilled in the art.

[0063] Polycaprolactone polyols include, but are not limited to, those prepared by condensing caprolactone in the presence of an initiator, such as water, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, dipropylene glycol, 1,3-propanediol, polyethylene glycol, polypropylene glycol, poly(ethylene oxide propylene) glycol, and similar polyalkylene glycols (which may be blocked, capped, or hybridized and contain up to about 40 or more alkylene oxides in the molecule). The following are examples of caprolactones that can react with an initiator: 3-methyl-1,5-pentanediol, cyclohexanediol, 4,4'-methylene-bis-cyclohexanol, 4,4'-isopropylidene-bis-cyclohexanol, xylenediol, 2-(4-hydroxymethylphenyl)ethanol, 1,4-butanediol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, triisopropanolamine, erythritol, pentaerythritol, and N,N,N',N'-tetra(2-hydroxyethyl)ethylenediamine. The caprolactone that reacts with the initiator may be caprolactone itself or a substituted caprolactone, as described in U.S. Patent No. 3,169,945, the contents of which are incorporated herein by reference.

[0064] Examples of other polyols may include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, polyoxyethylene bisphenol A ether, polyoxypropylene bisphenol A ether, polyoxyethylene bisphenol F ether, and polyoxypropylene bisphenol F ether.

[0065] In some embodiments, the polyisocyanate is a prepolymer having an NCO value of about 10% to about 30%. In some embodiments, the polyisocyanate is a prepolymer having a molecular weight of about 200 to about 2000.

[0066] In some embodiments, the composition further comprises a blowing agent. Blowing agents are commonly used in the manufacture of foams. They can be used to form a fine and regular honeycomb structure in the resulting foam. Blowing agents typically boil due to the heat generated by the exothermic reaction between the isocyanate and the isocyanate reactive component.

[0067] Examples of suitable blowing agents include, but are not limited to, water, carbon dioxide, hydrofluorocarbons, cyclopentane, methyl isobutyl ketone, dimethoxymethane, saturated hydrocarbons (including, but not limited to, n-hexane, n-heptane and pentane), chloromethane, or mixtures thereof.

[0068] In some embodiments, the composition further comprises an amine catalyst. Any catalyst known in the polyurethane field can be used. Known catalysts include amine catalysts and tin catalysts. Examples of suitable catalysts include tertiary amine catalysts. For example, suitable tertiary amine catalysts include, but are not limited to, 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-propanediamine, dimethylaminopropylamine, (N,N-dimethylaminoethoxy)ethanol, N-methyl -N'-hydroxyethylpiperazine, 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-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole, and N-(2-hydroxyethyl)imidazole, or combinations thereof.

[0069] In some embodiments, the composition may further comprise a crosslinking agent. Examples of suitable crosslinking agents include, but are not limited to, glycerol, diethanolamine, ((2-diethylamino)ethanol), triethanolamine, dimethylolpropane, 1,2,4-butanediol, diethylene glycol, 1,4-butanediol, propylene glycol, ethylene glycol, and mixtures thereof. Preferably, diethanolamine or ((2-diethylamino)ethanol is preferred.

[0070] In some embodiments, the composition may further comprise additives, including but not limited to at least one pigment, at least one filler, at least one surfactant, and mixtures thereof.

[0071] Examples of suitable additives include, but are not limited to, CaCO3, BaSO4, fumed silica, thixotropic agents such as hydrogenated castor oil, defoamers, wetting agents, catalysts, plasticizers, silane coupling agents, pigments, and combinations thereof.

[0072] Adding fillers can improve the physical or chemical properties of any resulting polyurethane foam.

[0073] Another aspect of this disclosure provides the use of the above-described composition in the manufacture of polyurethane materials.

[0074] Another aspect of this disclosure provides the use of aldehyde scavengers comprising borane-amine complexes for removing aldehydes from polyurethane compositions.

[0075] The aldehyde scavenger is as described above regarding the composition used in the preparation of polyurethane foam.

[0076] In some implementations, the aldehyde is selected from formaldehyde, acetaldehyde, and propionaldehyde. These aldehydes are common contaminants present in PU foam. Formaldehyde, acetaldehyde, and propionaldehyde are all considered toxic to animals and the environment. For example, formaldehyde is a highly toxic systemic poison that is readily absorbed through inhalation. Its vapors are severe respiratory and skin irritants and can cause dizziness or suffocation. Contact with formaldehyde solutions can cause severe burns to the eyes and skin. Acetaldehyde is a flammable, transparent liquid. Acetaldehyde has a strong fruity odor and can cause breathing difficulties at high concentrations. Studies have reported that inhalation exposure to high levels of propionaldehyde can lead to anesthesia and liver damage, and intraperitoneal exposure can cause elevated blood pressure.

[0077] In another aspect, this disclosure provides a method for preparing polyurethane, the method comprising:

[0078] i. Providing multifunctional isocyanate compositions;

[0079] ii. Provide isocyanate reactive compositions;

[0080] iii. Provide aldehyde scavengers comprising borane-amine complexes;

[0081] iv. Mix the multifunctional isocyanate composition, the isocyanate reactive composition, and the aldehyde scavenger; and

[0082] v. To solidify the resulting mixture.

[0083] The multifunctional isocyanate composition, isocyanate reactive composition, and aldehyde scavenger are the same as those defined above for compositions used in the preparation of polyurethane foam.

[0084] The composition can be cured by any method known to those skilled in the art. Typically, the curing process of polyurethane foam is characterized by: (1) the reaction mixture changing from a liquid to a solid state; (2) the curing reaction being completed within a short time; and (3) the volume of the reaction mixture expanding dramatically during foaming. For example, the curing time can range from several minutes to several hours. Curing may involve mixing the components of the composition at room temperature or elevated temperatures.

[0085] In some embodiments, the catalyst may be included in the mixture, the polyfunctional isocyanate composition, the isocyanate reactive composition, or the aldehyde scavenger composition. The catalyst may be the same as described above.

[0086] In another aspect, this disclosure provides articles obtained using the methods described above. These articles may have any shape or hardness suitable for their final use.

[0087] In another aspect, this disclosure provides polyurethanes comprising borane-amine complexes.

[0088] The polyurethane disclosed herein is preferably used in furniture and / or automotive applications.

[0089] In some embodiments, the polyurethane used in the compositions of this disclosure, the methods of this disclosure, or the uses described above may be a foam; for example, a thermosetting foam, a rigid foam, a flexible foam, a semi-rigid foam, or a monolithic foam, or may be a polyurethane coating and / or a polyurethane adhesive.

[0090] Example

[0091] Further details and advantages of this disclosure will become apparent from the following embodiments.

[0092] JEFFOL®G31-28, JEFFOL®PPG-3706, JEFFCAT®LE-310, JEFFCAT®ZF-10, JEFFCAT®LE-30, JEFFCAT ® ZR-50, JEFFAMINE® D-230, TETRATEMA, and SUPRASEC® 7320 are available from Huntsman International LLC. Ammoniaborane is available from Sigma Aldrich. TEGOSTAB® B8734 LF2 is supplied by Evonik Industries.

[0093] Example 1

[0094] To test the effectiveness of including an aldehyde scavenger in the composition used to form PU foam, a borane-triethylamine complex was added in situ to the formulated B-side (containing primary and secondary polyols, a silicone surfactant, water as a blowing agent, diethanolamine 85% low freezing point grade (DEOA 85% LFG) as a crosslinking agent, and an amine catalyst for foaming and gelation) in two different amounts (0.25 parts by weight (pbw) and 0.1 pbw). Detailed compositions of these materials are provided in Table 1 below.

[0095] Table 1: Composition of the formulation on side B

[0096]

[0097] A control foam was also prepared for comparison. This control foam had the same composition as the exemplary foam, but lacked the aldehyde scavenger.

[0098] Weigh the required amounts of side B (masterbatch) and borane-triethylamine complex into a paper cup and premix for 6 seconds, repeating this process twice in total to aid nucleation.

[0099] The required SUPRASEC ® 7320 isocyanate (MDI isocyanate MDI (isocyanate); NCO number: 29.8%; functionality: 2.20) was weighed into a disposable plastic cup and then transferred to a paper cup containing the premixed B side, and immediately mixed for 6 seconds at ambient temperature at a mixing cycle of 3000 RPM (speed per minute).

[0100] Then place the cup containing the fresh foam on the workbench fume hood to allow it to cure.

[0101] By using FOAMAT ® The device records the relationship between foam height and time to obtain the free-floating curve of the mixed foam, and provides it to... Figure 1 middle. Figure 1 The y-axis shows the foam height (mm), and the x-axis shows time (seconds). The dashed line represents the foam height over time for the control, while the solid line represents the foam height over time for the composition containing 0.25 pbw Et3NBH3. Figure 1 The results showed that adding 0.25 pbw of borane-triethylamine complex did not affect the reactivity of PU foam.

[0102] Example 2

[0103] Cup foams were prepared using the compositions described in Table 1 above, with 0.25 pbw of borane-triethylamine complex added. After the cup foams were prepared, they were left to cure on the surface for a few minutes, and then covered with several layers of plastic film to prevent VOCs from evaporating before testing.

[0104] The amount of aldehyde present was determined using a microchamber, a DNPH (2,4-dinitrophenylhydrazine) box, and high-performance liquid chromatography (HPLC). The microchamber was set to 65°C and 50% relative humidity. Any volatile aldehydes were then captured using the DNPH box. The resulting derivatives were then diluted in acetonitrile and analyzed by HPLC.

[0105] The results of Example 2 are shown in Figure 2 and Figure 3 middle. Specifically, Figure 2 Aldehyde emission results are provided, with the x-axis indicating the measured aldehyde concentrations (formaldehyde (FA), acetaldehyde (AA), propionaldehyde (PA), and total aldehyde emissions), and the y-axis showing aldehyde emissions in parts per billion (ppb). Total aldehyde emissions are determined by adding the FA, AA, and PA emissions. Figure 2In the figure, the bars with diagonal lines represent the aldehyde emissions in the control composition (i.e., without the presence of an aldehyde scavenger). Figure 2 The cross-hatched bar graph shows the aldehyde content when 0.25 pbw Et3NBH3 is present in the composition. Compared with the control, the foam containing the borane-triethylamine complex had low FA levels and AA and PA levels below the detection limit (e.g., less than 1 ppb).

[0106] Figure 3 The results (in ppb) for adding only 0.1 pbw of the borane triethylamine complex are shown. The x-axis and y-axis are compared with... Figure 2 The description is the same. The bar charts with diagonal lines correspond to the control composition, while the bar charts with crosshairs correspond to the case where an aldehyde scavenger is present. As shown, the exemplary compositions exhibit significantly lower aldehyde emission levels across all categories compared to the control.

[0107] Example 3

[0108] To test the effectiveness of the aldehyde scavenger in removing acetaldehyde, 0.01 g of acetaldehyde was spiked into 300 g of the formulation in Table 1 (minus isocyanate). The composition was thoroughly mixed and divided into two samples. 0.25 pbw of borane-triethylamine complex was added to the first sample, while the other sample was left untreated.

[0109] The aldehyde test results of Example 3 are shown in Figure 4 middle. Figure 4 The graphs in the table show aldehyde emissions (ppb) on the y-axis and the concentration of which aldehyde was measured on the x-axis. The bars with diagonal lines represent the aldehyde emissions in the control composition (i.e., without an aldehyde scavenger). The bars with crosshairs show the aldehyde content of the composition with 0.25 pbw Et3NBH3. Formaldehyde (FA) was detected in both samples; however, the composition containing the borane-triethylamine complex had significantly less aldehyde. As expected, the control foam had a high level of acetaldehyde (AA) (6460 ppb), while the exemplary composition containing the borane complex showed only 55 ppb. As clearly shown in the table, the test results clearly demonstrate the significant effectiveness of the borane-triethylamine complex as an acetaldehyde scavenger.

[0110] Figure 5 The results are shown after the B-side formulation described above was kept at a high temperature for a period of time. The following conditions were tested.

[0111] - The control is side B with acetaldehyde spiked (as described above).

[0112] -0.25 pbw boronane triethylamine complex (room temperature)

[0113] -0.25 pbw borane triethylamine complex (60°C for 30 minutes).

[0114] The results of this analysis are provided to Figure 5 middle. Figure 5 The y-axis shows aldehyde emissions (ppm), and the x-axis indicates the different aldehyde concentrations measured. The bars with upward sloping lines represent aldehyde emissions from the control composition (i.e., the spiked composition without an aldehyde scavenger). The bars with crosshairs show aldehyde emissions from the composition containing 0.25 pbw Et3NBH3 at room temperature. The bars with downward sloping lines (zero ppm for both FA and PA) show aldehyde emissions from the composition containing 0.25 pbw Et3NBH3 when the temperature is maintained at 60°C for 30 minutes. Figure 5 The results demonstrated that formaldehyde (FA) was not detected in any of the systems studied. As expected, a high level of acetaldehyde (AA) of 115 ppm was detected in the control composition, but significantly lower acetaldehyde emissions were observed in the exemplary composition, specifically 10 ppm for the composition containing the borane complex at room temperature, and only 1 ppm for the composition containing the borane complex after treatment at 60°C for 30 minutes. The control composition also showed significant propionaldehyde emissions, while propionaldehyde (PA) emissions from the exemplary composition were undetectable.

[0115] This further demonstrates that borane is effective as an aldehyde scavenger when acetaldehyde (AA) is added to the prepared B side.

[0116] Example 4

[0117] Formaldehyde (FA) is known to form over time in the presence of a pure tertiary amine catalyst, in open air, and in compositions containing methyl groups in their chemical structure. Tertiary amine catalysts are commonly used in the manufacture of polyurethane (PU) foam. Therefore, random tertiary amine catalysts were evaluated for 5 weeks in the presence and absence of a 0.05 pbw borane-triethylamine complex. Figure 6 A line graph is shown, illustrating the aldehyde content measured over five weeks (horizontal axis) (y-axis).

[0118] An initial formaldehyde (FA) level of 139 ppm was observed in the pure catalyst, and it continued to increase. In contrast, the composition including the borane-amine complex showed a significantly lower formaldehyde (FA) level, both initially (17 ppm) and throughout the five weeks. Under the same conditions as the control, the increase in FA content observed in the exemplary composition was negligible.

[0119] The experiment was repeated to test acetaldehyde (AA) emissions, and the results are shown in... Figure 7Formaldehyde emissions (in China) Figure 6 ) and acetaldehyde emissions ( Figure 7 The test results are shown in ppm, with control compositions indicated by circles and solid lines, and exemplary compositions containing 0.05 pbw borane-amine complexes indicated by boxes and dashed lines.

[0120] The results of the two tests clearly demonstrate the effectiveness of the borane-amine complex in removing aldehydes from the composition over a longer period of time.

[0121] Examples 5-8 use laboratory-prepared borane complexes JEFFCAT® LE30-borane, JEFFAMINE® D-230 borane, JEFFCAT® ZR-50 borane, and TETA borane. These borane complexes are prepared using the corresponding amines according to the following methods.

[0122] General procedure for amine-borane synthesis:

[0123]

[0124] Sodium borohydride (1.1 equivalents per nitrogen atom) and ammonium sulfate powder (0.5 equivalents relative to sodium borohydride) were transferred to a two-necked round-bottom flask equipped with a stir bar under an air atmosphere. Then, amine (100 g) and THF (0.5 M) were added to the flask (H2 gas was observed to escape). A condenser connected to a cooler set to 5 °C was attached to one neck of the reaction flask. The other neck was sealed with a stopper. The top of the condenser was sealed with a diaphragm fitted with an open needle to relieve any pressure buildup. The reaction was heated overnight under reflux with vigorous stirring. A 0.5 mL sample was removed and concentrated under vacuum. The progress of the reaction was examined using NMR (CDCl3) (for the products, ...). 11 B = approximately -10 to -20 ppm.

[0125] The reaction mixture was cooled to room temperature and filtered through diatomaceous earth to remove excess sodium salt. The diatomaceous earth was washed with THF and the combined filtrates were concentrated under vacuum to give the product, the structure of which is shown below:

[0126]

[0127] Borane complexes prepared in the laboratory were characterized by spectroscopic methods. 11 B NMR data are as follows: LE-30 borane, -9.90 ppm (broad peak); D-230 borane, -21.18 ppm (broad peak); ZR-50 borane, -10.09 ppm (broad peak); TETA borane, -14.5 to -19.70 ppm (broad peak); and trioctylamine-borane, -5.0 ppm (broad peak).

[0128] Cup foams were prepared similarly to those in Example 2 using the compositions described in Table 1 and the corresponding amine borane complexes at different dosage levels.

[0129] Example 5

[0130] Figure 8 The results are shown for a composition containing 0.25 pbw of the JEFFCAT® LE-30-borane (40%, in TETA solvent) complex compared to the control composition described above. The bars with diagonal lines represent emissions from the control, while the bars with crosshairs represent compositions including JEFFCAT® LE-30-borane. As shown, even at such low concentrations, JEFFCAT® LE30-borane effectively reduces formaldehyde (FA) emissions. No reduction in acetaldehyde (AA) and propionaldehyde (PA) emissions was observed in this example.

[0131] Example 6

[0132] Figure 9 The results show a comparison of aldehyde emissions between a control composition without additives (represented by solid bars) and compositions containing the JEFFAMINE® D-230-borane complex as described above, at concentrations of 0.25 pbw (represented by crosshair bar graphs), 0.75 pbw (represented by bar graphs with downward sloping lines), and 1.50 pbw (represented by bar graphs with upward sloping lines). As shown, each composition containing JEFFAMINE® D-230-borane effectively reduced formaldehyde (FA), acetaldehyde (AA), and propionaldehyde (PA) emissions (measured in ppb).

[0133] Example 7

[0134] Figure 10 The results of aldehyde emission tests are shown, comparing the control composition without additives (represented as solid bars) with compositions containing 0.25 pbw (represented as cross-hatched bar graphs) and 0.50 pbw (represented as bar graphs with downsloping lines), respectively. As shown, the addition of JEFFCAT® ZR-50-borane effectively reduced formaldehyde (FA), acetaldehyde (AA), and propionaldehyde (PA) emissions.

[0135] Example 8

[0136] Figure 11The results of aldehyde emission tests are shown, comparing a control composition without additives (represented by bar graphs with diagonal lines) and a composition with a TETA-borane complex of 0.25 pbw (25%, in solvent TETA, represented by bar graphs with crosshairs). As shown, the presence of the TETA-borane additive effectively reduced formaldehyde (FA) and acetaldehyde (AA) emissions. However, no reduction in propionaldehyde (PA) was observed.

[0137] Example 9

[0138] Figure 12 The results of aldehyde emission tests are shown, comparing a control composition without additives (represented by a bar graph with diagonal lines) and a composition with an aminoborane complex from Sigma Aldrich (0.25 pbw, represented by a bar graph with crosshairs on the formulation B side). As shown, the presence of the aminoborane additive effectively reduced the emissions of each of formaldehyde (FA), acetaldehyde (AA), and propionaldehyde (PA).

[0139] It should be understood that, although preferred embodiments and / or materials have been discussed to provide embodiments according to this disclosure, various modifications or changes may be made without departing from the spirit and scope of the disclosure described herein.

Claims

1. A composition comprising: Multifunctional isocyanate compositions; Isocyanate reactive compositions; and Aldehyde scavengers, including borane-amine complexes.

2. The composition according to claim 1, wherein the borane-amine complex is selected from mono, di, tri, or polyamines containing 0 to 100 carbon atoms of alkyl or aromatic amines.

3. The composition according to claim 1 or claim 2, wherein the borane-amine complex is selected from: ammonia; trimethylamine; triethylamine; trioctylamine; tripropylamine; triisopropylamine; tributylamine; tri-tert-butylamine; triisobutylamine; tricyclohexylamine; tricyclopentylamine; triphenylamine; dimethylamine; diethylamine; dipropylamine; dibutylamine; di-tert-butylamine; diisobutylamine; dicyclohexylamine; dicyclopentylamine; diphenylamine; tert-butylamine; isobutylamine; isopropylamine; propylamine; ethylamine; methylamine; diethanolamine, ((2-diethylamino)ethanol); triethanolamine; 1,2-ethylenediamine; 1,3-propylidenediamine; 1,4-butylidenediamine; 1,5-pentylidenediamine; 1,5-hexylidenediamine; N,N,N',N'-tetramethyl-1,2-ethylenediamine; N N,N',N'-Tetramethyl-1,3-propylidene diamine; N,N,N',N'-Tetramethyl-1,4-butylidene diamine; N,N,N',N'-Tetramethyl-1,5-pentanediamine; N,N,N',N'-Tetramethyl-1,6-hexylidene diamine; N,N-Dimethylaniline; Benzyldimethylamine; N,N-Dimethylcyclohexylamine; Pentamethyldiethylenetriamine; N,N,N',N'',N''-Pentamethyldipropylenetriamine; Bis(2-dimethylaminoethyl) ether; N-Methylmorpholine; N-Ethylmorpholine; 2,2'-Dimorpholinodiethyl ether; 1,3,5-Tris(3-(dimethylamino)propyl)-hexahydro-s-triazine; Having the formula (H2N(CH(CH3)CH2O) x The polyetheramine (CH2CH(CH3)NH2) has the formula (H2NCH(CH3)CH2(OCH2CH(CH3)) x (OCH2CH2) y (OCH2CH(CH3)) z Polyetheramines containing NH2, having the formula (H3C-(OCH2CH2)) x (OCH2CHR) y Polyetheramines of NH2, having the formula ((H2N(CH(CH3)CH2O) x CH2)CH2R((CH2) n (OCH2CH(CH3)) y NH2)(CH2(OCH2CH(CH3) z Polyetheramines containing NH2, having the formula (H2N(CH2)) x (OCH2CH2O)(CH2) x Polyetheramines of NH2, or secondary amine versions of any of the foregoing; diamines or triamines based on PTMEG / PPG copolymers; N,N-dimethylethanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N,N,N'-trimethylaminoethylethanolamine; N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether; 2-(2-dimethylaminoethoxy)ethanol; ethylenediamine (EDA); tetraethylenepentamine (TEPA); triethylenetetramine (TETA); aminoethylethanolamine (AEEA); aminoethylpiperazine (AEP); immobilized amines; or mixtures thereof.

4. The composition according to any one of claims 1 to 3, wherein the borane-amine complex is borane-triethylamine.

5. The composition according to any one of claims 1 to 4, wherein the aldehyde scavenger is present in an amount of about 0.05 parts by weight (pbw) to about 5 pbw, preferably about 0.05 to about 1.5, more preferably about 0.05 to 0.5 pbw.

6. The composition according to any one of the preceding claims, wherein the composition comprises two or more aldehyde scavengers comprising borane-amine complexes.

7. The composition according to any one of the preceding claims, wherein the composition further comprises an additional aldehyde scavenger, wherein the additional aldehyde scavenger is not a borane-amine complex.

8. The composition according to any one of the preceding claims, wherein the polyfunctional isocyanate component comprises a semi-prepolymer or prepolymer formed by the reaction of a polyisocyanate with a polyol.

9. The composition according to any one of the preceding claims, wherein the polyisocyanate component comprises one or more polyisocyanates, such as aliphatic polyisocyanates or aromatic polyisocyanates.

10. The composition according to any one of the preceding claims, wherein the composition further comprises a foaming agent.

11. The composition according to any one of the preceding claims, wherein the composition further comprises an amine catalyst.

12. The composition according to any one of the preceding claims, wherein the composition further comprises a crosslinking agent, preferably wherein the crosslinking agent is diethanolamine or ((2-diethylamino)ethanol).

13. The composition according to any one of the preceding claims, wherein the composition further comprises an additive selected from at least one pigment, at least one filler, at least one surfactant, and mixtures thereof.

14. Use of aldehyde scavengers containing borane-amine complexes for removing aldehydes from polyurethane foams.

15. The use according to claim 14, wherein the aldehyde is selected from formaldehyde, acetaldehyde, and propionaldehyde.

16. A method for preparing polyurethane foam, the method comprising: Provide polyol compositions; Provide isocyanate reactive compositions; Provide aldehyde scavengers containing borane-amine complexes; Mix a multifunctional isocyanate composition, an isocyanate reactive composition, and an aldehyde scavenger; and Allow the resulting mixture to solidify.

17. The article of manufacture obtained by the method of claim 16.

18. Polyurethane foam containing borane-amine complexes.

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