Aldehyde scavengers for polyurethane foam

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. Methods for removing aldehydes from a polyurethane foam, foam compositions and articles made using foam compositions.

Description

ALDEHYDE SCAVENGERS FOR POLYURETHANE FOAM Cross Reference to Related Applications

[0001] This application claims priority to U.S. Provisional Patent Application Serial Number 63 / 555,943 filed February 21, 2024. The noted application(s) are incorporated herein by reference. Background to the Invention

[0002] Polyurethane (“PU”) foam materials have excellent cushion properties and lightweight properties, mass productivity, economic efficiency, and the like. They are therefore commonly used in the automotive and furnishing industries as cushioning. PU foams are generally prepared by a high temperature synthesis process comprising mixing an isocyanate reactive compound and a polyol. However, the process may emit volatile organic compounds (“VOCs”) such as formaldehyde and other aldehydes.

[0003] It is generally believed that aldehydes in PU foams are formed from the auto-oxidation of components containing methyl or other side chain groups like methylene that are present in polyols or amine catalysts, or silicone surfactants, or the like, that are used for the synthesis of polyurethanes. Aldehydes could also be generated during or after the foaming process when the foam is exposed to air. Generated aldehydes include formaldehyde and higher molecular weight compounds such as acetaldehyde and propionaldehyde.

[0004] Aldehydes are commonly toxic and when present in PU foams may be responsible for causing nervous system disorders and sick house syndromes. There is therefore a demand from the automotive and furnishing (e.g., bedding) industries for additives to remove aldehydes from PU foams.

[0005] Several solutions to remove formaldehyde from PU foams are known. For example, US 2018 / 0171064 and US 2008 / 0281013 A1 describe the use of sulfurous 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 and ammonium salts to scavenge aldehydes.

[0006] There are commercially available products that are advertised to be able to remove formaldehyde, for example, JEFFADD® AS-53 and JEFFADD® AS-76 (commercially available from Huntsman International LLC).

[0007] Unfortunately, the solutions mentioned above only reduce the levels of formaldehyde in the PU foams. They are not as effective at removing higher molecular weight aldehydes.Object of the Invention

[0008] There is therefore a need to provide an aldehyde scavenger that can be included in a PU foam composition to scavenge aldehydes, including higher molecular weight aldehydes without negatively impacting the properties of the PU foam.

[0009] The composition of the present disclosure can solve problems associated with conventional compositions and methods by providing an aldehyde scavenger for use in PU compositions. The present disclosure relates to aldehyde scavenger compositions useful in the production of low or no aldehyde emission polyurethane foam. This reduced aldehyde emission can be accomplished by incorporating an aldehyde scavenger or scavengers into a “pre-mixed” formulation used for generating a PU foam. Brief Description of the Drawings

[0010] Figure 1 is a graph illustrating a comparison of the rise profile for a PU foam of Example 1 made with 0 pbw and 0.25 pbw borane-triethylamine complex present.

[0011] Figure 2 is a graph illustrating the evaluation of aldehyde concentration when 0 pbw and 0.25 pbw borane triethylamine complex is added.

[0012] Figure 3 is a graph illustrating the evaluation of aldehyde concentration when 0 pbw and 0.1 pbw borane triethylamine complex is added.

[0013] Figure 4 illustrates the aldehyde content in spiked PU foams in the presence of an aldehyde scavenger.

[0014] Figure 5 illustrates the aldehyde content in spiked PU foams in the presence of an aldehyde scavenger.

[0015] Figure 6 illustrates the evaluation of aldehydes in pure tertiary amine catalyst in the presence of 0.05 pbw borane-amine complex for formaldehyde.

[0016] Figure 7 illustrates the evaluation of aldehydes in pure tertiary amine catalyst in the presence of 0.05 pbw borane-amine complex for acetaldehyde.

[0017] Figures 8 to 12 illustrate the evaluations of aldehyde emission concentrations when different borane-amine complexes are included at various concentrations. Detailed Description

[0018] Unless otherwise defined, all terms used in disclosing the present disclosure, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. By means of further guidance, term definitions are included to better appreciate the teaching of the present disclosure.

[0019] It is to be noticed that the term “comprising”, as used in the claims and the present disclosure, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It is thus to be interpreted as specifying the presence of the stated features, steps or components as referred to, but does not preclude 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 only of components X and Y. It means that with respect to the present disclosure, the only relevant components of the compound are X and Y.

[0020] Throughout this specification, reference to “one embodiment” or “an embodiment” are made. Such references indicate that a particular feature, described in relation to the embodiment is included in at least one embodiment of the present disclosure. Thus, appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification do not necessarily all referring to the same embodiment, though they could. Furthermore, the particular features or characteristics may be combined in any suitable manner in one or more embodiments, as would be apparent to one of ordinary skill in the art.

[0021] The terms “preferred” and “preferably” as used herein refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the present disclosure.

[0022] Where substituent groups are specified by their conventional chemical formula, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, for example, -CH2O- is equivalent to -OCH2-.

[0023] The term “optional” or “optionally” as used herein means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0024] Throughout this disclosure, the term “about” as used herein indicates that a value includes the inherent variation of error for the quantifying device, mechanism, or method, or the inherent variation that exists among the subject(s) to be measured. For example, but not by way of limitation, when the term “about” is used, the designated value to which it refers may vary by plus or minus ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent, or one or more fractions therebetween.

[0025] The phrases “or combinations thereof” and “and combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC and, if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more items or terms such as BB, AAA, CC, AABB, AACC, ABCCCC, CBBAAA, CABBB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context. In the same light, the terms “or combinations thereof” and “and combinations thereof” when used with the phrases “selected from” or “selected from the group consisting of” refers to all permutations and combinations of the listed items preceding the phrase.

[0026] Unless otherwise stated the term “a” or “an” and “the” as used herein include both singular and plural referents unless the context clearly dictates otherwise. By way of example, “an isocyanate group” as used herein means one isocyanate group or more than one isocyanate group.

[0027] The term “aldehyde scavenger” and “aldehyde reducer” as used herein refers to compounds capable of reducing the emission of aldehydes in polyurea or polyurethane materials, and modified polyurethanes compared to polyurea or polyurethane materials, and modified polyurethanes made of a composition not comprising the aldehyde scavenger.

[0028] The term “aromatic” as used herein refers to a hydrocarbyl radical having 6 to 50 carbon atoms that contains at least one ring with delocalized pi electrons, such as a benzene ring.

[0029] The term “aliphatic” as used herein refers to a hydrocarbyl radical having 6 to 50 carbon atoms that does not contain a delocalized pi electron system.

[0030] The term "ambient temperature" as used herein refers to the temperature of the surrounding work environment (e.g., the temperature of the area, building or room where the composition is used), exclusive of any temperature changes that occur as a result of the direct application of heat to the composition to facilitate curing. The ambient temperature may be within a range from about 10°C to about 30°C, more specifically from about 15°C to about 25°C.

[0031] “Isocyanate index” or “NCO index” or “index” as used herein refers to the ratio of NCO-groups over isocyanate-reactive hydrogen atoms present in a formulation, given as a percentage: [NCO]x100 / [active hydrogen] (%). In other words, the NCO-index expresses the percentage of isocyanate actually used in a formulation with respect to the amount ofisocyanate theoretically required for reacting with the amount of isocyanate reactive hydrogens used in a formulation. It should be observed that the isocyanate index as used herein is considered from the point of view of the actual reaction process involving the isocyanate ingredients and the isocyanate-reactive ingredients. Any isocyanate groups consumed in a preliminary step to produce modified polyisocyanates (including such isocyanate derivatives referred to in the art as prepolymers) or any active hydrogens consumed in a preliminary step (e.g., reacted with isocyanate to produce modified polyols or polyamines) are not taken into account in the calculation of the isocyanate index. Only the free isocyanate groups and the free isocyanate-reactive hydrogens (including those of the water) present at the actual reaction stage are taken into account.

[0032] The term “hydroxyl value” as used herein refers to the concentration of hydroxyl groups, per unit weight of the polyol, which are able to react with the isocyanate groups. The hydroxyl number is reported as mg KOH / g and may be measured according to the standard ASTM D 1638.

[0033] The term “average functionality,” or “average hydroxyl functionality” of a polyol as used herein indicates the number of OH groups per molecule, on average. The average functionality of an isocyanate refers to the number of -NCO groups per molecule, on average.

[0034] The mass average molar mass (Mw) is sometimes referred to herein as weight average molecular weight. It can be measured using any technique known to the skilled person, for example, using small-angle laser light scattering.

[0035] The number average molar mass (Mn) is sometimes referred to herein as the number average molecular weight. It can be measured using any technique known to the skilled person, for example, using osmometry.

[0036] All references cited in the present specification are hereby incorporated by reference in their entirety. In particular, the teachings of all references herein specifically referred to are incorporated by reference.

[0037] In a first aspect the present disclosure relates to a composition for making a polyurethane foam, said composition comprising: (a) a polyfunctional isocyanate; (b) an isocyanate reactive composition; and (c) an aldehyde scavenger comprising a borane-amine complex.

[0038] It has been surprisingly found that when including a borane amine complex in a composition for preparing a polyurethane foam it is possible to reduce the concentration of aldehydes present in the resultant foam. The borane amine complexes are capable ofscavenging 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 the reduced emission of aldehydes compared to foams prepared in the absence of an aldehyde scavenger continues after the foam is cured and for the lifetime of the foam. Without wishing to be bound by any theory or explanation it is believed that the inventive aldehyde scavenger can interact or react with the aldehyde thereby either converting the aldehyde into another material or entrapping the aldehyde within the foam.

[0039] The inclusion of the borane-amine complex in a composition for preparing a polyurethane foam does not negatively impact either the physical or chemical properties of the resultant polyurethane foam.

[0040] As a result of including the aldehyde scavenger in the compositions, polyurethanes produced using the composition of the present disclosure do not need to be post treated to remove aldehyde impurities.

[0041] The polyfunctional isocyanate and isocyanate reactive component can be any compounds which react together to form a polyurethane foam. Polyurethanes are commonly produced by the reaction of compound comprising isocyanate-reactive hydrogens and a polyisocyanate. However, the present disclosure is not restricted to such components.

[0042] In some embodiments, the aldehyde scavenger consists essentially of a borane-amine complex. In some embodiments, the aldehyde scavenger consists of a borane-amine complex. That is, in some embodiments, the aldehyde scavenger contains no other compounds capable of acting as an aldehyde scavenger.

[0043] In some embodiments, the aldehyde scavenger comprises a borane-amine complex and an additional aldehyde scavenger. Any suitable aldehyde scavengers 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 a carbonamide and a nitrile group, hydrazine compounds, ureas, phosphorus containing compounds, halide- containing compounds, and mixtures thereof.

[0044] In some embodiments, the borane-amine complex may be any borane complex with mono-, di-, tri or polyamines of alkyl or aromatic amines that contains total of 0 to 100 carbon atoms. Examples thereof include, but are not limited to, ammonia, trimethyl amine, triethylamine, trioctylamine, tripropyl amine, tri-isopropylamine, tributylamine, tri-tert- butylamine, triisobutylamine, tricyclohexylamine, tricyclopentylamine, triphenylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, di-tert-butylamine, di- isobutylamine, 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-hexalenediamine, N,N,N',N'-tetramethyl 1,2- ethylenediamine, N,N,N',N'-tetramethyl 1,3-propylenediamine, N,N,N',N'-tetramethyl 1,4- butylenediamine, N,N,N',N'-tetramethyl 1,5-pentylenediamine, N,N,N',N'-tetramethyl 1,6- hexalenediamine, N,N-dimethylaniline, benzyldimethylamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-dipropylenetriamine, bis-(2- dimethylaminoethyl)ether, N-methylmorpholine, N-ethylmorpholine, 2,2'- dimorpholinodiethylether, 1,3,5-tris(3-(dimethylamino)propyl)-hexahydro-s-triazine, or the like. Alternatively or additionally, the borane-amine complex may be selected from one or more of polyetheramine families such as commercially available JEFFAMINE® amine products (commercially available through Huntsman International LLC) consists of monoamines, diamines, and triamines based on PEG, PPG or polytetramethylene glycol, (PTMEG)-based polyether backbone structures) such as JEFFAMINE® D-series (H2N(CH(CH3)CH2O)xCH2CH(CH3)NH2) for example, D-230 (Mw 230), D-400 (Mw 400), D-2000 (Mw 2000), and D-4000 (Mw 4000); JEFFAMINE® ED-series)x(OCH2CH2)y(OCH2CH(CH3))zNH2) for example, ED- 600 (Mw 600), ED-900 (Mw 900), ED-2003 (Mw 2000); JEFFAMINE® M-series (H3C- (OCH2CH2)x(OCH2CHR)yNH2) for example, M-600 (Mw600), M-1000 (Mw 1000), M-2005 (Mw 2000), M-2070 (Mw 2000); JEFFAMINE® T-series ((H2N(CH(CH3)CH2O)xCH2)CH2R((CH2)n(OCH2CH(CH3))yNH2)(CH2(OCH2CH(CH3)zNH2) for example, T-403 (R= C2H5, Mw = 440), and T-5000 (R= H, Mw = 5000); JEFFAMINE® EDR-series (H2N(CH2)x(OCH2CH2O)(CH2)xNH2) for example, EDR-148 (Mw 148), EDR- 176 (Mw 176); JEFFAMINE® THF-series (diamines or triamines based on PTMEG / PPG copolymer) for example, THF-100 (Mw 1000), THF-170 (Mw 1700); JEFFAMINE® SD & ST series (secondary amine versions of JEFFAMINE core products) for example, SD-231 (Mw 315), SD-401 (Mw 515), SD-2001 (Mw 2050), ST-404 (Mw 565); or any amines that contains 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-bisaminoethylether, 2-(2-dimehtylaminoethoxy)ethanol, or the like. In at least one embodiment, the borane-amine complex may be selected from one or more commercially available JEFFCAT® amine products including, without limitation, JEFFCAT® LE-30, ZR-50, Z-80, Z-130, DPA, and the like. In at least one embodiment, the borane-amine complex may be selected from one or more ethyleneamine products includingwithout limitation, ethylenediamine (EDA), tetraethylenepentamine (TEPA), triethylenetetramine (TETA), aminoethylethanolamine (AEEA), aminoethylpiperazine (AEP), or the like. In at least one embodiment, any immobilized amines including, without limitation, silica-bond amine may be used to generate the borane-amine complex.

[0045] In preferred embodiments, the borane-amine complex is borane-triethylamine. Borane- triethylamine complex is liquid at room temperature, and it is air stable.

[0046] In some embodiments, the aldehyde scavenger is present in an amount of from between about 0.05 part by weight (pbw) and about 5 pbw, preferably between about 0.05 and about 1.5 pbw, more preferably between about 0.05 and 0.5 pbw. The amount of aldehyde scavenger necessary to include in the present composition is dependent on the end use of the foam, the type of PU foam and any other additives present in the composition. By providing the aldehyde scavenger in a range of between 0.1 pbw and 5 pbw it is generally possible to ensure that all the aldehydes are removed from the composition without negatively impacting the chemical and physical properties of any resultant foam. The aldehyde scavenger may also be volatile. Therefore, if the concentration is too high, the volatile organic content (“VOC”) of the foam will be too high. If the concentration of aldehyde scavenger is too low, it may not remove all the aldehydes present in the PU foam.

[0047] In some embodiments, the composition comprises two or more aldehyde scavengers comprising a borane-amine complex. The second (or additional) borane-amine complex may be selected from the group described above in relation to a first borane-amine complex.

[0048] In some embodiments, the composition may further comprise an additional aldehyde scavenger which is not a borane-amine complex. Examples of suitable aldehyde scavengers will be known to the skilled person.

[0049] In some embodiments, the polyfunctional isocyanate component comprises a semi- prepolymer or prepolymer formed from the reaction of a polyisocyanate and a polyhydric alcohol.

[0050] According to one embodiment, the polyisocyanate component includes one or more polyisocyanates such as an aliphatic polyisocyanate or an aromatic polyisocyanate.

[0051] Examples of aliphatic polyisocyanates include, but are not limited to, hexamethylene diisocyanate (HDI), tetraalkyl xylene diisocyanate, cyclohexane diisocyanate, 1,12-dodecane diisocyanate, 1,4-tetramethylene diisocyanate, 1,3- and 1,4-cyclohexane diisocyanate, 1- isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate), 4,4′-, 2,2′- and 2,4′-dicyclohexyl-methane diisocyanate, as well as the corresponding isomer mixtures.

[0052] Examples of aromatic polyisocyanates include but are not limited to, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′- or 2,4′- or 2,2′-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene diisocyanate (mixtures of MDI and oligomers thereof known in the art as “crude” or polymeric MDI having an isocyanate functionality of greater than 2), 2,4- and 2,6-toluene diisocyanate (TDI), dianisidine diisocyanate, bitolylene diisocyanate, naphthalene-1,4-diisocyanate and diphenylene 4,4′-diisocyanate.

[0053] Alternatively, semi-prepolymers or prepolymers formed from the reaction of a polyisocyanate (e.g., MDI, modified MDI and / or p-MDI) with a polyhydric alcohol may also be employed as the polyisocyanate. The polyhydric alcohol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, or other suitable polyol. These polyols may be used either individually or in combinations of two or more. In addition, the polyhydric alcohol may be a copolymer of one or more of a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, or other suitable polyol. In one embodiment, the polyhydric alcohol is a copolymer of a polyester polyol and a polycarbonate polyol.

[0054] Examples of polyether polyols include, but are not limited to, polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymer, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and polyether polyols obtained by ring-opening co-polymerization of alkylene oxides, such as ethylene oxide and / or propylene oxide, with isocyanate-reactive initiators of functionality from 2 to 8. The isocyanate-reactive initiators include, but are not limited to, alcohols, glycols, or high molecular weight polyether polyols.^

[0055] Polyester polyols include, but are not limited to, those which may be obtained by reacting a diol and 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 acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid and sebacic acid.

[0056] Examples of polycarbonate polyols include, but are not limited to, aliphatic^polycarbonate^diols, for example those based upon alkylene glycols, ether glycols, alicyclic glycols, or mixtures thereof. In some embodiments, the alkylene groups for preparing the^polycarbonate^polyol can comprise from 5 to 10 carbon atoms and can be a straight chain, cycloalkylene or combinations thereof. Non-limiting^examples^of^such alkylene groups include hexylene, octylene, decylene, cyclohexylene and cyclohexyldimethylene. Thepolycarbonate^polyols^can be prepared, in non-limiting^examples, by reacting the alkylene glycol with a dialkyl carbonate, such as methyl, ethyl, n-propyl or n-butyl carbonate, or diaryl carbonate, such as diphenyl or dinaphthyl carbonate, or by reacting^a hydroxy-terminated alkylene diol with phosgene or bischoloroformate, in a manner well known to those skilled in the art.^

[0057] 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-propylene glycol, dipropylene glycol, 1,3-propylene glycol, polyethylene glycol, polypropylene glycol, poly(oxyethylene-oxypropylene)glycols and similar polyalkylene glycols, either blocked, capped or heteric containing up to about 40 or more alkyleneoxy units in the molecule, 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'-tetrakis-(2-hydroxyethyl)ethylene diamine. The caprolactone reacted with the initiator can be caprolactone itself or a substituted caprolactone as described in US Pat. No. 3,169,945, the contents of which are incorporated herein by reference.

[0058] Examples of other polyols may include ethylene glycol, propanediols, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, polyoxyethylene bisphenol A ether, polyoxypropylene bisphenol A ether, polyoxyethylene bisphenol F ether, and polyoxypropylene bisphenol F ether.

[0059] In some embodiments, the polyisocyanate is a prepolymer having an NCO value from about 10% to about 30%. In some embodiments, the polyisocyanate is a prepolymer having a molecular weight from about 200 to about 2000.

[0060] In some embodiments, the composition further comprises a blowing agent. Blowing agents are commonly used in the manufacture of foams. Blowing agents can be used to create fine and regular cellular structures in the resultant foam. Blowing agents commonly boiling due to the heat produced from the exothermic reaction between the isocyanate and the isocyanate reactive component.

[0061] Examples of suitable blowing agents include, but are not limited to, water, carbon dioxide, hydrofluorocarbon, cyclopentane, methyl isobutyl ketone, dimethoxymethane, saturated hydrocarbons (including but not limited to n-hexane, n-heptane, and pentane), methylene chloride, or mixtures thereof.

[0062] In some embodiments, the composition further comprises an amine catalyst. Any catalyst known in the field of polyurethane may 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 are N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N′-methyl ethanolamine, N,N,N′-trimethylaminopropyl ethanolamine, N,N-dimethylethanolamine, N,N- diethylethanolamine N,N-dimethyl-N′, N′-2-hydroxy(propyl)-1, 3-propylenediamine, dimethylaminopropylamine, (N,N-dimethylaminoethoxy) ethanol, N-methyl-N′- hydroxyethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl) amine, N,N- dimethylaminopropyl urea, diethylaminopropyl urea 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 a combination thereof.

[0063] In some embodiments the composition may further comprise a cross linking agent. Suitable examples of crosslinkers 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 ((2-diethylamino)ethanol).

[0064] In some embodiments the composition may further comprise additives include but are not limited to at least one pigment, at least one filler, at least one surfactant and mixtures thereof.

[0065] Suitable examples of additives include but are not limited to CaCO3, BaSO4,fumed Silica, a thixotropic agent such as hydrogenated castor oil, a defoamer, a wetting agent, a catalyst, a plasticizer, a silane coupling agent, a pigment, and combinations thereof.

[0066] The inclusion of a filler can improve the physical or chemical properties of any resultant polyurethane foam.

[0067] A further aspect of the present disclosure provides the use of the composition described above for the manufacture of a polyurethane material.

[0068] A further aspect of the present disclosure provides the use of an aldehyde scavenger comprising a borane-amine complex for removing aldehydes from a polyurethane composition.

[0069] The aldehyde scavenger is as described above in relation to the composition for making a polyurethane foam.

[0070] In some embodiments, the aldehydes are selected from formaldehyde, acetaldehyde and propionaldehyde. These aldehydes are found as common contaminates in PU foams. Formaldehyde, acetaldehyde and propionaldehyde are all considered toxic to both animals andthe environment. For example, formaldehyde is a highly toxic systemic poison that is easily absorbed by inhalation. The vapor is a severe respiratory tract and skin irritant and may cause dizziness or suffocation. Contact with formaldehyde solution may cause severe burns to the eyes and skin. Acetaldehyde is a clear liquid that burns easily. Acetaldehyde has a strong, fruity odour that in high concentrations can make breathing difficult. Studies have reported that exposure to high levels of propionaldehyde, via inhalation, results in aesthesia and liver damage, and intraperitoneal exposure results in increased blood pressure.

[0071] In a further aspect, the present disclosure provides a method for preparing a polyurethane, said method comprising: i. providing a polyfunctional isocyanate composition; ii. providing an isocyanate reactive composition; iii. providing an aldehyde scavenger comprising a borane-amine complex; iv. mixing the polyfunctional isocyanate composition, the isocyanate reactive composition and the aldehyde scavenger; and v. curing the resultant mixture.

[0072] The polyfunctional isocyanate composition, isocyanate reactive composition and aldehyde scavenger are the same as defined above in relation to composition for making a polyurethane foam.

[0073] Curing the composition can be achieved by any method known to the skilled person. Generally, the curing process for a polyurethane foam is characterized as follows: (1) The reaction mixture changes from the liquid state to the solid state; (2) The curing reaction is completed within a short timeframe; (3) The volume of the reaction mixture is expanded greatly with foaming. For example, the curing time may be a few minutes to a few hours. Curing may involve mixing the components of the composition at an ambient temperature or a raised temperature.

[0074] In some embodiments, a catalyst may be included in the mixture, in the polyfunctional isocyanate composition, in the isocyanate reactive composition, or in the aldehyde scavenger composition. The catalyst may be the same as described.

[0075] In a further aspect, the present disclosure provides an article obtained using the method described above. The article may have any shape or firmness appropriate for its end use.

[0076] In a further aspect, the present disclosure provides a polyurethane comprising a borane- amine complex.

[0077] The polyurethane of the present disclosure is preferably used in furniture and / or automotive applications.

[0078] In some embodiments, the polyurethane made using the composition of the present disclosure, by the method of the present disclosure or in the use described above may be a foam; for example, a thermoset foam, a rigid foam, a flexible foam, a semi-rigid foam, or an integral foam, or may be a polyurethane coating and / or a polyurethane binder. Examples

[0079] More details and advantages of the present disclosure will become obvious from the following examples.

[0080] JEFFOL® G31-28, JEFFOL® PPG-3706, JEFFCAT® LE-310, JEFFCAT® ZF-10, JEFFCAT® LE-30, JEFFCAT® ZR-50, JEFFAMINE® D-230, triethylenetetramine (TETA), and SUPRASEC® 7320 are available from Huntsman International LLC. Ammonia borane is available form Sigma Aldrich. TEGOSTAB® B8734 LF2 was supplied by Evonik Industries. Example 1

[0081] To test the effect of including an aldehyde scavenger in composition for forming a PU foam, borane-triethylamine complex was added in-situ to formulated B-side (containing primary and secondary polyols, silicone surfactant, water as blowing agent, diethanolamine 85% low freeze grade (DEOA 85% LFG) as crosslinker and amine catalysts for blowing and gelling) in two different amounts, 0.25 parts by weight (pbw) and 0.1 pbw. The detailed composition of these materials is provided in Table 1, below.Table 1: Composition of B-side formulation

[0082] A control foam was also generated for comparison. The control foam having the same composition as the exemplary foam, without the presence of an aldehyde scavenger.

[0083] The required amount of B-side (masterbatch) and borane triethylamine complex were weighted into a paper cup and premixed for 6 seconds for a total of two times, to aid with nucleation.

[0084] Required SUPRASEC® 7320 isocyanate (MDI-based polyisocyanate MDI (isocyanate); NCO number: 29.8%; functionality: 2.20) was weighed into a plastic disposable cup and then transferred into a paper cup containing prior mixed B-side and mixed immediately for 6 seconds at 3000 RPM (rotations per minute) mix cycle at ambient temperature.

[0085] Then the cup containing fresh foam was set on bench hood to finish curing.

[0086] The free rise profile of the foam after mixing was obtained by using a FOAMAT® device to record foam height vs time and is provided in Figure 1. The y-axis in Figure 1 shows the foam height in mm, the x-axis shows the time in seconds. The dashed line represents the foam height over time for the control, while the solid line represents the foam height over time for a composition comprising 0.25 pbw Et3NBH3. The results in Figure 1 demonstrates that the addition of 0.25 pbw of a borane-triethylamine complex does not affect the reactivity of the PU foam. Example 2

[0087] Cup foams are made using the composition described in Table 1, above, with the addition of 0.25 pbw of a borane-triethylamine complex. After the cup foams are made, they are left for several minutes to finish curing on the surface and then are covered with several layers of plastic wraps to prevent VOCs from evaporating prior to testing.

[0088] The amount of aldehyde present was tested using a microchamber, DNPH (2,4- dinitrophenyl hydrazine) cartridges and a liquid chromatography technique. The microchamber was set to 65 °C and 50% relative humidity. Any volatile aldehydes were then captured by the DNPH cartridges. The derivatives made are then diluted in acetonitrile and analyzed by liquid chromatography.

[0089] The results of Example 2 are shown in Figures 2 and 3. Specifically, Figure 2 provides the aldehyde emission results where the x-axis indicates the aldehyde concentration measured (formaldehyde (FA), acetaldehyde (AA), propionaldehyde (PA), and total Aldehyde emissions) and the y-axis shows the aldehyde emissions in parts per billion (ppb). Total aldehyde emissions are determined by adding the FA, AA, and PA emissions. In Figure 2, the bars having diagonal lines therein represent the amount of aldehyde emission in the control compositions (that is, with no aldehyde scavenger present). The bars having crossed hatching therein in Figure 2 show the aldehyde content when 0.25 pbw Et3NBH3is present in the composition. The level of FA was low and the levels of AA and PA were below the detection limit (for example, less than 1 ppb) in the foams containing borane-triethylamine complex compared to the control.

[0090] Figure 3 shows the results in ppb where only 0.1pbw of borane triethylamine complex was added. The x and y axes are the same as those described with respect to Figure 2. The bars having diagonal lines therein correspond to the control composition, whereas the bars having cross hatching therein correspond to when an aldehyde scavenger is present. As indicated, the aldehyde emission levels of the exemplary composition were significantly lower as compared to the control in each category. Example 3

[0091] To test the effectiveness of the aldehyde scavenger to remove acetaldehyde, 300g of the formulation of Table 1 (minus the isocyanate) was spiked with 0.01g of acetaldehyde. The composition was mixed well and divided into two samples. To the first sample, 0.25 pbw of borane-triethylamine complex was added, the other sample was left as is.

[0092] Aldehyde test results of Example 3 are shown in Figure 4. The y-axis of the graph in Figure 4 shows the aldehyde emissions in ppb and the x-axis shows which aldehyde concentrations were measured. The bars having diagonal lines therein represent the amount of aldehyde emission in the control compositions (that is, with no aldehyde scavenger present). The bars having cross hatching therein show the composition having an aldehyde content of 0.25 pbw Et3NBH3. Formaldehyde (FA) was detected in both samples, however significantly less aldehyde was present in the composition containing the borane amino complex. As expected, the control foam had a high level of acetaldehyde (AA) (6460ppb) while the exemplary composition comprising the borane complex only showed only 55ppb. As clearly indicated in the graph, the results of the test clearly demonstrates the borane-triethylamine complex has significant effectiveness as an acetaldehyde scavenger.

[0093] Figure 5 shows the results after the B side formulation, as described above, was held at a high temperature for a period of time. The following situations were tested. - Control is the acetaldehyde spiked B-side (as above) - 0.25 pbw borane triethylamine complex (room temperature) - 0.25 pbw borane triethylamine complex (60°C for 30min).

[0094] The results of this analysis are provided in Figure 5. The y-axis of Figure 5 shows the aldehyde emissions in ppm, and the x-axis indicates the different aldehyde concentrations measured. The bars having upward diagonal lines therein represent the amount of aldehyde emission in the control compositions (that is, spiked composition with no aldehyde scavenger present). The bars having cross hatching therein show the aldehyde emissions resulting from the composition containing 0.25 pbw Et3NBH3at room temperature. The bars having downward diagonal lines therein (zero ppm for both FA and PA) show the aldehyde emissions resulting from the composition containing 0.25 pbw Et3NBH3when the temperature is held at 60 °C for thirty minutes. The results in Figure 5 demonstrate that formaldehyde (FA) was not detected in any of the studied systems. Acetaldehyde (AA) was detected, as expected, at an elevated level of 115ppm in the control composition, but showed significantly lower amounts of acetaldehyde emissions in the exemplary compositions, specifically 10ppm for the composition having a borane complex at room temperature, and only 1ppm for the composition having a borane complex if treated at 60°C for 30min. The control composition also showed significant propionaldehyde emissions, whereas the propionaldehyde (PA) emissions of the exemplary compositions were undetectable.

[0095] Once again, the effectiveness of borane as aldehyde scavengers was proven effective when formulated B-side was spiked with acetaldehyde (AA). Example 4

[0096] It is known that formaldehyde (FA) will form overtime in the presence of pure tertiary amine catalysts, in open air, in compositions containing methyl groups in its chemical structure. Tertiary amine catalysts are commonly used in the manufacture of PU foams. Thus, a random tertiary amine catalyst was evaluated with and without the presence of 0.05 pbw borane- triethylamine complex for 5 weeks. Figure 6 shows a line graph illustrating the measured aldehyde content (y-axis) over the five week period (x-axis).

[0097] It was observed that initial formaldehyde (FA) levels of 139ppm were present in the pure catalyst, and it continued to increase. On the contrary, the composition including a borane- amine complex showed significantly lower formaldehyde (FA) levels both at the beginning at17ppm and throughout the five week period. The increase in FA content observed in the exemplary composition is minimal under the same conditions of the control.

[0098] The experiment was repeated to test for acetaldehyde (AA) emissions, the results of which are shown in Figure 7. The results of the formaldehyde emissions (Figure 6) and acetaldehyde emissions (Figure 7) tests are shown in ppm and indicate the control composition with a circle and solid line and the exemplary composition comprising 0.05 pbw borane-amine complex with a square and dashed line.

[0099] The results of both tests clearly demonstrate the effectiveness of a borane-amine complex to remove aldehydes from a composition over a longer period of time.

[0100] Examples 5-8 use lab-made borane complexes of JEFFCAT® LE30-borane, JEFFAMINE® D-230 borane, JEFFCAT® ZR-50 borane, and TETA borane. Such borane complexes were prepared using the corresponding amines in accordance with the following method.

[0101] General procedure for synthesis of amine-boranes:

[0102] Sodium borohydride (1.1 equiv per nitrogen atom) and ammonium sulfate powder (0.5 equiv relative to sodium borohydride) were transferred to a 2-neck round bottom flask equipped with a stir bar under an atmosphere of air. The amine (100 grams) and THF (0.5 M) were then added to the flask (evolution of H2gas was observed). A condenser connected to a chiller set to 5°C was attached to one of the necks of the reaction flask. The other neck was sealed using a stopper. The top of the condenser was sealed with a septum fitted with an open needle to relieve any pressure buildup. The reaction was heated at reflux with vigorous stirring overnight. A 0.5 mL aliquot was removed and concentrated in vacuo. NMR (CDCl3) was used to check the progress of the reaction (11B = approx. -10 to -20 ppm for the product).

[0103] The reaction mixture was cooled to room temperature and filtered through celite to remove excess sodium salts. The celite was washed with THF and the combined filtrate concentrated in vacuo to give the product, the structures of which are provided below:Triethylenetetramine (TETA) Borane

[0104] The lab-made borane complexes were characterized spectroscopically. The11B NMR data are: LE-30 borane, -9.90 ppm (broad); D-230 borane, -21.18 ppm (broad); ZR-50 borane, -10.09 ppm (broad); TETA borane, -14.5 to -19.70 ppm (broad); and trioctylamine-borane, - 5.0ppm (broad).

[0105] Cup foams are made similarly to Example 2 using the composition described in Table 1 above along with different usage levels of corresponding amine borane complex. Example 5

[0106] Figure 8 shows results for a composition containing 0.25 pbw of JEFFCAT® LE-30- borane (40% in solvent TETA) complex as compared to the control composition described above. The bar having diagonal lines therein represents the emissions for the control, while the bar having cross-hatching therein represents the composition including JEFFCAT® LE-30- borane. As shown, the JEFFCAT® LE30-borane was able to effectively reduce formaldehyde (FA) emissions even at such a low concentration. Reduction in acetaldehyde (AA) and propionaldehyde (PA) emissions were not observed in this case. Example 6

[0107] Figure 9 shows aldehyde emission results comparing a control composition having no additive, indicated as a solid bar, to compositions containing 0.25 pbw, indicated as a cross hatched bar, 0.75pbw, indicated as a bar having downward diagonal lines, and 1.50pbw, indicated as having a bar having upward diagonal lines, respectively of JEFFAMINE® D-230-borane complex as described above. As shown, each composition having JEFFAMINE® D- 230-borane therein was effective in reducing formaldehyde (FA), acetaldehyde (AA), and propionaldehyde (PA) emissions (as measured in ppb). Example 7

[0108] Figure 10 shows the results of aldehyde emissions testing comparing a control composition having no additive, indicated as a solid bar, to compositions containing 0.25 pbw, indicated as a cross hatched bar, and 0.50 pbw, indicated as a bar having downward diagonal lines, respectively of JEFFCAT® ZR-50-borane complex, as described above. As shown, the addition of JEFFCAT® ZR-50-borane was effective in reducing formaldehyde (FA), acetaldehyde (AA), and propionaldehyde (PA) emissions. Example 8

[0109] Figure 11 shows the results of aldehyde emission tests comparing a control composition having no additive, indicated by a bar having diagonal lines therein, and a composition having 0.25 pbw of TETA-borane complex (25% in solvent TETA), indicated as a bar having cross hatching therein. As shown, the presence of the TETA-borane additive was effective in reducing formaldehyde (FA) and acetaldehyde (AA) emissions. However, a reduction in propionaldehyde (PA) was not observed. Example 9

[0110] Figure 12 shows the results of aldehyde emission tests comparing a control composition having no additive, indicated by a bar having diagonal lines therein, and a composition having 0.75 pbw of Ammonia-borane complex from Sigma Aldrich (0.25pbw in in formulated B-side), indicated as a bar having cross hatching therein. As shown, the presence of the ammonia- borane additive was effective in reducing each of the formaldehyde (FA), acetaldehyde (AA), and propionaldehyde (PA) emissions.

[0111] It is to be understood that although preferred embodiments and / or materials have been discussed for providing embodiments according to the present disclosure, various modifications or changes may be made without departing from the spirit and scope of the disclosure described herein.

Claims

What is claimed:

1. A composition comprising: a polyfunctional isocyanate composition; an isocyanate reactive composition; and an aldehyde scavenger comprising a borane-amine complex.

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

3. The composition of one of claim 1 or claim 2, wherein the borane-amine complex is selected from the group consisting of ammonia; trimethyl amine; triethylamine; trioctylamine; tripropyl amine; tri-isopropylamine; tributylamine; tri-tert-butylamine; triisobutylamine; tricyclohexylamine; tricyclopentylamine; triphenylamine; dimethylamine; diethylamine; dipropylamine; dibutylamine; di-tert-butylamine; di-isobutylamine; dicylohexylamine; 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-hexalenediamine; N,N,N',N'-tetramethyl 1,2-ethylenediamine; N,N,N',N'-tetramethyl 1,3-propylenediamine; N,N,N',N'-tetramethyl 1,4-butylenediamine; N,N,N',N'-tetramethyl 1,5-pentylenediamine; N,N,N',N'-tetramethyl 1,6 -hexalenediamine; N,N-dimethylaniline; benzyldimethylamine; N,N-dimethylcyclohexylamine; pentamethyldiethylenetriamine; N,N,N',N",N"-pentamethyl-dipropylenetriamine; bis-(2- dimethylaminoethyl)ether; N-methylmorpholine; N-ethylmorpholine; 2,2'- dimorpholinodiethylether; 1,3,5-tris(3-(dimethylamino)propyl)-hexahydro-s-triazine; a polyetheramine having the formulaa polyetheramine having the formula (H2NCH(CH3)CH2(OCH2CH(CH3))x(OCH2CH2)y(OCH2CH(CH3))zNH2), a polyetheramine having the formula (H3C-(OCH2CH2)x(OCH2CHR)yNH2), a polyetheramine having formula ((H2N(CH(CH3)CH2O)xCH2)CH2R((CH2)n)yNH2)(CH2(OCH2CH(CH3)zNH2), a polyetheramine having formula (H2N(CH2)x(OCH2CH2O)(CH2)xNH2), or secondary amine versions of any of the foregoing; diamines or triamines based on PTMEG / PPG copolymer; N,N-dimethylethanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N,N,N'-trimethylaminoethyl-ethanolamine; N,N,N'-trimethyl-N'hydroxyethyl- bisaminoethylether; 2-(2-dimehtylaminoethoxy)ethanol; ethylenediamine (EDA);tetraethylenepentamine (TEPA); triethylenetetramine (TETA); aminoethylethanolamine (AEEA); aminoethylpiperazine (AEP); immobilized amines; or mixtures thereof.

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

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

6. The composition of any preceding claim, wherein the composition comprises two or more aldehyde scavengers comprising a borane-amine complex.

7. The composition of any preceding claim, wherein the composition further comprises an additional aldehyde scavenger, wherein said additional aldehyde scavenger is not a borane- amine complex.

8. The composition of any preceding claim, wherein the polyfunctional isocyanate component comprises a semi-prepolymer or prepolymer formed from the reaction of a polyisocyanate and a polyhydric alcohol.

9. The composition of any preceding claim, wherein the polyisocyanate component includes one or more polyisocyanates such as an aliphatic polyisocyanate or an aromatic polyisocyanate.

10. The composition of any preceding claim, wherein the composition further comprises a blowing agent.

11. The composition of any preceding claim, wherein the composition further comprises an amine catalyst.

12. The composition of any preceding claim, wherein the composition further comprises a cross linking agent, preferably wherein the cross-linking agent is diethanolamine ((2- diethylamino)ethanol).

13. The composition of any preceding claim, wherein the composition further comprises additives selected from at least one pigment, at least one filler, at least one surfactant and mixtures thereof.

14. Use of an aldehyde scavenger comprising a borane-amine complex to remove aldehydes from a polyurethane foam.

15. The use of claim 14, wherein the aldehydes are selected from formaldehyde, acetaldehyde and propionaldehyde.

16. A method for preparing a polyurethane foam comprising: providing a polyol composition;providing an isocyanate reactive composition; providing an aldehyde scavenger comprising a borane-amine complex; mixing the polyfunctional isocyanate composition, the isocyanate reactive composition and the aldehyde scavenger; and curing the resultant mixture.

17. An article obtained by the method of claim 16.

18. A polyurethane foam comprising a borane-amine complex.

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