Mixtures for the long-term control of aldehyde emissions from polyurethane foams.

Abstract

The present disclosure relates to isocyanate-reactive compositions for use in polyurethane formulations and methods of making polyurethane materials from the polyurethane formulations. The isocyanate-reactive compositions generally include an aldehyde scavenger blend capable of reducing aldehyde emissions from polyurethane materials produced from the polyurethane formulations over an extended period of time.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 330,803, filed April 14, 2022. The cited applications are incorporated herein by reference.

[0002] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT N / A

[0003] The present disclosure relates generally to polyurethane formulations including aldehyde scavenger blends, methods for making polyurethane materials using such formulations, and polyurethane materials resulting from such methods that exhibit reduced levels of aldehyde emissions over extended periods of time. [Background technology]

[0004] Polyurethane foams are widely known and used in many applications. For example, polyurethane foams are often used as insulation in electrical appliances and as cushioning in bedding and furniture. In automobiles and trucks, polyurethane foams are used as cushioning for seats, in headrests, in dashboards and instrument panels, in armrests, in ceilings, and in other areas. One drawback of using such foams in these applications is that they can release organic matter, specifically aldehydes, over time, which can cause unpleasant odors or, at high concentrations, can cause health-related problems, especially when exposure occurs in enclosed spaces. Aldehyde exposure limits are set by various government agencies, including limits for formaldehyde and acetaldehyde in particular. These exposure limits are of great concern to the automotive and slabstock industries as they collectively work to improve air quality in automobile interiors and bedding.

[0005] Therefore, various attempts have been made to reduce or lower the aldehyde emissions from polyurethane foam. For example, CH-acid compounds (see Patent Document 1), amine compounds having at least two secondary amine groups (see Patent Document 2), hydrazine compounds (see Patent Document 3), polyhydrazodicarbonamide compounds (see Patent Document 4), reducing agents (such as sodium borohydride) (see Patent Document 5), cyclic ureas and free radical scavengers (see Patent Document 6), and aldehyde scavengers such as cyanoacetamide (see Patent Document 7) are all used in the production of polyurethane foam to try to reduce aldehyde emissions to acceptable industrial levels.

[0006] While each of the above aldehyde scavengers is capable of reducing aldehyde emissions, there is a continuing need to develop new aldehyde scavenger systems that can reduce the levels of aldehyde emissions from polyurethane foams more efficiently and for a longer period of time. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] US Patent Application Publication No. 2016 / 0304686 [Patent Document 2] International Publication No. 2014 / 026802 Brochure [Patent Document 3] US Patent Application Publication No. 2006 / 0141236 [Patent Document 4] US Patent Application Publication No. 2013 / 0203880 [Patent Document 5] JP 2005154599 A [Patent Document 6] International Publication No. 2016 / 0200854 Brochure [Patent Document 7] International Publication No. 2015 / 082316 Brochure Summary of the Invention

[0008] The present disclosure provides an isocyanate-reactive composition that includes an aldehyde scavenger blend, an active hydrogen-containing compound, and a catalyst.

[0009] According to another embodiment, the present disclosure provides a polyurethane formulation comprising the isocyanate-reactive composition described above and a compound comprising an isocyanate functionality.

[0010] In yet another embodiment, there is provided a method for forming a polyurethane foam comprising contacting a compound comprising an isocyanate functional group and optional adjunct ingredients in the presence of an isocyanate-reactive composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The following terms shall have the following meanings:

[0012] The term "comprising" and its derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not it is disclosed herein. For the avoidance of any doubt, all compositions claimed herein through the use of the term "comprising" may include any additional additive or compound, unless stated to the contrary. In contrast, the term "consisting essentially of," as used herein, excludes any other component, step, or procedure from the scope of any succeeding description, except those that are not essential to operability. The term "consisting of," when used, excludes any component, step, or procedure not specifically described or listed. The term "or" refers to the listed members individually or in any combination, unless otherwise stated.

[0013] The articles "a" and "an" are used herein to refer to one or more (i.e., at least one) of the grammatical object of the article. By way of example, "an amine" means one amine or multiple amines. The phrases "in one embodiment," "according to one embodiment," and the like generally mean that the particular feature, structure, or characteristic that follows the phrase is included in at least one embodiment of the disclosure and may also be included in multiple embodiments of the disclosure. Importantly, such phrases do not necessarily refer to the same aspect. When a statement is made herein that an ingredient or feature "may," "can," "could," or "might" be included or have a characteristic, it does not require that the particular ingredient or feature be included or have that characteristic.

[0014] The term "about," as used herein, allows for a certain degree of variation in a value or range, for example, the degree of variation may be within 10%, within 5%, or within 1% of a stated value or a stated range limit.

[0015] Values ​​expressed in range format are to be interpreted in a flexible manner to include not only the numbers expressly recited as the limits of the range, but also all of the individual numbers or subranges subsumed within that range, as if each number and subrange were expressly recited. For example, a range (such as 1 to 6) shall be considered to have specifically disclosed subranges (such as 1 to 3, 2 to 4, 3 to 6, etc.) as well as individual numbers within that range (e.g., 1, 2, 3, 4, 5, and 6). This applies regardless of the breadth of the range.

[0016] The terms "preferred" and "preferably" refer to embodiments that may provide certain benefits, under certain circumstances, while 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.

[0017] The term "substantially free" refers to the amount of a particular compound or moiety present in a composition that does not significantly affect the composition.In some embodiments, "substantially free" can refer to the amount of a particular compound or moiety present in a composition being less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, or less than 0.05% by weight, or even less than 0.01% by weight, based on the total weight of the composition, or the amount of that particular compound or moiety present in each composition being completely absent.

[0018] The term "extended period" refers to a period (or time) that may range from 1 week up to 1 year or up to 2 years, or a period in the range of 1-2 weeks or 2-3 weeks or 3-4 weeks, or 1-2 months or 2-3 months or 3-4 months or 3-6 months or 6 months to 12 months or 12 months to 24 months, or a period in the range of a few days (such as 7, 10, or 12 days), or a period in the range of a few weeks (such as 2, 3, or 4 weeks), or a month, or a period in the range of several months (such as 2, 3, 4, 5, or 6 months), or even a longer period (such as 7, 8, 9, or 12 months).

[0019] The term "reduced emission levels" or the like refers to a reduction in the emission level or amount of a substance (such as an aldehyde) from a material (such as a polyurethane foam) when compared to a suitable reference level, such as the emission level or amount of the same aldehyde from a polyurethane foam known to be prepared in the presence of an aldehyde scavenger not according to the present disclosure or from a polyurethane foam known to be prepared in the absence of any aldehyde scavenger.

[0020] Where a substituent is specified by its conventional chemical formula (written from left to right), such substituent is intended to equally encompass the chemically identical substituent that would be obtained by writing the structure from right to left, e.g., -CH2O- is equivalent to -OCH2-.

[0021] The term "alkyl" refers to a straight or branched chain saturated hydrocarbon group having 1 to 50 carbon atoms, or 1 to 40 carbon atoms, or 1 to 30 carbon atoms, or 1 to 20 carbon atoms, or 1 to 10 carbon atoms. In some embodiments, the alkyl substituent can be a lower alkyl group. The term "lower" refers to the number of carbon atoms in the alkyl group being 1 to 6. Examples of "lower alkyl groups" include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, butyl, and pentyl groups.

[0022] The term "alkenyl" refers to straight or branched chain alkyl groups having one or more carbon-carbon double bonds and 2 to 20 carbon atoms, including, but not limited to, ethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, and 2-butenyl. In some embodiments, the alkenyl chain is 2 to 10 carbon atoms in length, 2 to 8 carbon atoms in length, 2 to 6 carbon atoms in length, or 2 to 4 carbon atoms in length.

[0023] The term "alkoxy" refers to the functional group -OR, where R is an alkyl group as defined above. Non-limiting examples of alkoxy groups are -OCH, -OCHCH, -OCHCHCH, -OCH(CH), -OCH(CH), -O-cyclopentyl, and -O-cyclohexyl.

[0024] The term "aryl" refers to a monovalent group that is aromatic and optionally carbocyclic. An aryl has at least one aromatic ring. Any additional rings may be unsaturated, partially saturated, saturated, or aromatic. Optionally, an aromatic ring may have one or more additional carbocyclic rings fused thereto. Unless otherwise specified, an aryl group typically contains 6 to 30 carbon atoms. In some embodiments, an aryl group contains 6 to 20, 6 to 18, 6 to 16, 6 to 12, or 6 to 10 carbon atoms. Examples of aryl groups include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl.

[0025] The term "arylalkyl" refers to a monovalent group that is an alkyl group substituted with an aryl group. The term "alkylaryl" refers to a monovalent group that is an aryl group substituted with an alkyl group. Unless otherwise specified, for both, the alkyl portion often has 1-10 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms, and the aryl portion often has 6-20 carbon atoms, 6-18 carbon atoms, 6-16 carbon atoms, 6-12 carbon atoms, or 6-10 carbon atoms.

[0026] The term "cycloalkyl" refers to a cyclized C3-C 30 refers to an alkyl group, suitably a cyclized C3-C 20 Refers to an alkyl group.

[0027] The term "halogenated olefin" refers to an olefinic compound or moiety that may contain fluorine, chlorine, bromine, or iodine.

[0028] The term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes cases where the event or circumstance occurs and cases where it does not occur.

[0029] The present disclosure is generally directed to an isocyanate-reactive composition comprising an aldehyde scavenger blend and an active hydrogen-containing compound, and its use in polyurethane formulations. The present disclosure is also directed to rigid or flexible polyurethane foams or other polyurethane materials made from the polyurethane formulations comprising the isocyanate-reactive compositions described herein and compounds containing isocyanate functionality. It is understood that the term "polyurethane" as used herein encompasses pure polyurethanes, polyurethane polyureas, and pure polyureas. Surprisingly, it has been found that the aldehyde scavenger blends of the present disclosure (when used in a process for producing polyurethane foam by reacting an isocyanate-reactive composition including the aldehyde scavenger blend with a compound containing an isocyanate functionality) can significantly reduce the emissions of aldehydes (such as formaldehyde, acetaldehyde, and propionaldehyde), and optionally also dimethylformamide (DMF), from polyurethane foam over extended periods of time, without detrimentally affecting the mechanical properties of the resulting foam or the appearance of the isocyanate-reactive composition during storage.

[0030] According to one embodiment, the isocyanate-reactive composition comprises (A) (i) a cyclic urea substituted with at least one isocyanate-reactive group; (ii) a cyclic urea of ​​formula (I): [ka] A compound of the formula: an aldehyde scavenger blend comprising a compound of formula (I) where X is O, S, or NHR5, and R1, R2, R3, R4, and R5 are independently selected from hydrogen, or an unsubstituted or substituted alkyl, alkenyl, aryl, alkylaryl, or alkoxy group, with the proviso that at least one of R3 and R4 is hydrogen; and (iii) an amine compound selected from ammonia, a primary amine, and mixtures thereof; (B) an active hydrogen-containing compound; and (C) a catalyst.

[0031] As described above, the aldehyde scavenger blend includes a cyclic urea substituted with at least one isocyanate reactive group. The cyclic urea substituted with at least one isocyanate reactive group can be a cycloaliphatic or bicycloaliphatic compound having the structural element -NH-CO-NH- within the ring structure. In one embodiment, the cyclic urea has a total number of ring atoms in the range of 5 to 7. Such cyclic ureas have one or both of the -N or -C atoms substituted with at least one isocyanate reactive group. In one particular embodiment, the cyclic urea substituted with at least one isocyanate reactive group is: Formula (II) [ka] is a compound having the formula In the formula, R, R 0 , R 1 , R 2 , R 3 , and R 4 are independently -H, -OH, -R 5 OH, -NH, or -COOH, and R 5 is a C1-C4 alkyl group, provided that R or R 0 is -H, and R, R 0 , R 1 , R 2 , R 3 , and R 4 At least one of the following is -OH, -COOH, -R 5OH or -NH, or R 1 R 2 Or R 3 R 4 The condition is that it is NH2.

[0032] Examples of such compounds of formula (II) include, but are not limited to, 4,5-dihydroxy-2-imidazolidinone, 4,5-dimethoxy-2-imidazolidinone, 4-hydroxyethylethyleneurea, 4-hydroxy-5-methylpropyleneurea, 4-methoxy-5-methylpropyleneurea, 4-hydroxy-5,5-dimethylpropyleneurea, and 1-(2-hydroxyethyl)-2-imidazolidinone.

[0033] In another embodiment, the cyclic urea substituted with at least one isocyanate group has the formula (III): [ka] and In the formula, R, R 0 , R 1 , R 2 , R 5 , and R 6 are independently -H, -OH, -R 7 OH, -NH, or -COOH, and R 3 and R 4 are, individually, absent, -H, -OH, -R 7 OH, -NH, or -COOH, and R 7 is a C1-C4 alkyl group, and X is C, O, or N, provided that when X is O, R 3 and R 4 are absent and X is N, then R 3 or R 4 is absent, and R or R 0 At least one of R 0 , R 1 , R 2 , R 3 , R 4 , R5 , R 6 One of the groups is OH, -COOH, or -R. 7 OH or -NH, or R 1 R 2 Or R 5 R 6 The condition is that it is NH2.

[0034] Examples of such compounds of formula (III) include, but are not limited to, tetrahydro-5-(2-hydroxyethyl)-1,3,5-triazin-2-one, tetrahydro-5-(ethyl)-1,3,5-triazin-2-one, tetrahydro-5-(propyl)-1,3,5-triazin-2-one, tetrahydro-5-(butyl)-1,3,5-triazin-2-one, or mixtures thereof.

[0035] In one embodiment, the amount of cyclic urea substituted with at least one isocyanate reactive group present can be at least about 10% by weight, or at least about 20% by weight, or at least about 30% by weight, or at least about 40% by weight, or at least about 50% by weight, or at least about 60% by weight, or at least about 70% by weight, or at least about 80% by weight, or at least about 90% by weight, based on the total weight of the aldehyde scavenger blend. In another embodiment, the amount of cyclic urea substituted with at least one isocyanate reactive group present can be about 5-95% by weight, or about 10-90% by weight, or about 20-80% by weight, or about 30-70% by weight, or about 40-60% by weight, based on the total weight of the aldehyde scavenger blend.

[0036] The aldehyde scavenger blend comprises a compound represented by formula (I): [ka] Also includes compounds of wherein X is O, S, or NHR5; and R1, R2, R3, R4, and R5 are individually -H or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, or alkoxy groups, provided that at least one of R3 and R4 is -H.

[0037] According to one embodiment, X is O, S, or NHR5, and R1, R2, R3, R4, and R5 can be the same or different, and are -H, C1-C 18 Alkyl groups, C2-C 18 Alkenyl groups, C3-C 10 Cycloalkyl groups, C7-C 18 Alkylaryl group, alkoxy group, or C6-C 18 An aryl group, provided that at least one of R3 and R4 is -H.

[0038] One of the radicals R1 to R4 is C1 to C 18 If it is an alkyl group, the radical may be straight or branched and may contain, for example, 1 to 10 carbon atoms or 1 to 6 carbon atoms. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, and isoamyl.

[0039] When one of the radicals R1 to R4 is an alkoxyl group, the alkoxy radical includes, for example, a C1 to C5 alkyl group, such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, or isoamyl.

[0040] One of the radicals R1 to R4 is C2 to C 18 In the case of an alkenyl group, a C2-C5 alkenyl radical is preferred.

[0041] One of the radicals R1 to R4 is C c ~C 10When it is a cycloalkyl group, C4 to C7 cycloalkyl radicals are preferred, such as cyclopentyl and cyclohexyl.

[0042] One of the radicals R1 to R4 is C6 to C 18 When it is an aryl group, phenyl and naphthyl are preferred.

[0043] Examples of compounds of formula (I) include barbituric acid, thiobarbituric acid, 1,3,5-trimethylbarbituric acid, 1-phenyl-5-benzylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 5-laurylbarbituric acid, 5-butylbarbituric acid, 5-allylbarbituric acid, 5-hydroxy-5-butylbarbituric acid, 5-phenylthiobarbituric acid, 1,3-dimethylthiobarbituric acid, 5,5-dibromobarbituric acid, trichlorobarbituric acid, 5-nitrobarbituric acid, 5-aminobarbituric acid, 5-hydroxybarbituric acid, and 5,5-dihydroxybarbituric acid.

[0044] In one embodiment, the amount of the compound of formula (I) present may be less than about 90% by weight, or less than about 80% by weight, or less than about 70% by weight, or less than about 60% by weight, or less than about 50% by weight, or less than about 40% by weight, or less than about 30% by weight, or less than about 20% by weight, or less than about 10% by weight, based on the total weight of the aldehyde scavenger blend. In another embodiment, the amount of the compound of formula (I) present may be about 0.5-90% by weight, or about 1-75% by weight, or about 1.5-50% by weight, or about 2-30% by weight, or about 3-20% by weight, based on the total weight of the aldehyde scavenger blend.

[0045] The aldehyde scavenger blend also includes an amine compound selected from ammonia, a primary amine, and mixtures thereof. In one embodiment, the primary amine is represented by formula (IV): [ka] is a compound having the formula wherein R5 and R6 are independently selected from hydrogen or an unsubstituted or substituted alkyl, alkenyl, aryl, alkylaryl, or alkoxy group; m is 2 or 3; n is 2; and q is 0 to 3.

[0046] In an embodiment of the present disclosure, the primary amine may be, but is not limited to, tetra-ethylene-pentamine (TEPA), dimethyl-amino-propylamine (DMAPA), triethylenetetraamine (TETA), pentaethylenehexamine (PEELA), hexaethyleneheptamine (HEHA), heptaethyleneoctamine (HEOA), octaethylenenonamine (OENO), a cyclic amine represented by formula (V): [ka] wherein m is an integer from 2 to about 100, and each R2 is independently hydrogen, methyl, or ethyl; or a compound having formula (VI): [ka] wherein n and p are each independently an integer from about 1 to about 10, and o is an integer from about 2 to about 40; or a compound having formula (VII): [ka] where g is 2 or 3), polyetheramine products supplied by Huntsman Corporation (which may include Jeffamine® D230 amine, Jeffamine® D400 amine, Jeffamine® D2000 amine, Jeffamine® EDR148 amine, Jeffamine® EDR176 amine, Jeffamine® ED600 amine, Jeffamine® ED900 amine, and Jeffamine® ED2003 amine), amines obtained by adding urea or guanidine compounds to polyetheramines or polyethyleneamines (such as amines obtained by reacting guanidine with TETA), and amines obtained by the Michael addition reaction of alcohol- or amino-containing tertiary amines followed by hydrogenation (such as amines obtained by reacting DMAPA with acrylonitrile followed by hydrogenation, and amines obtained by reacting DMEA (dimethylaminoethanol) with acrylonitrile followed by hydrogenation).

[0047] In one embodiment, the amine may be present in an amount of less than about 90% by weight, or less than about 80% by weight, or less than about 70% by weight, or less than about 60% by weight, or less than about 50% by weight, or less than about 40% by weight, or less than about 30% by weight, or less than about 20% by weight, or less than about 10% by weight, based on the total weight of the aldehyde scavenger blend. In another embodiment, the amine may be present in an amount of about 0.5-90% by weight, or about 1-75% by weight, or about 1.5-50% by weight, or about 2-30% by weight, or about 3-20% by weight, based on the total weight of the aldehyde scavenger blend.

[0048] In some embodiments, the aldehyde scavenger blend is present in an amount less than about 2.5 wt%, or less than about 2 wt%, or less than about 1.5 wt%, or less than about 1 wt%, or less than about 0.5 wt%, based on the total weight of the isocyanate-reactive composition, and in other embodiments, the aldehyde scavenger blend is present in an amount between about 0.01 and 3 wt%, or between about 0.05 and 1.0 wt%, or between about 0.05 and 0.5 wt%, based on the total weight of the isocyanate-reactive composition. The amount of the aldehyde scavenger blend may vary depending on the type of polyurethane being made, as well as the compound containing isocyanate groups and the active hydrogen-containing compound being used. Preferably, the aldehyde scavenger blend is present in an effective amount capable of reducing the emission of one or more of acetaldehyde, formaldehyde, and propionaldehyde.

[0049] The isocyanate-reactive composition also includes an active hydrogen-containing compound including a polyol, a polyfunctional amine, or mixtures thereof.

[0050] In one embodiment, the active hydrogen-containing compound is a polyol. Suitable polyols for use in the present disclosure include, but are not limited to, polyalkylene ether polyols, polyester polyols, biorenewable polyols, polymer polyols, non-flammable polyols (such as phosphorus-containing polyols or halogen-containing polyols). Such polyols may be used alone or in suitable combinations as mixtures. The total functionality of the polyols used in the present disclosure may be 2 to 6. The molecular weight of the polyol may be in an amount ranging from about 200 to 10,000 Daltons, preferably about 400 to 7,000 Daltons, the molecular weight being the weight average molecular weight as defined by the gel permeation chromatography (GPC) method with polystyrene as a reference.

[0051] Polyalkylene ether polyols include poly(alkylene oxide) polymers (such as poly(ethylene oxide) and polypropylene oxide) polymers) and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols, such as, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylolpropane, and similar low molecular weight polyols.

[0052] Polyester polyols include, but are not limited to, those made by reacting a dicarboxylic acid with an excess of a diol (e.g., reacting adipic acid with ethylene glycol or butanediol) or those made by reacting a lactone with an excess of a diol (such as reacting caprolactone with propylene glycol).

[0053] In addition to polyalkylene ether polyols and polyester polyols, polymer polyols are also suitable for use in the present disclosure. The use of polymer polyols in polyurethane materials increases resistance to deformation (e.g., improves the load-bearing properties of the foam or material). Examples of polymer polyols include, but are not limited to, graft polyols or polyurea-modified polyols (Polyharnstoff Dispersion polyols). Graft polyols include triols in which vinyl monomers are graft copolymerized. Suitable vinyl monomers include, for example, styrene or acrylonitrile. Polyurea-modified polyols are polyols that contain polyurea dispersions formed by reacting diamines and diisocyanates in the presence of a polyol. A different form of polyurea-modified polyol is polyisocyanate polyaddition (PIPA) polyols formed by the in situ reaction of isocyanates and alkanolamines in the polyol.

[0054] Biorenewable polyols suitable for use in the present disclosure include castor oil, sunflower oil, palm kernel oil, palm oil, canola oil, rapeseed oil, soybean oil, corn oil, peanut oil, olive oil, algae oil, and mixtures thereof.

[0055] The non-flammable polyol may be, for example, a phosphorus-containing polyol obtainable by addition of an alkylene oxide to a phosphoric acid compound. The halogen-containing polyol may be, for example, one obtainable by ring-opening polymerization of epichlorohydrin or trichlorobutylene.

[0056] In another embodiment, the active hydrogen-containing compound is a polyfunctional polyamine, such as a polyetheramine, a polyester polyamine, or a mixture thereof.

[0057] In one particular embodiment, the polyetheramine can be a polyetheramine as described above (i.e., having formulas (V)-(VII)). For example, the polyetheramine can be a compound having formula (V), where each R2 is independently hydrogen or methyl and m is an integer from 2 to about 70, or from 2 to about 35, or from 2 to about 7. In other embodiments, each R2 is independently hydrogen or methyl and m is an integer from 6 to about 70, or from about 6 to about 35. In yet other embodiments, each R2 is methyl and m is an integer from 2 to about 70.

[0058] In another embodiment, the polyetheramine can be a compound having formula (VI), where o is an integer from about 2 to about 40, or from about 2 to about 13, or from about 2 to about 10. In another embodiment, o is an integer from about 9 to about 40, or from about 12 to about 40, or from about 15 to about 40, or even from about 25 to about 40. In other embodiments, n+p is an integer in the range of about 1 to about 6, or in the range of about 1 to about 4, or in the range of about 1 to about 3. In another embodiment, n+p is an integer in the range of about 2 to about 6, or in the range of about 3 to about 6.

[0059] In another embodiment, the polyetheramine is represented by formula (VIII): [ka] wherein each R6 and R7 is independently hydrogen, methyl, or ethyl, and e is an integer from 1 to 10; or a compound having formula (IX): [ka] wherein each R8 and R9 is independently hydrogen, methyl, or ethyl, and f, g, and h are integers from 1 to 8.

[0060] In yet another embodiment, the polyfunctional amine can be a polyester polyamine. Examples of polyester polyamines include polyesters having two terminal amine groups prepared from polyesters such as poly(ethylene glutarate), poly(ethylene adipate), poly(ethylene azelate), poly(trimethylene glutarate), poly(tetramethylene glutarate), poly(pentamethylene glutarate), poly(diethylene glutarate), poly(diethylene adipate), poly(triethylene adipate), and poly(1,2-propylene adipate).

[0061] The amount of active hydrogen-containing compound present in the isocyanate-reactive composition can be at least about 40% by weight, or at least about 50% by weight, or at least about 60% by weight, or at least about 70% by weight, or at least about 80% by weight, or at least about 90% by weight, or at least about 95% by weight, based on the total weight of the isocyanate-reactive composition.

[0062] The isocyanate-reactive composition also includes a catalyst. In one embodiment, the catalyst is an amine catalyst. The amine catalyst of the present disclosure can be any amine useful as a catalyst in the reaction to form a polyurethane foam or polyurethane material. According to one embodiment, the amine catalyst is an amine that includes one or more tertiary amino groups. Examples include, but are not limited to, bis-(2-dimethylaminoethyl)ether (JEFFCAT® ZF-20 catalyst), N,N,N'-trimethyl-N'-hydroxyethyl bisaminoethyl ether (JEFFCAT® ZF-10 catalyst), N-(3-dimethylaminopropyl)-N,N-diisopropanolamine (JEFFCAT® DPA catalyst), N,N-dimethylethanolamine (JEFFCAT® DMEA catalyst), triethylenediamine (JEFFCAT® TEDA catalyst), blends of N,N-dimethylethanolamine and triethylenediamine (such as JEFFCAT® TD-20 catalyst), N,N-dimethylcyclohexylamine (JEFFCAT® DMCHA catalyst), benzyldimethylamine (JEFFCAT® BDMA catalyst), pentamethyldiethylenetriamine (JEFFCAT® PMDETA catalyst), and the like. catalyst), N,N,N',N",N"-Pentamethyldipropylenetriamine (JEFFCAT® ZR-40 catalyst), N,N-Bis(3-dimethylaminopropyl)-N-isopropanolamine (JEFFCAT® ZR-50 catalyst), N'-(3-(dimethylamino)propyl-N,N-dimethyl-1,3-propanediamine (JEFFCAT® Z-130 catalyst), 2-(2-dimethylaminoethoxy)ethanol (JEF FCAT® ZR-70 catalyst), N,N,N'-trimethylaminoethyl-ethanolamine (JEFFCAT® Z-110 catalyst), N-ethylmorpholine (JEFFCAT® NEM catalyst), N-methylmorpholine (JEFFCAT® NMM catalyst), 4-methoxyethylmorpholine, N,N'dimethylpiperzine (JEFFCAT® DMP catalyst), 2,2'-Dimorpholinodiethyl ether (JEFFCAT® DMDEE catalyst), 1,3,5-tris(3-(dimethylamino)propyl)-hexahydro-s-triazine (JEFFCAT® TR-90 catalyst), 1-propanamine, 3-(2-(dimethylamino)ethoxy), substituted imidazoles (such as 1,2-dimethlyimidazol and 1-methyl-2-hydroxyethylimidazole), N,N'-dimethylpiperazine or or bis-substituted piperazines (such as aminoethylpiperazine, N,N',N'-trimethylaminoethylpiperazine, or bis-(N-methylpiperazine)urea), N-methylpyrrolidine and substituted methylpyrrolidines (such as 2-aminoethyl-N-methylpyrrolidine or bis-(N-methylpyrrolidine)ethylurea), 3-dimethylaminopropylamine, N,N,N",N"-tetramethyldipropylenetriamine, tetramethylguanidine, and 1,2 bis-diisopropanol. Other examples of amine catalysts include N-alkylmorpholines (such as N-methylmorpholine, N-ethylmorpholine, N-butylmorpholine, and dimorpholinodiethyl ether), N,N'-dimethylaminoethanol, N,N-dimethylaminoethoxyethanol, bis-(dimethylaminopropyl)-amino-2-propanol, bis-(dimethylamino)-2-propanol, bis-(N,N-dimethylamino)ethyl ether, N,N,N'-trimethyl-N'hydroxyethyl-bis-(aminoethyl)ether, N,N-dimethylaminoethyl-N'-methylaminoethanol, tetramethyliminobispropylamine, and combinations thereof.

[0063] According to another embodiment, the above catalysts may be combined with non-amine catalysts in the formation of polyurethane foams or polyurethane masses. Examples of such additional non-amine catalysts include, for example: Tertiary phosphines (such as trialkylphosphines and dialkylbenzylphosphines), Chelates of various metals (such as those obtainable from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, and the like, with metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, and Ni), Metal carboxylates (such as potassium acetate and sodium acetate), Acidic metal salts of strong acids (such as ferric chloride, stannic chloride, stannous chloride, antimony trichloride, bismuth nitrate, and bismuth chloride), strong bases (such as alkali and alkaline earth metal hydroxides, alkoxides, and phenoxides); Alcoholates and phenolates of various metals (Ti(OR 6 )4, Sn(OR 6 )4, and Al(OR 6 )3(wherein, R 6 is alkyl or aryl), and reaction products of alcoholates with carboxylic acids and beta-diketones, and Included are alkaline earth metal, Bi, Pb, Sn, or Al carboxylates, as well as tetravalent tin compounds, and trivalent or pentavalent bismuth, antimony, or arsenic compounds.

[0064] The catalyst may be used in a catalytically effective amount to catalyze the reaction between a compound containing isocyanate functionality and an active hydrogen-containing compound for the purpose of making rigid or flexible polyurethane foams or other polyurethane materials. A catalytically effective amount of catalyst may range from about 0.01 to 15 parts per 100 parts of active hydrogen-containing compound, or in some embodiments, from about 0.05 to 12.5 parts per 100 parts of active hydrogen-containing compound, in yet other embodiments, from about 0.1 to 7.5 parts per 100 parts of active hydrogen-containing compound, and in yet other embodiments, from about 0.5 to 5 parts per 100 parts of active hydrogen-containing compound.

[0065] According to another embodiment, the isocyanate-reactive composition may optionally include a blowing agent. In one embodiment, the blowing agent may be a halogenated olefin compound. The halogenated olefin compound may include at least one haloalkene (e.g., a fluoroalkene or a chlorofluoroalkene) containing 3 to 4 carbon atoms and at least one carbon-carbon double bond. Suitable compounds may include hydrohaloolefins such as trifluoropropene, tetrafluoropropene (e.g., tetrafluoropropene (1234)), pentafluoropropene (e.g., pentafluoropropene (1225)), chlorotrifluoropropene (e.g., chlorotrifluoropropene (1233)), chlorodifluoropropene, chlorotrifluoropropene, chlorotetrafluoropropene, hexafluorobutene (e.g., hexafluorobutene (1336)), or combinations thereof. In certain embodiments, the tetrafluoropropene compounds, pentafluoropropene compounds, and / or chlorotrifluoropropene compounds have no more than one fluorine or chlorine substituent attached to a terminal carbon atom of the unsaturated carbon chain (e.g., 1,3,3,3-tetrafluoropropene (1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (1225ye), 1,1,1-trifluoropropene, (Z)-1,1,1,2,3-pentafluoropropene (1225yc), (Z)-1,1,1,2,3-pentafluoropropene (1225yez), 1-chloro-3,3,3-trifluoropropene (1233zd), 1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm), or combinations thereof.

[0066] According to one embodiment, the halogenated olefin blowing agent has the formula: [ka] and In the formula, each R 10are independently Cl, F, H, or CF3, provided that the total number of carbon atoms is either 3 or 4; R 11 is (C(R 10 )2) m Y, Y is CF3, m is 0 or 1. In one embodiment, Y is CF3 and at least two unsaturated carbons have chlorine substituents.

[0067] Examples of such compounds include 1,1,1,4,4.4-hexafluoro-2-butene (1336), 1-chloro-3,3,3-trifluoropropene (1233zd), and 1,3,3,3-tetrafluoropropene (1234ze). In certain highly preferred aspects of such embodiments, 1-chloro-3,3,3-trifluoropropene (1233zd) is trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), 1,3,3,3-tetrafluoropropene (1234ze) is trans-1,3,3,3-tetrafluoropropene (1234ze(E)), and 1,1,14.4.4-hexafluoro-2-butene (1336) is cis-1,1,1,4,4,4-hexafluoro-2-butene (1336(Z)).

[0068] According to another embodiment, the halogenated olefin blowing agent is of the formula [ka] and In the formula, each R 10 are independently Cl, F, or H; R 11 is (C(R 10 )2) n Y, Y is CF3, n is 0 or 1.

[0069] Examples of such compounds include 1-chloro-3,3,3-trifluoropropene (1233zd) (preferably trans-1233zd), 2,3,3,3-tetrafluoropropene (1234yf), and 1,3,3,3-tetrafluoropropene (1234ze) (preferably trans-1234ze). In certain such embodiments, 1-chloro-3,3,3-trifluoropropene (1233zd) is trans 1-chloro-3,3,3-trifluoropropene (1233zd(E)), 1,3,3,3-tetrafluoropropene (1234ze) is trans 1,3,3,3-tetrafluoropropene (1234ze(E)), and 1,1,14.4.4-hexafluoro-2-butene (1336) is cis 1,1,14.4.4-hexafluoro-2-butene (1336(Z)).

[0070] In another embodiment, the blowing agent may be a non-halogenated compound, including, but not limited to, water, air, nitrogen, carbon dioxide, hydrofluorocarbons ("HFCs"), alkanes, alkenes, mono-carboxylates, ketones, ethers, or combinations thereof. Suitable HFCs include 1,1-difluoroethane (HFC-152a), 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), or combinations thereof. Suitable alkanes and alkenes include n-butane, n-pentane, isopentane, cyclopentane, 1-pentene, or combinations thereof. Suitable mono-carboxylates include methyl formate, ethyl formate, methyl acetate, or combinations thereof. Suitable ketones and ethers include acetone, dimethyl ether, or combinations thereof.

[0071] The amount of blowing agent can vary widely depending on many factors, including the type of foam being made using the blowing agent. According to some embodiments, the amount of blowing agent present can be about 0.5 to 40 weight percent, or about 1 to 30 weight percent, or about 2 to 25 weight percent, or about 3 to 20 weight percent, based on the total weight of the isocyanate-reactive composition.

[0072] In yet another embodiment, polyurethane formulations may be produced by combining the above-described isocyanate-reactive compositions with compounds containing isocyanate functional groups and optional adjunct ingredients.

[0073] According to one embodiment, the compound containing isocyanate functionality is a polyisocyanate, an isocyanate-terminated prepolymer, or a mixture thereof.

[0074] Polyisocyanates include Q(NCO) d where d is a number from 2 to 5 (e.g., 2 to 3) and Q is an aliphatic hydrocarbon group containing 2 to 18 carbon atoms, a cycloaliphatic hydrocarbon group containing 5 to 10 carbon atoms, an araliphatic hydrocarbon group containing 8 to 13 carbon atoms, or an aromatic hydrocarbon group containing 6 to 15 carbon atoms.

[0075] Examples of polyisocyanates include, but are not limited to, ethylene diisocyanate; 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate, and mixtures of these isomers; isophorone diisocyanate; 2,4-hexahydrotoluene diisocyanate and 2,6-hexahydrotoluene diisocyanate, and mixtures of these isomers; dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI, or HMDI); 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate; 2,4- Toluene diisocyanate and 2,6-toluene diisocyanate and mixtures of these isomers (TDI); diphenylmethane-2,4'- and / or -4,4'-diisocyanate (MDI); naphthylene-1,5-diisocyanate; triphenylmethane-4,4',4"-triisocyanate; polyphenyl-polymethylene-polyisocyanates of the type which may be obtainable by condensation of aniline with formaldehyde followed by phosgenation (crude MDI); norbornane diisocyanate; m- and p-isocyanatophenylsulfonyl isocyanate; perchlorinated aryl polyisocyanates; polyisocyanates containing carbodiimide, urethane, allophanate or tertiary isocyanates with ... These include modified polyisocyanates containing isocyanurate, urea, or biruret groups; polyisocyanates obtained by telomerization reactions; polyisocyanates containing ester groups; and polyisocyanates containing polymeric fatty acid groups. Those skilled in the art will recognize that mixtures of the above polyisocyanates may also be used.

[0076] Isocyanate-terminated prepolymers may also be used in preparing polyurethanes. They may be prepared by reacting an excess of a polyisocyanate or mixtures thereof with a small amount of an active hydrogen-containing compound as described above, as determined by the well-known Zerewitinoff test.

[0077] The amount of compounds containing isocyanate functionality present in the polyurethane formulation is typically, but not limited to, within an NCOI index range known to those skilled in the art, such as an NCO index of about 70 to 150, or about 80 to 130, or about 90 to 115. As is known in the art, NCO index is defined as the number of equivalents of isocyanate divided by the total number of equivalents of active hydrogen multiplied by 100 and may be represented by the following formula: NCO index = [NCO / (OH+NH)] * 100

[0078] In addition, the polyurethane formulation may optionally include one or more auxiliary components, examples of which include, but are not limited to, cell stabilizers, crosslinkers, chain extenders, pigments, fillers, flame retardants, thermally expandable microspheres, thickeners, smoke suppressants, reinforcing agents, antioxidants, UV stabilizers, antistatic agents, infrared absorbers, dyes, mold release agents, antifungal agents, biocides, or any combination thereof.

[0079] The cell stabilizer may include, for example, silicone surfactants, and organic anionic, cationic, zwitterionic, or nonionic surfactants. Examples of suitable silicone surfactants include, but are not limited to, polyalkylsiloxanes, polyoxyalkylene polyol-modified dimethylpolysiloxanes, alkylene glycol-modified dimethylpolysiloxanes, or any combination thereof. Suitable anionic surfactants include, but are not limited to, salts of fatty acids, salts of sulfate esters, salts of phosphate esters, salts of sulfonic acids, and any combination thereof. Suitable cationic surfactants include, but are not limited to, quaternary ammonium salts (pH-dependent or permanently charged), such as cetyltrimethylammonium chloride, cetylpyridinium chloride, polyethoxylated tallow amine, benzalkonium chloride, benzethonium chloride, and the like. Suitable zwitterionic or amphoteric surfactants include, but are not limited to, sultaines, amino acids, imino acids, betaines, and phosphates. Suitable nonionic surfactants include, but are not limited to, fatty alcohols, polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, glucosides (such as decyl glucoside, lauryl glucoside, and octyl glucoside), polyoxyethylene glycol alkyl phenol ethers, and glycol alkyl esters. Suitable amounts for all cell stabilizers include, but are not limited to, about 0-20 parts by weight per 100 parts by weight of active hydrogen-containing compound, or about 0.15-10 parts by weight per 100 parts by weight of active hydrogen-containing compound, or about 0.2-5 parts by weight per 100 parts by weight of active hydrogen-containing compound.

[0080] Examples of crosslinkers include, but are not limited to, low molecular weight compounds containing at least two moieties selected from hydroxyl groups, primary amino groups, secondary amino groups, and other active hydrogen-containing groups that react with isocyanate groups. Crosslinkers include, for example, polyhydric alcohols (especially trihydric alcohols such as glycerol and trimethylolpropane), polyamines, and combinations thereof. Non-limiting examples of polyamine crosslinkers include diethyltoluenediamine, chlorodiaminobenzene, diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, 1,6-hexanediamine, and combinations thereof. Typical diamine crosslinkers contain 12 or fewer carbon atoms, more commonly 7 or fewer carbon atoms.

[0081] Examples of chain extenders include, but are not limited to, compounds having hydroxyl or amino functional groups, such as glycols, amines, diols, and water. Specific, non-limiting examples of chain extenders include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, ethoxylated hydroquinone, 1,4-cyclohexanediol, N-methylethanolamine, N-methylisopropanolamine, 4-aminocyclohexanol, 1,2-diaminoethane, 2,4-toluenediamine, or any mixture thereof. In some embodiments, the amount of crosslinker / chain extender present may be about 0-5 parts by weight per 100 parts by weight of active hydrogen-containing compound, preferably about 0.4-3.5 parts by weight per 100 parts by weight of active hydrogen-containing compound.

[0082] Pigments may be used to color polyurethane materials during manufacturing to identify product grades or to hide yellowing. Pigments may include any suitable organic or inorganic pigments. For example, organic pigments or colorants include, but are not limited to, azo / diazo dyes, phthalocyanines, dioxazines, or carbon black. Examples of inorganic pigments include, but are not limited to, titanium dioxide, iron oxide, or chromium oxide. In some embodiments, the pigment may be present in an amount of about 0-10 parts by weight per 100 parts by weight of active hydrogen-containing compound, preferably about 0.1-5 parts by weight per 100 parts by weight of active hydrogen-containing compound.

[0083] Fillers can be used to increase the density and load-bearing properties of polyurethane foams or polyurethane materials. Suitable fillers include, but are not limited to, barium sulfate, carbon black, or calcium carbonate. In some embodiments, the filler can be present in an amount of about 0-20 parts by weight per 100 parts by weight of active hydrogen-containing compound, preferably about 0.1-10 parts by weight per 100 parts by weight of active hydrogen-containing compound.

[0084] Flame retardants may be used to reduce flammability. For example, such flame retardants include, but are not limited to, chlorinated phosphate esters, chlorinated paraffins, or melamine powders. In some embodiments, the amount of flame retardant present may be about 0-20 parts by weight per 100 parts by weight of active hydrogen-containing compound, preferably about 0.1-10 parts by weight per 100 parts by weight of active hydrogen-containing compound.

[0085] Thermally expandable microspheres include those containing (cyclo)aliphatic hydrocarbons. Such microspheres are generally unexpanded or partially unexpanded dry microspheres consisting of small spherical particles with an average diameter typically between 10 and 15 microns. The spheres are formed from a gas-tight polymer shell (e.g., made of acrylonitrile or PVDC) encapsulating microdroplets of (cyclo)aliphatic hydrocarbons (e.g., liquid isobutane). When such microspheres are subjected to heat at elevated temperature levels (e.g., 150°C to 200°C) sufficient to soften the thermoplastic shell and volatilize the encapsulated (cyclo)aliphatic hydrocarbons, the resulting gas expands the shell and increases the volume of the microsphere. Upon expansion, the diameter of the microsphere increases by 3.5 to 4 times its original diameter, resulting in an expanded volume of the microsphere of about 50 to 60 times the initial volume of the microsphere in its unexpanded state. An example of such microspheres are EXPANCEL®-DU microspheres marketed by AKZO Nobel Industries of Sweden.

[0086] The polyurethane formulations according to the present disclosure can be used to make a wide variety of polyurethane materials, such as rigid foams, flexible foams, semi-rigid foams, microcellular elastomers, textile backings, spray elastomers, cast elastomers, polyurethane-isocyanurate foams, reaction injection molded polymers, structural reaction injection molded polymers, and the like.

[0087] 15~150kg / m 3 A non-limiting example of a typical flexible polyurethane foam formulation (e.g., for automotive seating) having a density of 100% would include the following components in parts by weight (pbw): [Table 1]

[0088] 15~70kg / m 3A non-limiting example of a typical rigid polyurethane foam formulation having a density of 100% may include the following components in parts by weight (pbw): [Table 2]

[0089] Thus, in yet another embodiment, the present disclosure provides a method of producing a polyurethane material comprising contacting a compound containing an isocyanate functional group, an isocyanate-reactive composition according to the present disclosure, and optional adjunct ingredients.

[0090] In one particular embodiment, the polyurethane material is a rigid or flexible foam prepared by combining an isocyanate-reactive composition, including at least one active hydrogen-containing compound (such as a polyol), an aldehyde scavenger blend, a catalyst, optional blowing agent, and auxiliary ingredients, with a compound containing isocyanate functionality to form a reaction mixture, and subjecting the reaction mixture to conditions sufficient for the active hydrogen-containing compound to react with the compound containing isocyanate functionality. The isocyanate-reactive composition and the compound containing isocyanate functionality may be heated before mixing them to form the reaction mixture. In other embodiments, the isocyanate-reactive composition and the compound containing isocyanate functionality may be mixed at ambient temperature (e.g., about 15-40° C.) and heat may be applied to the reaction mixture, although in some embodiments, application of heat may not be necessary. Polyurethane foams may be made in a free-rise (slabstock) process, which allows the foam to grow freely with minimal or no vertical constraints. Alternatively, molded foams can be made by introducing the reaction mixture into a closed mold and allowing the reaction mixture to form a foam within the mold. Depending on the desired characteristics of the resulting foam, the particular active hydrogen-containing compound and the compound containing isocyanate functionality are selected. Blowing agents and other auxiliary ingredients useful in making polyurethane foams (such as those described above) can also be included to produce the particular type of foam.

[0091] According to another embodiment, the polyurethane material may be produced in a one-step process in which an A-side reactant (a compound containing isocyanate functionality) reacts with a B-side reactant (an isocyanate-reactive composition). The compound containing isocyanate functionality may include a polyisocyanate, while the isocyanate-reactive composition may include an active hydrogen-containing compound (such as a polyol), a catalyst, and an aldehyde scavenger blend according to the present disclosure. In some embodiments, the A-side reactant and / or the B-side reactant may also optionally include other adjunct ingredients (such as those described above).

[0092] The polyurethane materials produced may be used in a variety of applications, such as precoats; backing materials for carpets; building composites; thermal insulation; spray foam insulation; applications requiring the use of impingement mix spray guns; urethane / urea hybrid elastomers; interior and exterior vehicle parts (such as bed liners, dashboards, door panels, and handles); flexible foams (such as furniture foams and vehicle part foams); integral skin foams; rigid spray foams; rigid pore-in-place foams; coatings; adhesives; sealants; filament winding; and other polyurethane composite, foam, elastomer, resin, and reaction injection molding (RIM) applications.

[0093] In one particular embodiment, polyurethane materials are used in enclosed spaces, e.g., as insulation materials in residential and commercial buildings, e.g., as insulation for pipes and refrigerators, in furniture construction, e.g., as decorative elements or seat cushioning, and in automotive interior parts, e.g., as seat cushioning, steering wheels, dashboards, door cladding, carpet backing foam, sound absorbing foam, e.g., ceiling upholstery, headrests, or control buttons.

[0094] The present disclosure will now be further described with reference to the following non-limiting examples. EXAMPLES

[0095] Aldehyde Release Test Description Formaldehyde and acetaldehyde were measured using a microchamber test. The size of the chamber was 128 mL. The temperature of the chamber during the test was set at 65°C and the relative humidity was set at 50%. The air exchange rate was 3.0 liters / hour. The exhaust stream containing the volatile aldehydes from the polyurethane was passed through a cartridge containing silica coated with 2,4-diuitrophenylhydrazine, followed by elution of the cartridge with a mixture of acetonitrile and water. The concentration of formaldehyde in the eluate was determined by HPLC. The detection limit of formaldehyde emission with this setup was 5.1 ugm. -2 h -1 It was.

[0096] Examples 1 to 3. Polyurethane foam Several polyurethane foams were prepared from the following ingredients: Polyol A (NJ-360N): Polyetherol (OH number 28 mg KOH / g) purchased from NingWu New Material Development Corporation Polyol B (KONIX KE-880S): Polyetherol purchased from KPX chemical (OH number 20mgKOH / g) DEOA: Diethanolamine TEPA: Tetraethylenepentamine HHEU: N-2(hydroxyethyl)ethyleneurea Tegostab® B8738 LF2: Foam stabilizer Jeffcat® ZF-10 Tertiary Amine Catalyst Jeffcat® DPA Tertiary Amine Catalyst Isocyanate: TM (TDI / polymeric MDI=80 / 20) Examples 1A-1D to 3A-3D were produced with Isocyanate™ supplied as the A-side reactant. The B-side reactants for Examples 1A-1D to 3A-3D are shown in Tables 1, 4, and 7 below. All values ​​in Tables 1, 4, and 7 refer to parts by weight. The A-side reactants and B-side reactants were mixed in a ratio of A:B=43:100 (by weight) to give an index of 1.05 and stirred in a polyethylene container. The polyurethane formulation was quickly poured into a polyethylene bag to allow the foaming reaction to proceed and result in free rise of the resulting foam. The resulting foam was then cured at room temperature for a minimum of 15 minutes. The foam samples were stored at room temperature (25±2°C) / 50% RH for 0-90 days and then subjected to microchamber testing. The results are given in Tables 2, 3, 5, 6, 8, and 9. [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] [Table 10] [Table 11]

[0097] As can be seen from the above examples, when barbituric acid and amine were used as aldehyde scavengers, the resulting foam showed increased acetaldehyde emission after 90 days of storage. When HEEU was used alone as an aldehyde scavenger, the resulting foam did not show good control of formaldehyde and acetaldehyde. On the other hand, when all three of these aldehyde scavengers were combined (as shown in Examples 3A-3D), the resulting foam was able to significantly control both formaldehyde and acetaldehyde emissions during at least 90 days of storage.

Claims

1. (A) (i) A cyclic urea substituted with at least one isocyanate reactive group, (ii) Formula (I) 【Chemistry 1】 A compound of, In the formula, X is O, S, or NHR 5 And R 1 , R 2 , R 3 , R 4 , and R 5 However, hydrogen, or an unsubstituted or substituted alkyl group, alkenyl group, aryl group, alkylaryl group, or alkoxy group are individually selected, however, R 3 and R 4 An isocyanate-reactive composition comprising (B) an active hydrogen-containing compound and (C) a catalyst, comprising an aldehyde scavenger blend comprising (I) a compound of formula (I) wherein at least one of the compounds is hydrogen, and (iii) an amine compound selected from ammonia, primary amines, and mixtures thereof;

2. The cyclic urea substituted with at least one isocyanate reactive group is given by formula (II) 【Chemistry 2】 Contains a compound having In the formula, R, R 0 , R 1 , R 2 , R 3 , and R 4 are independently -H, -OH, -R 5 OH, -N H, or -COOH, R 5 However, C 1 ~C 4 It is an alkyl group, however, R or R 0 The condition is that at least one of them is -H, and furthermore, R, R 0 , R 1 , R 2 , R 3 , and R 4 At least one of them is -OH, -COOH, -R 5 It is either OH, -NH, or R 1 R 2 Or R 3 R 4 NH 2 The isocyanate-reactive composition according to claim 1, wherein the condition is that...

3. The isocyanate-reactive composition according to claim 2, wherein the compound of formula (II) is selected from 4,5-dihydroxy-2-imidazolidinone, 4,5-dimethoxy-2-imidazolidinone, 4-hydroxyethylethyleneurea, 4-hydroxy-5-methylpropyleneurea, 4-methoxy-5-methylpropyleneurea, 4-hydroxy-5,5-dimethylpropyleneurea, and 1-(2-hydroxyethyl)-2-imidazolidinone.

4. The isocyanate-reactive composition according to claim 1, wherein the compound of formula (I) is selected from barbituric acid, thiobarbituric acid, 1,3,5-trimethylbarbituric acid, 1-phenyl-5-benzylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 5-laurylbarbituric acid, 5-butylbarbituric acid, 5-allylbarbituric acid, 5-hydroxy-5-butylbarbituric acid, 5-phenylthiobarbituric acid, 1,3-dimethylthiobarbituric acid, 5,5-dibromobarbituric acid, trichlorobarbituric acid, 5-nitrobarbituric acid, 5-aminobarbituric acid, 5-hydroxybarbituric acid, and 5,5-dihydroxybarbituric acid.

5. The amine compound is of formula (IV) 【Transformation 3】 Contains a compound having In the formula, R 5 and R 6 The isocyanate-reactive composition according to claim 1, wherein the isocyanate is individually selected from hydrogen, or an unsubstituted or substituted alkyl group, alkenyl group, aryl group, alkylaryl group, or alkoxy group, and m is 2 or 3, n is 2, and q is 0 to 3.

6. The isocyanate-reactive composition according to claim 1, wherein the active hydrogen-containing compound is selected from polyalkylene ether polyols, polyester polyols, biorenewable polyols, polymer polyols, non-flammable polyols, and mixtures thereof.

7. The isocyanate-reactive composition according to claim 1, wherein the catalyst comprises an amine catalyst.

8. The isocyanate-reactive composition according to claim 1, further comprising a foaming agent.

9. A polyurethane compound comprising the isocyanate-reactive composition described in claim 1 and a compound containing an isocyanate functional group.

10. The polyurethane compound according to claim 9, further comprising a foaming agent and / or a nonamine catalyst.

11. The polyurethane compound according to claim 10, further comprising one or more auxiliary components.

12. A method for producing a polyurethane material, comprising contacting an isocyanate-reactive composition with a compound containing an isocyanate functional group and one or more optional auxiliary components, wherein the isocyanate-reactive composition is (A) (i) a cyclic urea substituted with at least one isocyanate reactive group, (ii) formula (I) 【Chemistry 4】 A compound of, In the formula, X is O, S, or NHR 5 And R 1 , R 2 , R 3 , R 4 , and R 5 However, hydrogen, or an unsubstituted or substituted alkyl group, alkenyl group, aryl group, alkylaryl group, or alkoxy group are individually selected, however, R 3 and R 4 A method for producing the product, comprising: (B) an active hydrogen-containing compound; and (C) a catalyst.

13. A polyurethane material produced according to the method described in claim 12.

14. The polyurethane material according to claim 13, wherein the polyurethane material is a rigid foam or a flexible foam.

15. The polyurethane material according to claim 14, wherein the polyurethane material exhibits a decrease in aldehyde emission levels over a long period of time.

16. The polyurethane material according to claim 15, wherein the aforementioned long period is at least three months.

17. The polyurethane material according to claim 16, wherein the polyurethane material is a precoat, a backing material for carpets, a composite material for buildings, a thermal insulation material, a spray foam thermal insulation material, a urethane / urea hybrid elastomer, a vehicle interior part and a vehicle exterior part, a soft foam, an integral skin foam, a rigid spray foam, a rigid pore-in-place foam, a coating, an adhesive, a sealant, or a filament winding.

18. A thermal insulation material comprising the polyurethane material described in claim 13.

19. A seat cushioning material comprising the polyurethane material described in claim 13.

20. A vehicle interior part or vehicle exterior part comprising the polyurethane material described in claim 13.

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