Polyurethane composition, polyurethane foam with reduced odor prepared using the same, and method for preparing the same

Abstract

A polyurethane composition is provided, comprising: (A) an isocyanate compound; (B) a polyol compound; and (C) an amine-based catalyst system comprising (C1) at least one amine-based catalyst and (C2) at least one deodorant represented by formula (1) or formula (2). Polyurethane foams prepared using the polyurethane composition exhibit extremely low odor intensity and excellent performance characteristics, such as foaming degree and mechanical strength. A method for preparing the polyurethane foam with reduced odor is also provided. [Formula 1] JPEG2024539085000015.jpg38170

Description

[Technical Field]

[0001] The present invention relates to a polyurethane (PU) composition, a polyurethane foam having reduced odor prepared using the composition, and a method for preparing the polyurethane foam having reduced odor. The polyurethane composition exhibits high odor removal effect while maintaining good foaming or lathering reactivity, and the polyurethane foam prepared using the polyurethane composition exhibits extremely low odor intensity and excellent mechanical strength. [Background technology]

[0002] Polyurethane foams are widely used in various office, home, and vehicle applications, such as noise, vibration, and harshness (NVH), seating for household goods, bedding, and the automotive industry, thermal insulation, and shoe manufacturing (e.g., shoe soles). A long-standing drawback of polyurethane foams is their unpleasant, pungent odor, which is essentially caused by the release of small molecule amines, such as dimethylamine (DMA) and trimethylamine (TMA), derived from amine-type substances used to catalyze the reaction between isocyanates and polyol raw materials. Due to increasingly stringent environmental regulations worldwide and frequent complaints from customers, extensive research has been conducted to develop polyurethane foams with reduced odor or even essentially odorless. Nevertheless, several challenges remain to be overcome. For example, one challenge is the extremely low odor thresholds of DMA and TMA, and their amounts must be reduced to very low levels, such as less than 0.047 ppm for DMA and less than 0.00021 ppm for TMA, to completely eliminate the fishy odor, for example, by chemically modifying the molecular structure of the catalyst or selecting an alternative catalyst. Such chemical modifications are also challenging because they can have further adverse effects on the performance properties of the polyurethane composition or the resulting polyurethane foam, such as poor foaming reactivity or reduced mechanical strength.

[0003] For the above reasons, there remains a need in the polyurethane foam manufacturing industry to develop a polyurethane composition that has effectively eliminated odor, excellent foaming reactivity, and mechanical properties in an economical manner. As a result of continuous research, the present inventors have surprisingly developed a polyurethane composition that can achieve the above goals. Summary of the Invention

[0004] The present disclosure provides unique polyurethane compositions, polyurethane foam articles or products prepared using the compositions, methods for preparing polyurethane foam products, and methods for reducing odor in polyurethane foam products.

[0005] In a first aspect of the present disclosure, the present disclosure provides a polyurethane composition for preparing a polyurethane foam having reduced odor, the polyurethane composition comprising: (A) at least one isocyanate compound containing at least two isocyanate groups; (B) at least one polyol compound, and (C) an amine-based catalyst system, (C1) at least one amine catalyst selected from the group consisting of aliphatic diamines, aliphatic triamines, alicyclic monoamines, alicyclic diamines, alicyclic triamines, araliphatic monoamines, araliphatic diamines, araliphatic triamines, aromatic monoamines, aromatic diamines, aromatic triamines, heterocyclic monoamines, heterocyclic diamines, heterocyclic triamines, and any combination thereof; (C2) Formula (1) or Formula (2):

[0006] [ka] [Wherein R1 is hydrogen or methyl, R2 is C1 to C 12 Alkyl, hydroxy substituted C1-C 12 Alkyl and (meth)acryloxy (C1-C 12 alkylene)-O-(C1-C 12) alkyl, and R3 is a divalent C2-C 12 Alkylene, trivalent C3-C 12 Alkylene and tetravalent C4-C 12 and at least one deodorizing agent represented by the formula: wherein n is an integer from 2 to 4 and n is selected from the group consisting of alkylenes.

[0007] In a second aspect of the present disclosure, the present disclosure provides a polyurethane foam article prepared using a polyurethane composition of the present disclosure, the polyurethane foam article having reduced odor.

[0008] In a third aspect of the present disclosure, the present disclosure provides a method for producing a polyurethane foam having reduced odor, the method comprising: (i) combining at least one amine-based catalyst with at least one deodorizing agent to form an amine-based catalyst system; (ii) reacting at least one isocyanate compound containing at least two isocyanate groups with at least one polyol compound in the presence of an amine-based catalyst system to produce the reduced odor polyurethane foam; the amine catalyst is selected from the group consisting of aliphatic diamines, aliphatic triamines, alicyclic monoamines, alicyclic diamines, alicyclic triamines, araliphatic monoamines, araliphatic diamines, araliphatic triamines, aromatic monoamines, aromatic diamines, aromatic triamines, heterocyclic monoamines, heterocyclic diamines, heterocyclic triamines, and any combination thereof; The deodorant may be a compound represented by formula (1) or (2):

[0009] [ka] [Wherein R1 is hydrogen or methyl, R2 is C1 to C 12 Alkyl, hydroxy substituted C1-C 12 Alkyl and (meth)acryloxy (C1-C 12 alkylene)-O-(C1-C12 ) alkyl, and R3 is a divalent C2-C 12 Alkylene, trivalent C3-C 12 Alkylene and tetravalent C4-C 12 and at least one deodorizing agent represented by the formula: wherein n is an integer from 2 to 4 and n is selected from the group consisting of alkylenes.

[0010] In a fourth aspect of the disclosure, the disclosure provides a method for reducing odor in polyurethane foam, the method comprising: (i) combining at least one amine-based catalyst with at least one deodorizing agent to form an amine-based catalyst system; (ii) catalyzing the reaction of an isocyanate compound containing at least two isocyanate groups with a polyol compound using an amine-based catalyst system to produce a polyurethane foam having reduced odor; The amine catalyst and deodorizer are as described above.

[0011] In a fifth aspect of the disclosure, the disclosure provides a method for reducing odor of a catalyst system for preparing polyurethane foam, the method comprising combining at least one amine-based catalyst as described above with at least one deodorizer as described above to form an amine-based catalyst system for preparing polyurethane foam.

[0012] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. DETAILED DESCRIPTION OF THE INVENTION

[0013] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Additionally, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.

[0014] As disclosed herein, "and / or" means "and, or alternatively." All ranges are inclusive of endpoints unless otherwise indicated. All percentages and ratios are calculated by weight and all molecular weights are number average molecular weights unless otherwise specified.

[0015] Without being limited to any particular theory, the technical breakthrough of the present disclosure mainly resides in the specially designed formulation of an amine-based catalyst system for preparing polyurethane foam. In particular, it has been found that the amine-based catalyst system obtained by combining a deodorizer represented by Formula (1) or Formula (2) with a specifically selected amine-based catalyst has a substantially reduced or diminished concentration of odor-causing substances, particularly DMA and / or TMA, and the PU foam prepared using the amine-based catalyst system can successfully obtain a desirable combination of performance properties such as reduced odor, good foaming degree, and excellent mechanical strength.

[0016] In the context of this disclosure, the terms "polyurethane foam with reduced odor" and "polyurethane foam having reduced odor" are used interchangeably and refer to polyurethane foam that emits reduced, significantly reduced, or undetectable amounts of DMA and / or TMA into the surrounding environment. For example, it has been reported that the odor thresholds for DMA and TMA in air are 0.047 ppm and 0.00021 ppm, respectively, and therefore, the concentrations of DMA and / or TMA emitted into the air from odor-reduced polyurethane foams can be close to or lower than these thresholds. Furthermore, "odor-reduced polyurethane foam" exhibits a reduction in DMA and / or TMA emissions of 35% to 100% by weight for DMA and 40 to 99% by weight (e.g., 50 to 65%) for TMA.

[0017] According to an embodiment of the present disclosure, the amine-based catalyst system includes at least one amine-based catalyst and at least one deodorizing agent represented by Formula (1) or Formula (2), and may optionally include one or more other components, such as a catalyst other than the amine-based catalyst, a cocatalyst, an accelerator, an inhibitor, a solvent, a cosolvent, a diluent, a pH adjuster, a buffer, and any combination thereof. For example, the catalyst other than the amine-based catalyst may include glycine salts; tertiary phosphines such as trialkylphosphines and dialkylbenzylphosphines; chelates of various metals, such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, and Ni, such as those obtainable from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, and the like; acidic metal salts of strong acids, such as ferric chloride and stannic chloride; organic chelates containing various metals, such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni, and Cu; Examples of suitable amine-based catalysts include acid salts; tin(II) salts of organic carboxylic acids, such as tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate; and dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate; bismuth salts of organic carboxylic acids, such as bismuth octoate; organometallic derivatives of trivalent and pentavalent As, Sb, and Bi, and metal carbonyls of iron and cobalt; or mixtures thereof. According to one embodiment of the present disclosure, the amine-based catalyst system contains only the amine-based catalyst and no other catalysts. According to another embodiment of the present disclosure, the amine-based catalyst system comprises at least one amine-based catalyst and at least one deodorizer represented by Formula (1) or Formula (2), and does not contain any other components, such as those described above.According to an embodiment of the present disclosure, the weight ratio of the deodorizer to the amine catalyst is 0.5:100 to 15:100, or 1:100 to 10:100, or 1:100 to 5:100, for example, the following ratio values: 0.5:100, 0.8:100, 1:100, 1.2:100, 1.4:100, 1.5:100, 1.8:100, 2:1 00, 2.2:100, 2.5:100, 2.8:100, 3:100, 3.2:100, 3.5:100, 3.8:100, 4:100, 4.2:100, 4.5:100, 4.8:100, 5:100, 5.2:100, 5.5:100, 5.8:100, 6:100, 6.2:100, 6.5:100, 6.8:100, 7:1 00, 7.2:100, 7.5:100, 7.8:100, 8:100, 8.2:100, 8.5:100, 8.8:100, 9:100, 9.2:100, 9.5:100, 9.8:100, 10:100, 10.2:100, 10.5:100, 10.8:100, 11:100, 11.2:100, 11.5:100, 11.8 :100, 12:100, 12.2:100, 12.5:100, 12.8:100, 13:100, 13.2:100, 13.5:100, 13.8:100, 14:100, 14.2:100, 14.5:100, 14.8:100, and 15:100.

[0018] As used herein, the term "amine catalyst" refers to at least one amine-type catalyst capable of accelerating the reaction of an isocyanate group in an isocyanate compound with a hydroxy group and any other isocyanate-reactive group in a polyol compound. According to embodiments of the present disclosure, the amine catalyst is selected from the group consisting of an aliphatic diamine, an aliphatic triamine, an alicyclic monoamine, an alicyclic diamine, an alicyclic triamine, an araliphatic monoamine, an araliphatic diamine, an araliphatic triamine, an aromatic monoamine, an aromatic diamine, an aromatic triamine, a heterocyclic monoamine, a heterocyclic diamine, a heterocyclic triamine, and any combination thereof. Exemplary amine catalysts include ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, neopentylenediamine, hexylenediamine, heptylenediamine, neoheptylenediamine, and the like. diamine), N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl)ether, methyltriethylenediamine, dimethylaminopropylamine, bis(N,N-dimethyl-3-aminopropyl)amine, bis(2-dimethylaminoethyl)ether, 1,1'-((3-(dimethylamino)propyl)azanediyl)bis(propan-2-ol), 2,4,6-tridimethylaminomethyl)phenol, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylbutylenediamine amine, N,N,N',N'-tetramethyl-pentylenediamine, N,N,N',N'-tetramethyl-hexylenediamine, N,N-dimethylbenzylamine, triethylenediamine, pentamethyldiethylenetriamine, diethylenetriamine, N-methylmorpholine, N-ethylmorpholine, 2-methylpropanediamine, N,N'-diethylpiperazine, N,N'-dimethylpiperazine, pyridine, N,N'-dimethylpyridine, quinoline, N,N',N"-tris(dimethylamino-propyl)sym-hexahydrotriazine, and any combination thereof.

[0019] According to another embodiment of the present application, the amine catalyst is represented by formula (3):

[0020] [ka] [In the formula, m is an integer of 2 to 12, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; each of R3 to R6 independently represents H, C1 to C6 12 Alkyl, hydroxy substituted C1-C 12 Alkyl, amino substituted C1-C 12 Alkyl and amine substituted C1-C 12 For example, each of R3 to R6 can be independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-methyl-2-hydroxyethyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, 1-aminoethyl, 2-aminoethyl, 1-aminopropyl, 2-aminopropyl, 3-aminopropyl, 1-methyl-2-aminoethyl, aminobutyl, aminopentyl, aminohexyl, N,N-dimethylaminoethyl, N,N-dimethylaminopropyl, N,N-dimethylaminobutyl, N,N-dimethylaminopentyl, N,N-dimethylaminohexyl, and any isomers thereof. According to another embodiment of the present application, the amine catalyst may be selected from the group consisting of N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl)ether, dimethylaminopropylamine, bis(N,N-dimethyl-3-amino-propyl)amine, 1,1′-((3-(dimethylamino)propyl)azanediyl)bis(propan-2-ol), and any combination thereof.

[0021] According to embodiments of the present disclosure, the amine-based catalyst specifically excludes small aliphatic monoamines, particularly trimethylamine and dimethylamine, intentionally incorporated therein. For example, the amine-based catalyst of the present disclosure does not include pure or essentially pure aliphatic monoamines, such as methylamine, dimethylamine (DMA), or trimethylamine (TMA), nor does the amine-based catalyst include any of the aliphatic monoamines intentionally incorporated therein.

[0022] Without being limited to a particular theory, small or trace amounts of DMA and TMA may be unavoidably present in various commercially produced and purchased amine-type catalysts, such as those listed above. It is also believed that small or trace amounts of DMA and TMA may originate from different sources, including impurities in raw materials, residual reactants and by-products of the preparation process, and isomerization products, decomposition products, and incidental contaminants introduced during storage and transportation of commercially available amine-type catalysts. The content of undesirable DMA and TMA in amine-type catalysts may vary based on the specific category and source of the amine-type catalyst. According to one embodiment of the present application, the amine-type catalyst may have a DMA content of up to 1 wt %, or up to 0.1 wt %, or 0.1 ppm to 0.01 wt %, based on the weight of the amine-type catalyst, or within a numerical range obtained by combining any two of the following endpoint values: 0.047 ppm, 0.05 ppm, 0.08 ppm, 0.1 ppm, based on the weight of the amine-type catalyst. 0.2ppm, 0.3ppm, 0.4ppm, 0.5ppm, 0.6ppm, 0.7ppm, 0.8ppm, 0.9ppm, 1ppm, 3ppm, 5ppm, 10ppm, 20ppm, 50ppm , 80ppm, 100ppm, 120ppm, 150ppm, 180ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, 500ppm, 550ppm m, 600ppm, 650ppm, 700ppm, 750ppm, 800ppm, 850ppm, 900ppm, 950ppm, 1000ppm, 1050ppm, 1100ppm, 1150ppm m, 1200ppm, 1250ppm, 1300ppm, 1400ppm, 1500ppm, 1550ppm, 1600ppm, 1700ppm, 1800ppm, 1900ppm, 2000ppm m, 2200 ppm, 2500 ppm, 2700 ppm, 2800 ppm, 2900 ppm, 3000 ppm, 3500 ppm, 3800 ppm, 4000 ppm, 4500 ppm, 4800 ppm, 5000 ppm, 5500 ppm, 6000 ppm, 6500 ppm, 7000 ppm, 7500 ppm, 8000 ppm, 8500 ppm, 9000 ppm, 9500 ppm, and 1 wt.%.According to another embodiment of the present application, the amine-type catalyst may have a TMA content of up to 1 wt. %, or up to 0.1 wt. %, or 0.01 ppm to 0.01 wt. %, based on the weight of the amine-type catalyst, or a TMA content within a numerical range obtained by combining any two of the following endpoint values: 0.00021 ppm, 0.00025 ppm, 0.0003 ppm, 0.0004 ppm, 0.0005 ppm, 0.0006 ppm, 0.0008 ppm, 0.0009 ... 009ppm, 0.001ppm, 0.0015ppm, 0.002ppm, 0.003ppm, 0.004ppm, 0.005ppm, 0.006ppm, 0.008ppm, 0.01ppm, 0.02ppm, 0.03ppm, 0.04ppm , 0.05ppm, 0.08ppm, 0.1ppm, 0.2ppm, 0.3ppm, 0.4ppm, 0.5ppm, 0.6ppm, 0.7ppm, 0.8ppm, 0.9ppm, 1ppm, 3ppm, 5ppm, 10ppm, 20ppm, 50pp m, 80ppm, 100ppm, 120ppm, 150ppm, 180ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, 500ppm, 550ppm, 600ppm, 650ppm, 700p pm, 750ppm, 800ppm, 850ppm, 900ppm, 950ppm, 1000ppm, 1050ppm, 1100ppm, 1150ppm, 1200ppm, 1250ppm, 1300ppm, 1400ppm, 1500ppm, 1 550 ppm, 1600 ppm, 1700 ppm, 1800 ppm, 1900 ppm, 2000 ppm, 2200 ppm, 2500 ppm, 2700 ppm, 2800 ppm, 2900 ppm, 3000 ppm, 3500 ppm, 3800 ppm, 4000 ppm, 4500 ppm, 4800 ppm, 5000 ppm, 5500 ppm, 6000 ppm, 6500 ppm, 7000 ppm, 7500 ppm, 8000 ppm, 8500 ppm, 9000 ppm, 9500 ppm, and 1 wt. %. According to one embodiment of the present application, the amine-type catalyst contains DMA as an undesired impurity in excess of this amount, but does not contain TMA. According to another embodiment of the present application, the amine-type catalyst contains more than said amount of TMA as an undesirable impurity and does not contain DMA.According to another embodiment of the present application, the amine-type catalyst contains more than said amount of both TMA and DMA as undesirable impurities.

[0023] According to an embodiment of the present disclosure, the deodorizer for reducing DMA and TMA in an amine-based catalyst is represented by Formula (1) or Formula (2):

[0024] [ka] [Wherein R1 is hydrogen or methyl, R2 is C1 to C 12 Alkyl, hydroxy substituted C1-C 12 Alkyl and (meth)acryloxy (C1-C 12 alkylene)-O-(C1-C 12 ) alkyl, and R3 is a divalent C2-C 12 Alkylene, trivalent C3-C 12 Alkylene and tetravalent C4-C 12 and at least one deodorizing agent represented by the formula: alkylene, wherein n is an integer from 2 to 4. According to one embodiment of the present disclosure, R1 is hydrogen and R2 is C1 to C 12 Alkyl, hydroxy substituted C1-C 12 Alkyl and acryloxy (C1-C 12 alkylene)-O-(C1-C 12 ) alkyl, and hydroxy-substituted C1-C 12 The hydroxy group in the alkyl is preferably bonded to a terminal carbon atom of the alkyl group, and R is a divalent C-C 12 Alkylene, trivalent C3-C 12 Alkylene and tetravalent C4-C 12alkylene, and n is an integer from 2 to 4. According to another embodiment of the present disclosure, the deodorizing agent is selected from the group consisting of ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, glycidyl diacrylate, ethylene diol diacrylate, propylene diol diacrylate, butylene diol diarcylate, hexanediol diacrylate, glycerol triacrylate, erythritol tetra(acrylate), pentaerythritol tetra(acrylate), and any combination thereof.

[0025] According to one embodiment of the present application, a deodorizer of Formula (1) or Formula (2) is combined with an amine-type catalyst to form an amine-based catalyst system having a DMA and TMA content reduced to a level determined by relevant environmental regulations or consumer demand, and polyurethane foam articles produced using the amine-based catalyst system have DMA and TMA amounts below the consumer-perceivable odor threshold. According to one embodiment of the present invention, the amine-based catalyst system can be formed by blending a deodorizer of Formula (1) or Formula (2) with an amine-type catalyst and then maintaining the blend at a temperature of 0 to 200°C and a pressure of 0.01 to 10 MPa for 0.5 to 100 hours, either statically or under stirring. The aforementioned temperature can be 5 to 180°C, or 10 to 150°C, or 15 to 120°C, or 20 to 100°C, or 25 to 80°C, or 25 to 50°C. The pressure may be 0.02 to 8 MPa, or 0.04 to 7 MPa, or 0.05 to 5 MPa, or 0.06 to 4 MPa, or 0.08 to 2 MPa, or 0.09 to 1 MPa, or 0.1 to 0.5 MPa. The period for maintaining the blend may be 0.5 to 100 hours, or 1 to 90 hours, or 2 to 80 hours, or 5 to 70 hours, or 6 to 60 hours, or 8 to 48 hours, or 10 to 24 hours. According to one embodiment of the present disclosure, the blend of the deodorizing agent of Formula (1) and the amine-type catalyst is allowed to stand overnight at ambient temperature and pressure.

[0026] Without being limited to any theory, the amine-based catalyst system so formed exhibits a DMA level of up to 100 ppm, or up to 80 ppm, or up to 70 ppm, or up to 60 ppm, or up to 50 ppm, or up to 40 ppm, or up to 30 ppm, or up to 20 ppm, or up to 19 ppm, or up to 16 ppm, or up to 15 ppm, or up to 13 ppm, or up to 12 ppm, or up to 10 ppm, or up to 8 ppm, or up to 6 ppm, or up to 5 ppm, or up to 3 ppm, or up to 1 ppm, or up to 0.5 ppm, or up to 0.2 ppm, or up to 0.1 ppm, or up to 0.05 ppm, or up to 0.01 ppm, based on the total weight of the amine-based catalyst system. According to another embodiment of the present disclosure, the polyurethane foam, polyurethane foam article, or polyurethane foam product prepared by using the amine-based catalyst system exhibits a DMA level of up to 80 ppm, or up to 70 ppm, or up to 60 ppm, or up to 50 ppm, or up to 40 ppm, or up to 30 ppm, or up to 20 ppm, or up to 19 ppm, or up to 16 ppm, or up to 15 ppm, or up to 13 ppm, or up to 12 ppm, or up to 10 ppm, or up to 8 ppm, or up to 6 ppm, or up to 5 ppm, or up to 3 ppm, or up to 1 ppm, or up to 0.5 ppm, or up to 0.2 ppm, or up to 0.1 ppm, or up to 0.05 ppm, or up to 0.01 ppm, or up to 0.005 ppm, or up to 0.001 ppm, based on the total weight of the polyurethane foam. For example, the addition of a deodorizing agent represented by formula (1) may reduce the DMA content in the amine-based catalyst system or polyurethane foam by 35 wt%, or 40 wt%, or 45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 98 wt%, or 99 wt%, or 99.5 wt%, or 99.9 wt%, or 99.95 wt%, or 99.99 wt%, or even 100 wt%, compared to the initial amount of DMA contained in the amine-type catalyst.According to another embodiment of the present disclosure, the amine-based catalyst system thus formed exhibits a TMA level of up to 100 ppm, or up to 80 ppm, or up to 70 ppm, or up to 60 ppm, or up to 50 ppm, or up to 40 ppm, or up to 30 ppm, or up to 20 ppm, or up to 19 ppm, or up to 16 ppm, or up to 15 ppm, or up to 13 ppm, or up to 12 ppm, or up to 10 ppm, or up to 8 ppm, or up to 6 ppm, or up to 5 ppm, or up to 3 ppm, or up to 1 ppm, or up to 0.5 ppm, or up to 0.2 ppm, or up to 0.1 ppm, or up to 0.05 ppm, or up to 0.01 ppm, based on the total weight of the amine-based catalyst system. According to another embodiment of the present disclosure, the polyurethane foam, polyurethane foam article, or polyurethane foam product prepared by using the amine-based catalyst system exhibits a TMA level of up to 70 ppm, or up to 60 ppm, or up to 50 ppm, or up to 40 ppm, or up to 30 ppm, or up to 20 ppm, or up to 19 ppm, or up to 16 ppm, or up to 15 ppm, or up to 13 ppm, or up to 12 ppm, or up to 10 ppm, or up to 8 ppm, or up to 6 ppm, or up to 5 ppm, or up to 3 ppm, or up to 1 ppm, or up to 0.5 ppm, or up to 0.2 ppm, or up to 0.1 ppm, or up to 0.05 ppm, or up to 0.01 ppm, or up to 0.005 ppm, or up to 0.001 ppm, based on the total weight of the polyurethane foam. For example, the addition of the deodorizing agent represented by formula (1) can reduce the TMA content in the amine-based catalyst system or polyurethane foam by 40 wt%, or 45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 98 wt%, or 99 wt%, compared to the initial amount of TMA contained in the amine-based catalyst.According to one embodiment of the present disclosure, the content of the amine-based catalyst system may be 0.01 wt % to 5 wt %, for example, 0.05 wt % to 4 wt %, or 0.08 wt % to 3.5 wt %, or 0.1 wt % to 3 wt %, or 0.5 wt % to 2.5 wt %, or 0.8 wt % to 2 wt %, or 0.85 wt % to 1.5 wt %, or 0.9 wt % to 1.2 wt %, or 0.92 wt % to 1.0 wt %, based on the total weight of the polyurethane composition.

[0027] In various embodiments, an isocyanate compound having at least two isocyanate groups, also known as a polyisocyanate compound, refers to an aliphatic, cycloaliphatic, aromatic, araliphatic, or heteroaryl compound having at least two isocyanate groups. The isocyanate compound may have an average functionality of at least about 2.0, e.g., about 2 to 10, or about 2 to about 8, or about 2 to about 6. Exemplary isocyanate compounds include C2 to C6 isocyanate compounds containing at least two isocyanate groups. 12 Aliphatic isocyanate compounds, C6-C containing at least two isocyanate groups 15 Alicyclic isocyanate compounds, C6-C containing at least two isocyanate groups 15 Aromatic isocyanate compounds, C7-C containing at least two isocyanate groups 15 In another embodiment, the isocyanate compound may be selected from the group consisting of m-phenylene diisocyanate, 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate (TDI), various isomers of diphenylmethane diisocyanate (MDI), methylenebis(cyclohexylisocyanate) (HMDI), hexamethylene-1,6-diisocyanate (HDI), tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate, hydrogenated MDI, naphthylene-1,5-diisocyanate, isophorone diisocyanate (IPDI), or mixtures thereof, among others.

[0028] According to another embodiment of the present disclosure, the isocyanate compound may be a modified isocyanate compound, i.e., a product obtained by chemical modification of the above-mentioned isocyanate compound. Exemplary modified isocyanate compounds are polyisocyanates containing esters, ureas, biurets, isocyanurates, allophanates, carbodiimides, or uretonimines, such as 4,4'-carbodiimide-modified MDI products. For example, liquid isocyanate compounds containing carbodiimide groups, uretonimine groups, or isocyanurate rings and having an isocyanate group (NCO) content of 10 to 40 weight percent, for example, 20 to 35 weight percent, may be used.

[0029] Alternatively or additionally, the isocyanate compound may comprise an isocyanate prepolymer having an NCO functionality ranging from 2 to 10, e.g., from 2 to 8, or from 2 to 6. The isocyanate prepolymer may comprise one or more of the above-mentioned monomeric isocyanate compounds, a C2-C3 isocyanate compound containing at least two hydroxy groups, provided that the isocyanate prepolymer contains at least two free isocyanate groups. 16 Aliphatic polyhydric alcohols, C5-C containing at least two hydroxy groups 16 Alicyclic polyhydric alcohols, C6-C containing at least two hydroxy groups 16 Aromatic polyhydric alcohols, C7-C containing at least two hydroxy groups 15It can be obtained by reacting with one or more isocyanate-reactive compounds selected from the group consisting of araliphatic polyhydric alcohols, polyester polyols having a molecular weight of 500 to 5,000, polycarbonate polyols having a molecular weight of 200 to 5,000, polyether polyols having a molecular weight of 200 to 5,000, or any combination thereof. For example, the isocyanate-reactive compound for preparing the isocyanate prepolymer can be selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, n-neopentyl glycol, bis(hydroxymethyl)cyclohexane, such as 1,4-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1,3-diol, methylpentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, bishydroxyethyl-bisphenol-A, bishydroxypropyl-bisphenol-A, cyclohexanedimethanol, and bishydroxyethylhydroquinone. Suitable prepolymers for use as the isocyanate compound are those having an NCO group content of 2 to 40 weight percent, for example, 4 to 30 weight percent. The amount of the isocyanate compound can vary based on the actual requirements of the polyurethane foam. For example, in one exemplary embodiment, the content of the isocyanate compound can be about 5% to about 60% by weight, such as about 10% to about 50% by weight, or about 15% to about 45% by weight, or about 20% to about 40% by weight, or about 30% to about 38% by weight, based on the total weight of the polyurethane composition. According to an embodiment of the present disclosure, the amount of the isocyanate compound is appropriately selected so that the isocyanate groups are present in a stoichiometrically equivalent amount or a slight excess amount relative to the total molar amount of isocyanate-reactive groups (e.g., hydroxyl groups and amino groups) contained in the polyol compound, catalyst system, and any additional additives or modifiers.

[0030] According to one embodiment of the present disclosure, the polyol compound is a C2-C hydroxyl group-containing polyol. 16 Aliphatic polyhydric alcohols, C6-C containing at least two hydroxyl groups 16 Alicyclic polyhydric alcohols, C6-C containing at least two hydroxyl groups 16 Aromatic polyhydric alcohols, C7-C containing at least two hydroxyl groups 15 The polyol may be selected from the group consisting of araliphatic polyols, polyester polyols having a molecular weight of 500 to 12,000, polycarbonate polyols having a molecular weight of 200 to 8,000, polyether polyols having a molecular weight of 200 to 8,000, core-shell polymer polyols having a core phase and a shell phase based on polyols, or any combination thereof. The shell phase of the core-shell polymer polyol may be selected from the group consisting of at least one poly(C2-C6) 10For example, the polyol of the shell phase may be selected from the group consisting of polyethylene, (methoxy)polyethylene glycol (MPEG), polyethylene glycol (PEG), poly(propylene glycol), polytetramethylene glycol, poly(2-methyl-1,3-propane glycol), or a copolymer of ethylene epoxide and propylene epoxide (polyethylene glycol-propylene glycol) having primary or secondary hydroxyl end groups. The core-shell polymer polyol core phase may be microsized and may comprise any polymer compatible with the shell phase. For example, the core phase may comprise polystyrene, polyacrylonitrile, polyester, polyolefin, or polyether, which differs (either in composition or degree of polymerization) from that of the shell phase. According to an embodiment of the present application, the polyol may be a composite particle having a core-shell structure, in which the core is a microsized core composed of SAN (styrene and acrylonitrile) and the shell phase is composed of PO-EO polyol. Such polymer polyols can be prepared by radical copolymerization of styrene, acrylonitrile, and poly(EO-PO) polyols containing ethylenically unsaturated groups. According to embodiments of the present disclosure, polyether polyols can be prepared by polymerization of one or more linear or cyclic alkylene oxides selected from propylene oxide (PO), ethylene oxide (EO), butylene oxide, tetramethylene glycol, tetrahydrofuran, 2-methyl-1,3-propane glycol, and mixtures thereof. Exemplary polyester polyols include the reaction product of a polyol, preferably a diol, with a polycarboxylic acid or an anhydride thereof, such as a dicarboxylic acid or dicarboxylic acid anhydride. The polycarboxylic acid or anhydride may be aliphatic, alicyclic, aromatic, and / or heterocyclic and may be substituted, for example, with halogen atoms. The polycarboxylic acid may be unsaturated. Examples of such polycarboxylic acids include succinic acid, adipic acid, terephthalic acid, isophthalic acid, trimellitic anhydride, phthalic anhydride, maleic acid, maleic anhydride, and fumaric acid.The polyols used to make the polyester polyols preferably have an equivalent weight of about 150 or less and include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, cyclohexanedimethanol, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methylglycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, dibutylene glycol, etc. The amount of polyol compound can vary based on the actual requirements of the polyurethane foam. For example, in one exemplary embodiment, the content of the polyol compound may be about 30% by weight to about 90% by weight, for example, about 40% by weight to about 85% by weight, or about 45% by weight to about 80% by weight, or about 50% by weight to about 75% by weight, or about 52% by weight to about 70% by weight, or about 55% by weight to about 65% by weight, or about 58% by weight to about 60% by weight, based on the total weight of the polyurethane composition.

[0031] In various embodiments of the present disclosure, the polyurethane composition includes one or more additives selected from the group consisting of surfactants, chain extenders, crosslinkers, antioxidants, blowing agents, foaming agents, foam stabilizers, defoamers, tackifiers, plasticizers, rheology modifiers, UV absorbers, light stabilizers, cocatalysts, fillers, colorants, pigments, water scavengers, solvents, diluents, flame retardants, anti-slip agents, antistatic agents, preservatives, biocides, and any combination thereof. These additives may be delivered and stored as separate components and incorporated into the polyurethane composition shortly before or immediately before combining the isocyanate compound and polyol. Alternatively, these additives may be contained in either the isocyanate compound or the polyol if they are chemically inert or substantially inert to isocyanate groups or isocyanate-reactive groups.

[0032] Suitable surfactants are substances that stabilize the foam formed during the foaming reaction until the foam is sufficiently cured and self-supporting. A wide variety of silicone surfactants commonly used to make polyurethane foams can be used in the present disclosure. Examples of such silicone surfactants are commercially available as Tegostab (Evonik Corporation), Niax (Momentive), and Dabco (Air Products and Chemicals). The surfactant is typically present in an amount of up to 5 wt. %, e.g., 0.1 to 4 wt. %, or 0.2 to 3 wt. %, or 0.3 to 2 wt. %, or 0.4 to 1 wt. %, or 0.5 to 0.8 wt. %, based on the total weight of the polyurethane composition.

[0033] One or more crosslinking agents may also be present in the polyurethane compositions of the present disclosure. For purposes of the present disclosure, a "crosslinking agent" is a substance having three or more isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 300, e.g., less than 200. The crosslinking agent typically contains 3 to 8, particularly 3 to 4, hydroxyl (including primary, secondary, and tertiary hydroxyl), primary amine, secondary amine, or tertiary amine groups per molecule and has an equivalent weight of 30 to about 200, particularly 50 to 125. According to embodiments of the present disclosure, the crosslinking agent may be selected from the group consisting of diethanolamine, triethanolamine, di(isopropanol)amine, tri(isopropanol)amine, glycerin, trimethylolpropane, pentaerythritol, and any combination thereof, such as a combination of diethanolamine and triethanolamine. In the context of the present disclosure, the crosslinking agent has a molecular structure different from that of the amine-based catalyst.

[0034] A chain extender is a chemical substance having two or more isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 300, e.g., less than 200. The isocyanate-reactive groups can be hydroxyl groups, primary aliphatic or aromatic amino groups, or secondary aliphatic or aromatic amino groups. Exemplary chain extenders include monoethylene glycol (MEG), diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, cyclohexanedimethanol, ethylenediamine, phenylenediamine, bis(3-chloro-4-aminophenyl)methane, dimethylthio-toluenediamine, or diethyltoluenediamine. According to an embodiment of the present disclosure, the chain extender is a short-chain (e.g., C2-C4) polyol containing only hydroxyl groups as isocyanate-reactive groups, such as monoethylene glycol. According to another embodiment of the present disclosure, the chain extender is an aliphatic or cycloaliphatic C2-C6 alkyl ester having a hydroxyl functionality of 2.0 to 8.0, e.g., 3.0 to 7.0, or 4.0 to 6.0, or 5.0 to 5.5. 12 The polyol may be selected from the group consisting of ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, 1,4-cyclohexanedimethanol, and isomers thereof. A chain extender may be included as part of component (B).

[0035] Chain extenders and crosslinkers are suitably used in small amounts, since increasing the amount of either of these materials increases hardness. The crosslinker is typically present in an amount of up to 3 wt%, e.g., 0.05-3 wt%, or 0.1-2.5 wt%, or 0.2-2 wt%, or 0.3-1 wt%, or 0.4-0.8 wt%, or 0.5-0.6 wt%, based on the total weight of the polyurethane composition. The chain extender content can be up to 5 wt%, e.g., 0-3 wt%, or 0.01-2.5 wt%, or 0.05-2 wt%, or 0.1-1 wt%, or 0.4-0.8 wt%, or 0.5-0.6 wt%, based on the total weight of the polyurethane composition.

[0036] One or more fillers may be present in the polyurethane composition. Fillers are included primarily to reduce cost. Particulate rubber-like materials are particularly useful fillers. The filler content may comprise 0 to 50% or more by weight of the polyurethane composition.

[0037] Blowing agents may be chemical (exothermic), physical (endothermic), or a mixture of at least one of each type. Chemical types typically react or decompose under the conditions of the foaming reaction to produce carbon dioxide or nitrogen gas. Water and various carbamate compounds are examples of suitable chemical blowing agents. Physical blowing agents include carbon dioxide, various low-boiling hydrocarbons, hydrofluorocarbons, hydrofluorochlorocarbons, ethers, etc. Water is one typical blowing agent, either alone or in combination with one or more physical blowing agents.

[0038] According to one embodiment of the present disclosure, the polyurethane composition includes one or more antioxidants, and exemplary antioxidants include substituted or unsubstituted phenolic antioxidants, thiocarboxylate ester antioxidants, phosphite antioxidants, phosphonite antioxidants, substituted or unsubstituted benzofuranones, substituted or unsubstituted indolinones, tocopherols, hydroxylated thiodiphenyl ethers, O-, N-, and S-benzyl compounds, hydroxybenzylated malonates, and triazine compounds. According to an embodiment of the present disclosure, the amount of antioxidant is 0 to 5 wt %, for example, 0.1 to 4 wt %, or 0.5 to 3 wt %, or 0.8 to 2 wt %, or 1 to 1.5 wt %, based on the total weight of the polyurethane composition.

[0039] The process for preparing polyurethane foam may further include additional additives such as foam stabilizers, defoamers, tackifiers, plasticizers, rheology modifiers, UV absorbers, light stabilizers, cocatalysts, fillers, colorants, pigments, water scavengers, solvents, diluents, flame retardants, anti-slip agents, antistatic agents, preservatives, biocides, and any combination thereof.

[0040] According to embodiments of the present disclosure, there are provided methods for producing polyurethane foams with reduced odor and methods for reducing / eliminating odor in polyurethane foams, the methods comprising the steps of: (i) combining at least one amine-based catalyst with at least one deodorizing agent to form an amine-based catalyst system; and (ii) reacting at least one isocyanate compound containing at least two isocyanate groups with at least one polyol compound in the presence of the amine-based catalyst system, or catalyzing the reaction of the isocyanate compound and the polyol compound with the amine-based catalyst system, to form the polyurethane foam with reduced odor.

[0041] According to embodiments of the present disclosure, polyurethane foam products can be produced by blending components to form a reaction mixture and curing it. Free-rise processes, such as continuous slabstock production techniques, can be used. Alternatively, various molding methods can be used. Processing equipment and parameters for slabstock production and molding methods are generally known in the relevant arts. For example, the various components can be introduced individually or in various subcombinations into a mixhead or other mixing device, where they are mixed and dispensed into an area to be cured (such as a trough or other open vessel, or a closed mold). Often, particularly when producing molded foams, it is convenient to form a compounded polyol component containing the polyol compound(s), the amine-based catalyst system, the crosslinker and / or chain extender (if present), and any other additives, such as surfactant(s) and blowing agent(s). This compounded polyol component is then contacted with an isocyanate compound (and any other components not present in the compounded polyol component) to produce the foam.

[0042] Some or all of the various ingredients and / or components may be heated prior to mixing to form a reaction mixture. In another example, the ingredients and / or components are mixed at about ambient temperature (e.g., 15-40°C). After all ingredients are mixed, heat may be applied to the reaction mixture, although this is often unnecessary. Suitable conditions for accelerating the curing of the polyurethane polymer include temperatures of about 20°C to about 150°C. In some embodiments, curing occurs at a temperature of about 30°C to about 120°C. In other embodiments, curing occurs at a temperature of about 35°C to about 110°C. In various embodiments, the temperature for curing may be selected at least in part based on the duration required for the polyurethane polymer to cure at that temperature. The curing time will also depend on other factors, including, for example, the specific ingredients (e.g., catalyst and amount thereof) and the size and shape of the article being produced.

[0043] According to embodiments of the present disclosure, the polyurethane foam product formed by the curing reaction can be flexible or rigid, and is particularly flexible polyurethane foam. Flexible polyurethane foam products have a hardness of 5 to 200 kg / m 3 , e.g., 8 to 180 kg / m 3 , or 10 to 160 kg / m 3 , or 12 to 150 kg / m 3 , or 15 to 140 kg / m 3 , or 18 to 120 kg / m 3 , or 20 to 100 kg / m 3 , or 24 to 80 kg / m 3 , or 30 to 60 kg / m 3 , or 40 to 50 kg / m 3 or within a numerical range obtained by combining any two of the above endpoints. The flexible polyurethane foam may have a resilience of at least 50% in the ball rebound test of ASTM 3574-H.

[0044] The above description is intended to be general and is not intended to include all possible embodiments of the present invention. Similarly, the following examples are provided for illustrative purposes only and are not intended to define or limit the present invention in any way. Those skilled in the art will fully recognize that other embodiments within the scope of the claims will be apparent from consideration of the specification and / or practice of the invention disclosed herein. Such other embodiments may involve selection of specific ingredients and their configurations and proportions; mixing and reaction conditions; containers, development equipment and protocols; performance and selectivity; product and by-product identification; subsequent processing and use; and the skilled artisan will recognize that such may vary within the scope of the claims appended hereto. [Example]

[0045] Some embodiments of the present invention will now be described in the following examples. However, the scope of the present disclosure is not, of course, limited to the formulations shown in these examples. Rather, the examples merely relate to the invention of the present disclosure.

[0046] Information on the raw materials used in the examples is listed in Table 1 below.

[0047] [Table 1]

[0048] Characterization Technology A. The DMA or TMA concentration in each sample of the comparative examples and inventive examples was determined with a GC-FID instrument as shown in Table 2 below.

[0049] [Table 2]

[0050] Each sample was prepared by dissolving 0.100 g of catalyst or amine-based catalyst system in 1.00 mL of THF, and then 1 μL of the sample was injected into the autosampler. A series of external standard solutions of DMA or TMA in THF were prepared, and external standard fitting plots were generated based on the GC-FID integrated peak areas of these solutions to quantify the DMA / TMA concentration of each comparative example or inventive example.

[0051] Comparative Examples 1-3: Spontaneous generation of DMA in amine-based catalysts.

[0052] In the comparative examples, the presence and further spontaneous formation of DMA during aging of three typical commercially available amine-based catalysts (Polycat 15 for Comparative Example 1, DPA for Comparative Example 2, and DMAPA for Comparative Example 3) was characterized.

[0053] Polycat 15, DPA, and DMAPA samples were commercially available and used directly without any pretreatment such as purification. The initial DMA concentration in each sample was measured by GC-FID.

[0054] Each sample was then aged in a sealed vial and aged for two weeks in an oven maintained at a constant temperature of 50°C, after which the DMA concentration in the aged sample was further measured by GC-FID. Without being limited by any theory, the above aging process is an accelerated model that mimics the normal storage / transport of these amine-based catalysts under ambient conditions.

[0055] As shown by the experimental results in Table 3, all commercial amine-based catalysts inevitably contained DMA as an impurity, and the concentration of DMA increased significantly after aging. All catalysts exhibited an unpleasant fishy odor, with the odor being much stronger in the aged samples.

[0056] [Table 3]

[0057] Examples 1 to 10 of the present invention and Comparative Examples 4 to 8 In Examples 1 to 10 of the present invention, the amine-based catalyst systems were prepared by directly mixing different amounts of deodorizers, as listed in Table 4, with the amine-based catalyst at ambient temperature and allowing the mixture to stand overnight at ambient temperature and pressure. The deodorizer content is expressed in "weight percentage (wt%)" based on 100 wt% of the amine-based catalyst. The DMA concentration of each sample was measured by GC-FID. The measurement results are summarized in Table 4.

[0058] [Table 4]

[0059] In Comparative Examples 4 to 8, the procedures of Examples 1 to 10 of the present invention were repeated except that the formulation of the amine catalyst system was changed to that shown in Table 5 below.

[0060] [Table 5]

[0061] It can be seen that all of the above examples of the present invention can effectively reduce or even completely eliminate the DMA impurities contained in the commercial amine-based catalysts, while none of the comparative examples can achieve such effective improvement.

[0062] Example 11 of the present invention In the examples of the present invention, the amine-based catalyst system was prepared by directly mixing 99 parts by weight of DPA with 1 part by weight of HBA at ambient temperature and allowing the mixture to stand overnight at ambient temperature and pressure. The amine-based catalyst system was thoroughly mixed with the polyol, crosslinker, surfactant, and water shown in Table 6 below using a stirrer at a speed of 3000 RPM for 3 minutes to form the polyol component. The combined polyol component was then stored at room temperature for 12 to 24 hours.

[0063] A 100g aliquot of the compounded polyol prepared above was mixed with 60g of NE496K isocyanate, and the reaction between the polyol and isocyanate occurred, accompanied by significant foaming. The foam product samples were wrapped in aluminum foil and stored at ambient temperature for 7 days until the reaction was complete. A 0.2g sample of the foam was transferred to a vial with a 20mL headspace. The vial was sealed and heated at 80°C for 2 hours. The headspace gas was then sampled and analyzed by GC-FID to determine the concentrations of DMA and TMA released into the headspace from the polyurethane foam.

[0064] Additionally, sensory evaluation was performed by six trained panelists based on the VDA270 method from the automotive industry. The trained human panelists consisted of six in-house employees certified by SGS Co., Ltd. for odor intensity, pleasantness / unpleasantness, and odor description training. Six cubic ingots weighing 6 g were cut from the polyurethane foam samples prepared above. Each ingot was sealed separately in a 1-liter clean glass vial and heated at 80°C for 2 hours. The vials were then cooled to 60°C for sensory evaluation. Odor intensity and amine odor intensity values ​​were evaluated and scored according to VDA270 using the following ranking criteria: (1) not perceptible; (2) perceptible but not noticeable; (3) clearly perceptible but not noticeable; (4) noticeable; (5) very noticeable; and (6) unacceptable. The average score was reported as the final result.

[0065] A 150 g aliquot of the polyol component prepared above was mixed with 90 g of NE496K isocyanate at 3000 RPM for 6-8 seconds to ensure complete mixing, and the contents were then immediately poured into a popcorn barrel with a top diameter of 17 cm and a bottom diameter of 14 cm. The reaction between the polyol and isocyanate occurred with significant foaming. Creaming time was defined as the time at which the foam began to expand, and rise time was defined as the time at which the foam was fully expanded or had expanded to its maximum height. Foam height was also recorded in centimeters (cm). Creaming time, rise time, and foam height were reported as measures of the catalytic activity of the catalyst system.

[0066] The specific formulation and characterization results of this example are summarized below in Table 6. In Table 6, the contents of DMA and TMA in the headspace are expressed as percentage ratios (%) compared to the corresponding contents measured in Comparative Example 4. Notably, the DMA level in the headspace was too low to be detectable, and the TMA level in the headspace was reduced by 54.5% (100% - 45.5%).

[0067] Example 12 of the Present Invention In this inventive example, the procedure of Inventive Example 11 was repeated, except that the amine-based catalyst system was prepared by directly mixing 95 parts by weight of DPA with 5 parts by weight of HBA and heating the mixture at room temperature overnight. The specific formulation and characterization results for this example are summarized in Table 6 below.

[0068] Comparative Example 9 In this comparative example, the procedure of Inventive Example 11 was repeated, except that fresh DPA purchased from Evonik was used directly as the catalyst without the addition of HBA or any other deodorizing agent. The specific formulation and characterization results for this comparative example are summarized in Table 6 below.

[0069] Comparative Example 10 In this comparative example, the procedure of Comparative Example 9 was repeated, except that the aged DPA prepared in Comparative Example 2 was used as the catalyst. The specific formulation and characterization results for this comparative example are summarized in Table 6 below.

[0070] [Table 6]

[0071] As can be seen from Table 6 above, polyurethane foams prepared using the catalyst system of the present invention exhibited effective removal of DMA and significant removal of TMA, with no substantial effect on the catalytic reactivity of the catalyst observed. Examples of the invention of this application include the following. [1] A polyurethane composition for preparing a polyurethane foam, comprising: (A) at least one isocyanate compound containing at least two isocyanate groups; (B) at least one polyol compound, and (C) an amine-based catalyst system, (C1) at least one amine catalyst selected from the group consisting of aliphatic diamines, aliphatic triamines, alicyclic monoamines, alicyclic diamines, alicyclic triamines, araliphatic monoamines, araliphatic diamines, araliphatic triamines, aromatic monoamines, aromatic diamines, aromatic triamines, heterocyclic monoamines, heterocyclic diamines, heterocyclic triamines, and any combination thereof; (C2) Formula (1) or Formula (2): [ka] [In the formula, R 1 is hydrogen or methyl, and R 2 is C 1 ~C 12 Alkyl, hydroxy-substituted C 1 ~C 12 Alkyl, and (meth)acryloxy (C 1 ~C 12 alkylene)-O-(C 1 ~C 12 ) alkyl, and R 3 is a divalent C 2 ~C 12 Alkylene, trivalent C 3 ~C 12 Alkylene, and tetravalent C 4 ~C 12 and at least one deodorizing agent selected from the group consisting of alkylenes, wherein n is an integer from 2 to 4; and an amine-based catalyst system comprising: [2] R 1 is hydrogen and R 2 But C 1 ~C12 Alkyl, hydroxy-substituted C 1 ~C 12 Alkyl and acryloxy (C 1 ~C 12 )-O-(C 1 ~C 12 alkylene)alkyl; R 3 But divalent C 2 ~C 6 Alkylene, trivalent C 3 ~C 6 Alkylene, and tetravalent C 4 ~C 6 The polyurethane composition according to the above item [1], wherein the alkylene is selected from the group consisting of alkylenes. [3] The polyurethane composition according to [1] above, wherein the deodorizing agent is selected from the group consisting of ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, glycidyl diacrylate, ethylene diol diacrylate, propylene diol diacrylate, butylene diol diarcylate, hexanediol diacrylate, glycerol triacrylate, erythritol tetra(acrylate), pentaerythritol tetra(acrylate), and any combination thereof. [4] The amine catalyst is selected from the group consisting of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, neopentylenediamine, hexylenediamine, heptylenediamine, neoheptylenediamine, N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl)ether, methyltriethylenediamine, dimethylaminopropylamine, bis(N,N-dimethyl-3-aminopropyl)amine, bis(2-dimethylaminoethyl)ether, 1,1'-((3-(dimethylamino)propyl)azanediyl)bis(propan-2-ol), 2,4,6-tridimethylaminomethyl)phenol, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylbutylenediamine, N,N,N

[0023] The polyurethane composition according to [1] above, wherein the alkyl group is selected from the group consisting of N,N'-tetramethyl-pentylenediamine, N,N,N',N'-tetramethyl-hexylenediamine, N,N-dimethylbenzylamine, triethylenediamine, pentamethyldiethylenetriamine, diethylenetriamine, N-methylmorpholine, N-ethylmorpholine, 2-methylpropanediamine, N,N'-diethylpiperazine, N,N'-dimethylpiperazine, pyridine, N,N'-dimethylpyridine, quinoline, N,N',N"-tris(dimethylamino-propyl)sym-hexahydrotriazine, and any combination thereof. [5] The amine catalyst is a catalyst represented by the formula (3):

change

[10] A method for producing a polyurethane foam, comprising: (i) combining at least one amine-based catalyst with at least one deodorizing agent to form an amine-based catalyst system; (ii) reacting at least one isocyanate compound containing at least two isocyanate groups with at least one polyol compound in the presence of the amine-based catalyst system to produce the polyurethane foam; the amine catalyst is selected from the group consisting of aliphatic diamines, aliphatic triamines, alicyclic monoamines, alicyclic diamines, alicyclic triamines, araliphatic monoamines, araliphatic diamines, araliphatic triamines, aromatic monoamines, aromatic diamines, aromatic triamines, heterocyclic monoamines, heterocyclic diamines, heterocyclic triamines, and any combination thereof; The deodorant may be a compound represented by formula (1) or (2):

change

Claims

1. 1. A polyurethane composition for preparing a polyurethane foam, comprising: (A) at least one isocyanate compound containing at least two isocyanate groups; (B) at least one polyol compound, and (C) an amine-based catalyst system, (C1) at least one amine catalyst selected from the group consisting of aliphatic diamines, aliphatic triamines, alicyclic monoamines, alicyclic diamines, alicyclic triamines, araliphatic monoamines, araliphatic diamines, araliphatic triamines, aromatic monoamines, aromatic diamines, aromatic triamines, heterocyclic monoamines, heterocyclic diamines, heterocyclic triamines, and any combination thereof; (C2) Formula (1) or Formula (2): 【Chemistry 1】 [In the formula, R １ is hydrogen, and R ２ is C １ ~C １２ Alkyl, hydroxy-substituted C １ ~C １２ Alkyl, and (meth)acryloxy (C １ ~C １２ alkylene)-O-(C １ ~C １２ ) alkyl; R ３ is a divalent C ２ ~C １２ Alkylene, trivalent C ３ ~C １２ Alkylene, and tetravalent C ４ ~C １２ and at least one deodorizer represented by the formula (C1), wherein the weight ratio of the at least one deodorizer (C2) to the at least one amine catalyst (C1) is 0.5:100 to 15:

100.

2. R ２ But C １ ~C １２ Alkyl, hydroxy-substituted C １ ~C １２ Alkyl, and acryloxy (C １ ~C １２ )—O—(C １ ~C １２ alkylene) alkyl, and R ３ But divalent C ２ ~C ６ Alkylene, trivalent C ３ ~C ６ Alkylene, and tetravalent C ４ ~C ６ The polyurethane composition of claim 1 , wherein the alkylene group is selected from the group consisting of alkylenes.

3. 2. The polyurethane composition of claim 1, wherein the deodorizing agent is selected from the group consisting of ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, glycidyl diacrylate, ethylene diol diacrylate, propylene diol diacrylate, butylene diol diarcylate, hexanediol diacrylate, glycerol triacrylate, erythritol tetra(acrylate), pentaerythritol tetra(acrylate), and any combination thereof.

4. The amine catalyst is selected from the group consisting of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, neopentylenediamine, hexylenediamine, heptylenediamine, neoheptylenediamine, N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl)ether, methyltriethylenediamine, dimethylaminopropylamine, bis(N,N-dimethyl-3-aminopropyl)amine, bis(2-dimethylaminoethyl)ether, 1,1'-((3-(dimethylamino)propyl)azanediyl)bis(propan-2-ol), 2,4,6-tridimethylaminomethyl)phenol, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylbutylenediamine, N,N, 2. The polyurethane composition of claim 1, wherein the alkyl group is selected from the group consisting of N',N'-tetramethyl-pentylenediamine, N,N,N',N'-tetramethyl-hexylenediamine, N,N-dimethylbenzylamine, triethylenediamine, pentamethyldiethylenetriamine, diethylenetriamine, N-methylmorpholine, N-ethylmorpholine, 2-methylpropanediamine, N,N'-diethylpiperazine, N,N'-dimethylpiperazine, pyridine, N,N'-dimethylpyridine, quinoline, N,N',N"-tris(dimethylamino-propyl)sym-hexahydrotriazine, and any combination thereof.

5. The amine catalyst is a catalyst represented by the formula (3): 【Chemistry 2】 [wherein m is an integer from 2 to 12; R ３ ~R ６ each independently represents H, C １ ~C １２ Alkyl, hydroxy-substituted C １ ~C １２ Alkyl, amino-substituted C １ ~C １２ Alkyl and amine substituted C １ ~C １２ 2. The polyurethane composition of claim 1, wherein the alkyl group is selected from the group consisting of alkyl.

6. The isocyanate compound is a) C containing at least two isocyanate groups ２ ~C １２ Aliphatic isocyanate compounds, C containing at least two isocyanate groups ６ ~C １５ Alicyclic isocyanate compounds, C containing at least two isocyanate groups ６ ~C １５ Aromatic isocyanate compounds, C containing at least two isocyanate groups ７ ~C １５ araliphatic isocyanate compounds, or combinations thereof, and b) reacting one or more monomeric isocyanate compounds of a) with a C hydroxy group-containing isocyanate prepolymer, provided that the isocyanate prepolymer contains at least two free isocyanate groups; ２ ~C １６ aliphatic polyhydric alcohols, C containing at least two hydroxy groups ５ to C16 alicyclic polyhydric alcohols, C containing at least two hydroxy groups ６ ~C １６ Aromatic polyhydric alcohols, C containing at least two hydroxy groups ７ ~C １５ the isocyanate prepolymer prepared by reacting with one or more isocyanate-reactive components selected from the group consisting of an araliphatic polyol, a polyester polyol having a molecular weight of 500 to 5000, a polycarbonate polyol having a molecular weight of 200 to 5000, a polyether polyol having a molecular weight of 200 to 5000, or any combination thereof; The polyol compound is a C ２ C to C16 aliphatic polyhydric alcohols, C containing at least two hydroxyl groups ６ ~C １６ Alicyclic polyhydric alcohols, C containing at least two hydroxyl groups ６ ~C １６ Aromatic polyhydric alcohols, C containing at least two hydroxyl groups ７ ~C １５ 2. The polyurethane composition of claim 1, wherein the polyol is selected from the group consisting of an araliphatic polyol, a polyester polyol having a molecular weight of 500 to 12,000, a polycarbonate polyol having a molecular weight of 200 to 8,000, a polyether polyol having a molecular weight of 200 to 8,000, a core-shell polymer polyol having a polyol-based core phase and a shell phase, or any combination thereof.

7. 10. The polyurethane composition of claim 1, further comprising at least one additive selected from the group consisting of surfactants, chain extenders, crosslinkers, antioxidants, blowing agents, foaming agents, foam stabilizers, defoamers, tackifiers, plasticizers, rheology modifiers, UV absorbers, light stabilizers, cocatalysts, fillers, colorants, pigments, water scavengers, solvents, diluents, flame retardants, anti-slip agents, antistatic agents, preservatives, biocides, and any combination thereof.

8. A polyurethane foam article prepared by using the polyurethane composition of any one of claims 1 to 7.

9. 1. A method for producing a polyurethane foam, comprising: (i) combining at least one amine-based catalyst with at least one deodorizing agent to form an amine-based catalyst system; (ii) reacting at least one isocyanate compound containing at least two isocyanate groups with at least one polyol compound in the presence of the amine-based catalyst system to produce the polyurethane foam; the amine catalyst is selected from the group consisting of aliphatic diamines, aliphatic triamines, alicyclic monoamines, alicyclic diamines, alicyclic triamines, araliphatic monoamines, araliphatic diamines, araliphatic triamines, aromatic monoamines, aromatic diamines, aromatic triamines, heterocyclic monoamines, heterocyclic diamines, heterocyclic triamines, and any combination thereof; The deodorant may be a compound represented by formula (1) or formula (2): 【Transformation 3】 [In the formula, R １ is hydrogen, and R ２ is ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, C １ ~C １２ Alkyl, hydroxy-substituted C １ ~C １２ Alkyl, and (meth)acryloxy (C １ ~C １２ alkylene)-O-(C １ ~C １２ ) alkyl; R ３ is a divalent C ２ ~C １２ Alkylene, trivalent C ３ ~C １２ Alkylene, and tetravalent C ４ ~C １２ wherein n is an integer of 2 to 4; and the weight ratio of the at least one deodorizing agent to the at least one amine catalyst is 0.5:100 to 15:100.

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