Additive composition and method for using the same

Abstract

The additive composition includes a polyol and a zeolite composite. The zeolite composite includes a zeolite substrate and a nitrogen-containing compound adsorbed within at least a portion of the pores in the surface of the zeolite substrate. The nitrogen-containing compound includes (A) a first functional group including a carbon atom doubly bonded to a nitrogen atom and (B) a second functional group including a hydrogen atom covalently bonded to a nitrogen atom. The method for making a polyurethane polymer includes the steps of providing a first polyol, providing an isocyanate compound, providing the additive composition described above, combining the first polyol, the isocyanate compound, and the additive composition to form a reaction mixture, and reacting the isocyanate compound with the first and second polyols to form the polyurethane polymer.

Description

Technical field of inventions

[0001]

[0001] This application relates to additive compositions for reducing volatile organic emissions (e.g., aldehyde emissions) from polymer materials, such as polyurethane polymers and foams. This application also relates to methods for producing polyurethane polymers and foams using such additive compositions. Background

[0002]

[0002] Polyurethane polymers are used in a wide variety of applications, such as the production of polyurethane foams. These polyurethane foams are then used in many different end applications. For example, polyurethane foams are frequently used as cushioning and filling in, for example, seats in transportation (e.g., car seats) and furniture, such as mattresses and other cushioned furniture. When these polyurethane foams are used in enclosed environments, such as inside automobiles or other vehicles, the foams typically must pass tests to limit the amount of volatile organic compounds that the foam may release. The volatile organic compounds released by the polyurethane foam during testing may be produced as byproducts of the reaction that produces the polyurethane polymer. Volatile organic compounds (e.g., aldehydes, such as formaldehyde, acetaldehyde, and propionaldehyde) may also be present in the raw materials (e.g., polyols) used to make the foam. These volatile organic compounds may impart an undesirable odor to the raw materials and the polyurethane polymers / foams made using those raw materials. Therefore, it is desirable to find compositions or methods that reduce the detectable levels of volatile organic compounds present in polyurethane polymers / foams. This application seeks to provide such compositions and methods. [Overview of the project]

[0003]

[0003] In a first embodiment, the present invention provides an additive composition comprising a polyol and a zeolite composite. Preferably, the additive composition is (a) Polyols; (b) A zeolite complex dispersed in a polyol, (i) A zeolite substrate having a surface and a plurality of pores on the surface; and (ii) A nitrogen-containing compound adsorbed within at least a portion of the pores on the surface of a zeolite substrate, comprising (A) a first functional group containing a carbon atom double-bonded to a nitrogen atom and (B) a second functional group containing a hydrogen atom covalently bonded to a nitrogen atom. Zeolite complex containing Includes.

[0004]

[0004] In a second embodiment, the present invention provides a method for producing a polyurethane polymer (for example, a polyurethane foam) using the additive composition of the first embodiment. Preferably, the method is: (a) A step of preparing the first polyol; (b) A step of preparing an isocyanate compound containing two or more isocyanate groups; (c) A step of preparing an additive composition, (i) Second polyol; and (ii) A zeolite complex dispersed in a second polyol, (A) A zeolite substrate having a surface and a plurality of pores on the surface; and (B) A process comprising a zeolite composite comprising a nitrogen-containing compound adsorbed in at least a portion of the pores on the surface of a zeolite substrate, the nitrogen-containing compound comprising (1) a first functional group comprising a carbon atom double-bonded to a nitrogen atom and (2) a second functional group comprising a hydrogen atom covalently bonded to a nitrogen atom; (d) A step of preparing a reaction mixture by combining a first polyol, an isocyanate compound, and an additive composition; and (e) A step of reacting an isocyanate compound with a first and a second polyol to produce a polyurethane polymer, wherein the zeolite composite is dispersed in the polyurethane polymer. Includes. Detailed description of the invention

[0005]

[0005] In a first embodiment, the present invention provides an additive composition comprising a polyol and a zeolite composite dispersed in the polyol. The zeolite composite comprises a zeolite substrate and a nitrogen-containing compound adsorbed in at least a portion of the pores on the surface of the zeolite substrate.

[0006]

[0006] The additive composition may contain any suitable polyol. Suitable polyols include polyether polyols and polyester polyols. Suitable polyether polyols include those prepared by reacting epoxides, such as ethylene oxide, propylene oxide, butylene oxide, and glycidol, with a polyfunctional initiator compound, such as a polyfunctional alcohol or amine. Examples of suitable polyfunctional initiator compounds include, but are not limited to, water, glycerin, pentaerythritol, ethylene glycol, propylene glycol (e.g., 1,2-propylene glycol), trimethylolpropane, and ethylenediamine. Suitable polyester polyols include those prepared by reacting polycarboxylic acids or anhydrides with polyfunctional alcohols, such as glycerin, pentaerythritol, ethylene glycol, diethylene glycol, propylene glycol (e.g., 1,2-propylene glycol), and trimethylolpropane. Suitable examples of polycarboxylic acids and anhydrides include, but are not limited to, adipic acid, maleic acid, maleic anhydride, succinic acid, succinic anhydride, azelaic acid, glutaric acid, phthalic acid, and phthalic anhydride. Preferably, the polyol is a polyether polyol.

[0007]

[0007] The polyol can have any suitable molar mass. In a preferred embodiment, the polyol has a molar mass of about 400 g / mol or more. More preferably, the polyol has a molar mass of about 500 g / mol or more, about 750 g / mol or more, or about 1,000 g / mol or more. Preferably, the polyol has a molar mass of about 20,000 g / mol or less, more preferably about 15,000 g / mol or less, or about 10,000 g / mol or less. Therefore, in a series of preferred embodiments, the polyol is approximately 400 g / mol to approximately 20,000 g / mol (for example, approximately 400 g / mol to approximately 15,000 g / mol or approximately 400 g / mol to approximately 10,000 g / mol), approximately 500 g / mol to approximately 20,000 g / mol (for example, approximately 500 g / mol to approximately 15,000 g / mol or approximately 500 g / mol to approximately 10,000 g / mol) It has a molar mass of approximately 750 g / mol to approximately 20,000 g / mol (for example, approximately 750 g / mol to approximately 15,000 g / mol or approximately 750 g / mol to approximately 10,000 g / mol), or approximately 1,000 to approximately 20,000 g / mol (for example, approximately 1,000 g / mol to approximately 15,000 g / mol or approximately 1,000 g / mol to approximately 10,000 g / mol).

[0008]

[0008] As previously described, the additive composition includes a zeolite complex, the zeolite complex includes a zeolite substrate and a nitrogen-containing compound. The zeolite substrate may include any suitable zeolite. The zeolite may contain a wide variety of cations, for example, H + na + Ca 2+ Mg 2+is an aluminosilicate mineral that can contain and others. Zeolites are members of a family of microporous solids known as "molecular sieves" and are a group of materials that can selectively classify molecules mainly based on a size exclusion process. This classification ability is due to the very regular pore structure at the molecular dimension in zeolites. The maximum size of molecular or ionic species that can enter the pores of a zeolite is defined by the dimensions of the zeolite channels, which are defined by the ring size of the tetrahedrally coordinated silicon / aluminum and oxygen atoms that make up the zeolite. The zeolite substrate may include any naturally occurring or synthetic zeolite, and synthetic zeolites are preferred because there is no contamination by other minerals. In a preferred embodiment, the zeolite is H + cation zeolite (i.e., a zeolite in which at least a part of the counter cations in the aluminosilicate mineral is H + cation).

[0009] As described above, zeolites have a microporous structure, and the pores constituting this microporous structure can be of any suitable size. Preferably, the pore diameter of the zeolite is about 0.1 nm or more, more preferably about 0.2 nm or more or 0.3 nm or more. The pore diameter of the zeolite generally does not exceed about 1 nm, preferably about 0.9 nm or less. Therefore, in a series of preferred embodiments, the pore diameter of the zeolite is about 0.1 nm to about 1 nm (for example, about 0.1 nm to about 0.9 nm), about 0.2 nm to about 1 nm (for example, about 0.2 nm to about 0.9 nm), or about 0.3 nm to about 1 nm (for example, about 0.3 nm to about 0.9 nm).

[0010] The microporous structure of zeolites can also (or alternatively) be characterized using the BET specific surface area. Zeolites suitable for use in the preparation of zeolite composites preferably have about 1 hundred square meters 2 per gram or more, about 150 square meters 2 per gram or more, or about 200 square meters 2The zeolite has a BET specific surface area of ​​1 / g or more. Preferably, the zeolite is about 1,000 m 2 / g or less, approximately 900m 2 / g or less, or approximately 800m 2 It has a BET specific surface area of ​​less than or equal to / g. Therefore, in a series of preferred embodiments, the zeolite used to prepare the zeolite composite is about 100m 2 / ~about 1,000m 2 / g (for example, about 100m 2 / g ~ approx. 900m 2 / g or approximately 100m 2 / g~about 800m 2 / g), approx. 150m 2 / g ~ approx. 1,000m 2 / g (for example, about 150m) 2 / g ~ approx. 900m 2 / g or approximately 150m 2 / g~about 800m 2 ( / g), or approximately 200m 2 / g ~ approximately (for example, approximately 200m) 2 / g ~ approx. 900m 2 / g or approximately 200m 2 / g~about 800m 2 It has a BET ratio surface of ( / g).

[0011]

[0011] The zeolite used in the preparation of the zeolite composite can have any suitable particle size. A suitable zeolite preferably has particles of about 2 μm or larger. A suitable zeolite preferably has a particle size of about 10 μm or larger. Therefore, the zeolite preferably has a particle size of about 2 μm to about 10 μm.

[0012]

[0012] The zeolite composite contains a nitrogen-containing compound. The nitrogen-containing compound is preferably adsorbed within at least a portion of the pores on the surface of the zeolite substrate. The nitrogen-containing compound can be any suitable organic compound containing a nitrogen atom. Preferably, the nitrogen-containing compound contains a first functional group (i.e., an imine group) containing a carbon atom double-bonded to the nitrogen atom. More preferably, the nitrogen-containing compound contains (A) a first functional group (i.e., an imine group) containing a carbon atom double-bonded to the nitrogen atom and (B) a second functional group (e.g., a primary amine group or a secondary amine group) containing a hydrogen atom covalently bonded to the nitrogen atom. In a preferred embodiment, the nitrogen-containing compound contains at least two second functional groups containing hydrogen atoms covalently bonded to the nitrogen atom (i.e., the nitrogen-containing compound contains two or more primary amine groups or secondary amine groups). Preferred nitrogen-containing compounds include any compound having the above characteristics. Suitable examples of such preferred nitrogen-containing compounds include, but are not limited to, guanidine compounds, aminoguanidine compounds, biguanide compounds, guanamine compounds, and mixtures thereof. Suitable guanidine compounds include, but are not limited to, guanidine itself and its salts, such as guanidine hydrochloride, guanidine carbonate, guanidine nitrate, guanidine sulfate, and mixtures thereof. Suitable aminoguanidine compounds include, but are not limited to, aminoguanidine itself and its salts, such as aminoguanidine sulfate, aminoguanidine hydrochloride, aminoguanidine nitrate, diaminoguanidine hydrochloride, diaminoguanidine sulfate, triaminoguanidine hydrochloride, and mixtures thereof. Suitable biguanide compounds include, but are not limited to, biguanides and their salts, metformin and its salts (e.g., metformin hydrochloride), buformin and its salts (e.g., buformin hydrochloride), phenformin and its salts (e.g., phenformin hydrochloride), and mixtures thereof.Suitable guanamine compounds include, but are not limited to, benzoguanamine and its salts, acetoguanamine and its salts, adipoguanamine (i.e., 6,6'-(1,4-butanediyl)bis-1,3,5-triazine-2,4-diamine) and its salts, 2-methylglutaloguanamine (i.e., 6,6'-(2-methyl-1,3-propanediyl)bis-1,3,5-triazine-2,4-diamine) and its salts, isoadipoguanamine and its salts, 6,6'-(1-ethyl-1,2-ethanediyl)bis-1,3,5-triazine-2,4-diamine and its salts, 6,6'-(1-methyl-1,3-propanediyl)bis-1,3,5-triazine-2,4-diamine and its salts, and mixtures of the foregoing. In a preferred embodiment, the nitrogen-containing compound is selected from the group consisting of aminoguanidine compounds, biguanide compounds, guanamine compounds, and mixtures thereof. Preferably, the nitrogen-containing compound is soluble in water, meaning that it exhibits a solubility of 500 g / L or more in water. In another preferred embodiment, the nitrogen-containing compound is an aminoguanidine compound, more preferably a water-soluble aminoguanidine compound selected from the group consisting of aminoguanidine sulfate, aminoguanidine hydrochloride, aminoguanidine nitrate, diaminoguanidine hydrochloride, diaminoguanidine sulfate, triaminoguanidine hydrochloride, and mixtures of the foregoing.

[0013]

[0013] The zeolite composite can contain any appropriate amount of nitrogen-containing compound. Preferably, the nitrogen-containing compound is present in the zeolite composite in an amount of about 5% by weight or more, based on the total weight of the zeolite substrate and the nitrogen-containing compound. More preferably, the nitrogen-containing compound is present in the zeolite composite in an amount of about 10% by weight or more, about 15% by weight or more, or about 20% by weight or more, based on the total weight of the zeolite substrate and the nitrogen-containing compound. There appears to be no upper limit to the amount of nitrogen-containing compound that can be present in the zeolite composite. Rather, the maximum amount of nitrogen-containing compound appears to depend on the structure of the zeolite substrate and its ability to adsorb nitrogen-containing compounds. However, increasing the amount of nitrogen-containing compound is thought to result in a decrease in reward if the mass of the added nitrogen-containing compound is equal to or exceeds the mass of the zeolite substrate. Therefore, in a preferred embodiment, the nitrogen-containing compound is present in the zeolite composite in an amount of about 50% by weight or less, based on the total weight of the zeolite substrate and the nitrogen-containing compound. In a series of preferred embodiments, the nitrogen-containing compound is present in the zeolite composite in an amount of about 5% to 50% by weight, about 10% to about 50% by weight, about 15% to about 50% by weight, or about 20% to about 50% by weight, based on the total weight of the zeolite substrate and the nitrogen-containing compound.

[0014]

[0014] The zeolite composite can be prepared by any suitable method. Preferably, the zeolite composite is prepared by dissolving a desired amount of the nitrogen-containing compound in a suitable solvent (e.g., water). Then, the zeolite substrate is added to the resulting solution of the nitrogen-containing compound, and the resulting slurry is mixed / stirred. While stirring the slurry, the zeolite substrate is completely wetted with the solution, which results in the nitrogen-containing compound adsorbed within at least a portion of the pores of the zeolite substrate. Next, the wetted zeolite substrate is dried to remove the residual solvent, obtaining the zeolite composite as described above. The wetted zeolite substrate can be dried using any suitable method, e.g., by heating the wetted zeolite substrate to a high temperature (e.g., when the solvent is water, it is heated at a temperature of about 120 °C for approximately 8 hours). The wetted zeolite is preferably dried such that the residual solvent content (e.g., the moisture content when water is used as the solvent) is less than 2% by weight. The resulting zeolite composite can be used as is, or the zeolite composite can be crushed or ground to reduce the particle size of any aggregates that may have formed during the production process.

[0015]

[0015] The zeolite complex can be present in the additive composition in any appropriate amount. Preferably, the zeolite complex is present in the additive composition in an amount of about 1% by weight or more, based on the total weight of the polyol and zeolite complex present in the additive composition. More preferably, the zeolite complex is present in the additive composition in an amount of about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, about 5% by weight or more, about 6% by weight or more, about 7% by weight or more, about 8% by weight or more, about 9% by weight or more, or about 10% by weight or more, based on the total weight of the polyol and zeolite complex present in the additive composition. Preferably, the zeolite complex is present in the additive composition in an amount of about 50% by weight or less, based on the total weight of the polyol and zeolite complex present in the additive composition. More preferably, the zeolite composite is present in the additive composition in an amount of about 45% by weight or less, about 40% by weight or less, about 35% by weight or less, about 30% by weight or less, or about 25% by weight or less, based on the total weight of the polyol and zeolite composite present in the additive composition.Therefore, in a series of preferred embodiments, the zeolite composite is present in the additive composition in an amount of about 1% to about 50% by weight (for example, about 1% to about 45%, about 1% to about 40%, about 1% to about 35%, about 1% to about 30%, or about 1% to about 25%), based on the total weight of the polyol and zeolite composite present in the additive composition. %), approximately 3% to approximately 50% (for example, approximately 3% to approximately 45%, approximately 3% to approximately 40%, approximately 3% to approximately 35%, approximately 3% to approximately 30%, or approximately 3% to approximately 25%), approximately 4% to approximately 50% (for example, approximately 4% to approximately 45%, approximately 4% to approximately 40%, approximately 4% to approximately 35%, approximately 4% to approximately 30%, or approximately 4% to approximately 25%), approximately 5% to approximately 50% (for example, approximately 5% to approximately 45%, approximately 5% to approximately 40%, approximately 5% to approximately 35%, approximately 5% to approximately 30% by weight, or approximately 5% to approximately 25% by weight), approximately 6% to approximately 50% by weight (for example, approximately 6% to approximately 45%, approximately 6% to approximately 40%, approximately 6% to approximately 35%, approximately 6% to approximately 30%, or approximately 6% to approximately 25%), approximately 7% to approximately 50% by weight (for example, approximately 7% to approximately 45%, approximately 7% to approximately 40%, approximately 7% to approximately 35%, approximately 7% to approximately 30%, or approximately 7% to approximately 25%), approximately 8% to approximately 50% by weight (for example, approximately 8% to approximately 45%, approximately 8% to approximately 40%), It is present in the additive composition in amounts of approximately 8% to 35% by weight, approximately 8% to 30% by weight, or approximately 8% to 25% by weight), approximately 9% to 50% by weight (for example, approximately 9% to 45% by weight, approximately 9% to 40% by weight, approximately 9% to 35% by weight, approximately 9% to 30% by weight, or approximately 9% to 25%), or approximately 10% to 50% by weight (for example, approximately 10% to 45% by weight, approximately 10% to 40% by weight, approximately 10% to 35% by weight, approximately 10% to 30% by weight, or approximately 10% to 25%).In a preferred embodiment, the zeolite complex is present in the additive composition in an amount of about 5% to about 30% by weight (for example, about 10% to about 30% by weight, about 10% to about 25% by weight, about 15% to about 30% by weight, or about 15% to about 25% by weight) based on the total weight of the polyol and zeolite complex present in the additive composition.

[0016]

[0016] In addition to the polyol and zeolite complex, the additive composition may also contain other components. Suitable additional components for the additive composition include, but are not limited to, antioxidants, dispersants (e.g., surfactants, e.g., polydimethylsiloxane-polyoxyalkylene block copolymer, silicone oil, and alcohol ethoxylates [e.g., nonylphenol ethoxylate]), aldehyde scavengers, and mixtures thereof. In a preferred embodiment, the additive composition includes a dispersant, e.g., those listed above.

[0017]

[0017] As previously mentioned, many polyurethane foams have been observed to emit various volatile organic compounds, such as aldehyde compounds and amine compounds. These volatile organic compounds may have a pungent odor, and prolonged exposure to such compounds can have adverse health effects. These odors and exposure risks are typically exacerbated when the foam is placed in a confined space, such as inside a vehicle. In such a confined space, the volatile organic compounds (e.g., aldehyde compounds and amine compounds) emitted by the polyurethane foam can accumulate rapidly and rise to concentrations that are unpleasant or harmful to the health of the vehicle's occupants. When used as an additive in the manufacture of polyurethane foams, the additive compositions of the present invention have been shown to dramatically reduce the amount of aldehyde compounds and amine compounds emitted by the polyurethane foam. Experimental observations have shown that, as shown in the examples below, the additive compositions of the present invention reduce, for example, the levels of formaldehyde, acetaldehyde, and triethylenediamine emitted by the foam. The observed reduction in the emission of these compounds was significantly greater than the emission observed from the simple addition of the zeolite substrate and nitrogen-containing compounds. The results demonstrate that the described zeolite complex (in which the nitrogen-containing compounds are absorbed into the pores of the zeolite) exhibits synergistic effects that outweigh the effects attributable to the components themselves.

[0018]

[0018] Accordingly, in a second embodiment, the present invention provides a method for producing a polyurethane polymer (for example, a polyurethane foam) using the additive composition of the first embodiment. The method generally involves combining the additive composition with a suitable polyol and isocyanate compound, and reacting the resulting mixture to produce a polyurethane polymer. If a suitable blowing agent is included in the reaction mixture, it is blown into the polyurethane polymer to produce a polyurethane foam.

[0019]

[0019] Preferably, the method includes the steps of (a) preparing a first polyol; (b) preparing an isocyanate compound containing two or more isocyanate groups; (c) preparing an additive composition; (d) combining the first polyol, the isocyanate compound, and the additive composition to produce a reaction mixture; and (e) reacting the isocyanate compound with the first and second polyols to produce a polyurethane polymer, wherein the zeolite composite is dispersed in the polyurethane polymer. As previously described, the additive composition used in the method is the additive composition described above. Therefore, the additive composition includes (i) a second polyol; and (ii) a zeolite composite dispersed in the second polyol. The zeolite composite includes (A) a zeolite substrate having a surface and a plurality of pores on the surface; and (B) a nitrogen-containing compound adsorbed in at least a portion of the pores on the surface of the zeolite substrate. The nitrogen-containing compound preferably comprises (1) a first functional group containing a carbon atom double-bonded to a nitrogen atom and (2) a second functional group containing a hydrogen atom covalently bonded to a nitrogen atom.

[0020]

[0020] The first polyol used in the method can be any suitable polyol or a mixture of polyols. Suitable polyols for use in the method include polyether polyols and polyester polyols. Suitable polyether polyols are those produced by reacting epoxides, such as ethylene oxide, propylene oxide, butylene oxide, and glycidol, with a polyfunctional initiator compound, such as a polyfunctional alcohol or amine. Examples of suitable polyfunctional initiator compounds include, but are not limited to, water, glycerin, pentaerythritol, ethylene glycol, propylene glycol (e.g., 1,2-propylene glycol), trimethylolpropane, and ethylenediamine. Suitable polyester polyols are those produced by reacting polycarboxylic acids or anhydrides with polyfunctional alcohols, such as glycerin, pentaerythritol, ethylene glycol, diethylene glycol, propylene glycol (e.g., 1,2-propylene glycol), and trimethylolpropane. Suitable examples of polycarboxylic acids and anhydrides include, but are not limited to, adipic acid, maleic acid, maleic anhydride, succinic acid, succinic anhydride, azelaic acid, azelaic anhydride, glutaric acid, glutaric anhydride, phthalic acid, and phthalic anhydride. The polyol or mixture of polyols used in the production of the polyurethane polymer will depend, at least in part, on the desired properties of the final polyurethane polymer. Preferably, the first polyol is a polyether polyol.

[0021]

[0021] The first polyol used in the method can have any suitable molar mass. In a preferred embodiment, the first polyol has a molar mass of about 400 g / mol or more. More preferably, the first polyol has a molar mass of about 500 g / mol or more, about 750 g / mol or more, or about 1,000 g / mol or more. Preferably, the first polyol has a molar mass of about 20,000 g / mol or less, more preferably about 15,000 g / mol or less, or about 10,000 g / mol or less. Therefore, in a series of preferred embodiments, the first polyol is approximately 400 g / mol to approximately 20,000 g / mol (for example, approximately 400 g / mol to approximately 15,000 g / mol or approximately 400 g / mol to approximately 10,000 g / mol), approximately 500 g / mol to approximately 20,000 g / mol (for example, approximately 500 g / mol to approximately 15,000 g / mol or approximately 500 g / mol to approximately 10,000 g / mol). It has a molar mass of approximately 00 g / mol, approximately 750 g / mol to approximately 20,000 g / mol (for example, approximately 750 g / mol to approximately 15,000 g / mol or approximately 750 g / mol to approximately 10,000 g / mol), or approximately 1,000 to approximately 20,000 g / mol (for example, approximately 1,000 g / mol to approximately 15,000 g / mol or approximately 1,000 g / mol to approximately 10,000 g / mol).

[0022]

[0022] The isocyanate compound used in the method can be any suitable isocyanate compound containing two or more isocyanate groups. Suitable isocyanate compounds include, but are not limited to, aliphatic diisocyanates (e.g., hexamethylene diisocyanate, methylenedicyclohexyl diisocyanate, and isophorone diisocyanate), aromatic diisocyanates (e.g., toluene diisocyanate and methylenediphenyl diisocyanate), and mixtures thereof. Preferably, the isocyanate compound is an aromatic diisocyanate, such as toluene diisocyanate, methylenediphenyl diisocyanate, or a mixture thereof.

[0023]

[0023] The additive composition used in the method may be any embodiment of the above-described additive composition. In particular, the additive composition may include any suitable combination of the polyol, zeolite substrate, and nitrogen-containing compound described above in relation to the additive composition.

[0024]

[0024] The additive composition can be combined with the first polyol and isocyanate compound in any suitable amount. The amount of additive composition added is typically selected to bring about a desired amount of zeolite complex in the resulting reaction mixture (i.e., a combination of the first polyol, isocyanate compound, additive composition, and any other components). The amount of zeolite complex present is preferably expressed as parts by weight of zeolite complex per 100 parts by weight of polyol (i.e., the total mass of both the first polyol and the second polyol derived from the additive composition), which is abbreviated as "php" below. Preferably, the additive composition is added to bring about a zeolite complex concentration of about 0.01 php or more, about 0.05 php or more, about 0.1 php or more, about 0.15 php or more, or about 0.2 php or more. Preferably, the additive composition is added to bring about a zeolite complex concentration of about 1 php or less, about 0.9 php or less, about 0.8 php or less, about 0.7 php or less, or about 0.6 php or less. Therefore, in a series of preferred embodiments, the additive composition is preferably about 0.01 php to about 1 php (e.g., about 0.01 php to about 0.9 php, about 0.01 php to about 0.8 php, about 0.01 php to about 0.7 php, or about 0.01 php to about 0.6 php), about 0.05 php to about 1 php (e.g., about 0.05 php to about 0.9 php, about 0.05 php to about 0.8 php, about 0.05 php to about 0.7 php, or about 0.05 php to about 0.6 php), or about 0.1 php to about 1 php (e.g., about 0.1 php to about 0.9 php, about 0. It is added to result in a zeolite complex concentration of 1 php to approximately 0.8 php, approximately 0.1 php to approximately 0.7 php, or approximately 0.1 php to approximately 0.6 php), approximately 0.15 php to approximately 1 php (for example, approximately 0.15 php to approximately 0.9 php, approximately 0.15 php to approximately 0.8 php, approximately 0.15 php to approximately 0.7 php, or approximately 0.15 php to approximately 0.6 php), or approximately 0.2 php to approximately 1 php (for example, approximately 0.2 php to approximately 0.9 php, approximately 0.2 php to approximately 0.8 php, approximately 0.2 php to approximately 0.7 php, or approximately 0.2 php to approximately 0.6 php).

[0025]

[0025] In addition to the first polyol, isocyanate compound, and additive composition, the method may utilize a suitable catalyst to catalyze the reaction between the polyol and the isocyanate compound. Suitable catalysts include amine catalysts (e.g., tertiary amine catalysts), Lewis acid catalysts, and mixtures thereof. Suitable amine catalysts for use in the method include, but are not limited to, triethylenediamine, dimethylcyclohexylamine, dimethylethanolamine, bis-(2-dimethylaminoethyl) ether, and mixtures thereof. Suitable Lewis acid catalysts for use in the method include, but are not limited to, alkyltin carboxylates, oxides, and mercaptides, such as dibutyltin dilaurate, stannous octanoate, methyltin mercaptides, and mixtures thereof.

[0026]

[0026] The reaction mixture of the method may include other components in addition to the first polyol, isocyanate compound, additive composition and, if present, the catalyst. As previously stated, the reaction mixture may further include a blowing agent so that the method produces a polyurethane foam. Suitable blowing agents for use in the method include, but are not limited to, water, pentane, 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, and mixtures thereof. Preferably, the blowing agent is water. The reaction mixture may further include one or more surfactants that can help emulsify the liquid components, regulate the bubble size of the foam, and stabilize the bubble structure of the foam to prevent collapse and subsurface gaps. Suitable surfactants include, but are not limited to, polydimethylsiloxane-polyoxyalkylene block copolymers, silicone oils, and alcohol ethoxylates (e.g., nonylphenol ethoxylate), and mixtures thereof. The reaction mixture may further include chain extenders, crosslinking agents, and mixtures thereof. Suitable chain extenders include, but are not limited to, diols with relatively low molar masses (e.g., typically 200 g / mol or less), such as ethylene glycol, diethylene glycol, ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, ethanolamine, diethanolamine, methyldiethanolamine, and phenyldiethanolamine. Suitable crosslinking agents include, but are not limited to, polyols having three or more hydroxyl groups with a relatively low molar mass (for example, typically 200 g / mol or less), such as glycerol, trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, pentaerythritol, and N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine.

[0027]

[0027] The polyurethane polymer produced by the method (e.g., polyurethane foam) can be used in any suitable application or end use. Preferably, the polyurethane foam is flexible and suitable for use as cushioning material in mattresses, furniture, and vehicle seats, for example. The foam produced by the method of the present invention is considered particularly suitable for use as such cushioning material in vehicle seats (e.g., automobile seats), given the relatively large volume of the interior of the vehicle occupied by the cushioning material, where the reduction of volatile organic compounds emitted by the foam is particularly advantageous.

[0028]

[0028] The following examples further illustrate the above subject matter, but of course, they should not be interpreted as limiting its scope.

[0029] Example 1

[0029] This example demonstrates the generation of several zeolite composites suitable for use in the preparation of additive compositions according to the present invention.

[0030]

[0030] The zeolite composites were prepared by the following general procedure. First, the indicated amount (by weight) of nitrogen-containing compound was added to 10 parts by weight of water and mixed until the nitrogen-containing compound was completely dissolved. Next, 10 parts by weight of zeolite was added to the solution of nitrogen-containing compound and mixed for approximately 10 minutes. Finally, the resulting zeolite dispersion was placed in an oven maintained at a temperature of approximately 120°C for approximately 18 hours or until the moisture content of the resulting zeolite composite was less than 2% (whichever was last). All zeolite composites in this example were prepared using HSZ-385 HUA zeolite (manufactured by Tosoh USA, Inc.). HSZ-385 HUA zeolite is 600m 2 H has been reported to have a BET specific surface area of ​​1 / g and an average particle size of 2-3 μm. + It is a cationic zeolite.

[0031]

[0031] Using 2 parts by weight of aminoguanidine in the above procedure, a zeolite composite represented as "Sample 1A" was prepared. Using 4 parts by weight of aminoguanidine in the above procedure, a zeolite composite represented as "Sample 1B" was prepared. Using 3 parts by weight of metformin in the above procedure, a zeolite composite represented as "Sample 1C" was prepared. Using 3 parts by weight of adipoguanamine in the above procedure, a zeolite composite represented as "Sample 1D" was prepared. The resulting zeolite composites were used to prepare polyurethane foam as described in Example 2 below.

[0032] Example 2

[0032] This example demonstrates the reduction in volatile organic compound emissions resulting from the use of an additive composition containing the zeolite composite according to the present invention.

[0033]

[0033] Polyurethane foams were prepared using the general formulations provided in Table 1 below in batch sizes based on 200 grams of polyol. Each foam was cured for 5 minutes in an oven maintained at a temperature of approximately 360°F (182°C), then removed from the oven and allowed to cool to room temperature. Each cooled foam was then sealed in aluminum foil to capture all volatile components until an emission test could be performed.

[0034] [Table 1]

[0035]

[0034] Once the foam was formed, emission tests were performed by cutting a 1.5-inch diameter and 1.0-inch height sample from each foam. These cylindrical samples were placed in a microchamber and equilibrated at 65°C for 20 minutes before sampling the effluent. Nitrogen humidified to 50% RH was flowed into the chamber at 50 mL / min. The effluent analytes were captured with Tenax® TA adsorbent resin and analyzed by gas chromatography / mass spectrometry. Identifiable emissions were quantified in toluene equivalent. The "% reduction in VOCs" reported in Table 2 below were calculated by comparing the total VOCs measured for the target foam with the total VOCs measured for the control foam.

[0036] [Table 2]

[0037]

[0035] The data in Table 2 shows that all foams made with the zeolite composite according to the present invention showed significantly lower VOC emissions than the control foam. For example, the VOC emissions for foam 2B were less than half of those for the control foam, a reduction achieved by adding only 0.4 php of zeolite composite sample 1B.

[0038] Example 3

[0036] This example demonstrates the production of zeolite composites and additive compositions according to the present invention.

[0039]

[0037] Using 3 parts by weight of aminoguanidine and 10 parts by weight of HSZ-385 HUA zeolite, a first zeolite composite was prepared according to the general procedure described in Example 1. After drying, the resulting zeolite composite was dispersed in Carpol PGP-400 polyol at a solid content level of 25% (by weight). The resulting additive composition is referred to as "Sample 3A".

[0040]

[0038] A second zeolite composite was prepared using 3 parts by weight of aminoguanidine and 10 parts by weight of HSZ-980 HOA zeolite (manufactured by Tosoh USA, Inc.) following the general procedure described in Example 1. The HSZ-980 HOA zeolite was 500 g / m² 2 This is an H+ cation zeolite reported to have a BET specific surface area and an average particle size of 2.5 μm. After drying, the resulting zeolite composite was dispersed in Arcol F-3222 polyol at a solid content level of 35% (by weight). The resulting additive composition is referred to as "Sample 3B".

[0041] Example 4

[0039] This example demonstrates the reduction in volatile organic compound emissions resulting from the use of an additive composition containing the zeolite composite according to the present invention.

[0042]

[0040] Polyurethane foams were prepared using typical formulations provided in Table 3 below, in batch sizes based on 100 grams of polyol. Each foam was cured for 5 minutes in an oven maintained at approximately 360°F (182°C), then removed from the oven and allowed to cool to room temperature. Each cooled foam was then sealed in aluminum foil to capture all volatile components until an emission test could be performed.

[0043] [Table 3]

[0044]

[0041] Once the foam was formed, emission tests were performed by cutting a 1.5-inch diameter and 1.0-inch height sample from each foam. These cylindrical samples were placed in a microchamber and equilibrated at 65°C for 20 minutes before sampling the effluent. Nitrogen humidified to 50% RH was flowed into the chamber at 50 mL / min. The effluent analytes were captured with Tenax® TA adsorbent resin and analyzed by gas chromatography / mass spectrometry. Triethylenediamine catalyst (TEDA) emission contributing to the foam odor was quantified in toluene equivalent. (Dabco 33LV amine catalyst is a triethylenediamine catalyst.) The amount of triethylenediamine catalyst emission detected is reported in Table 4 below.

[0045] [Table 4]

[0046]

[0042] As can be seen from the data in Table 4, all foams produced with the additive composition according to the present invention did not show detectable amine catalyst (TEDA) emission under the test conditions used. In contrast, the control foam showed 1,087.7 ​​μg / m² 2 The amine catalyst (TEDA) emission of hr was observed. Based on these results, it is considered that foams produced with the additive composition of the present invention will exhibit dramatically reduced VOC emissions and amine odor compared to foams produced without the additive composition.

[0047] Example 5

[0043] This example demonstrates the reduction in volatile organic compound emissions resulting from the use of an additive composition containing the zeolite complex according to the present invention. The example further demonstrates how the zeolite complex causes a greater reduction in VOCs compared to the separate addition of zeolite and nitrogen-containing compounds.

[0048]

[0044] Using 3 parts by weight of aminoguanidine and 10 parts of HSZ-385HUA zeolite, a zeolite complex was prepared according to the general procedure described in Example 1. The resulting zeolite complex is hereafter referred to as "Sample 5A".

[0049]

[0045] Polyurethane foams were prepared using general formulations provided in Table 5 below, in batch sizes based on 200 grams of polyol. Foam 5A was produced by separately adding HSZ-385HUA zeolite and aminoguanidine to the reaction mixture during foam formation (i.e., not in the composite form described above). Each foam was cured for 5 minutes in an oven maintained at a temperature of approximately 360°F (182°C), then removed from the oven and allowed to cool to room temperature. Each cooled foam was then sealed in aluminum foil to capture all volatile components until an emission test could be performed.

[0050] [Table 5]

[0051]

[0046] Once the foam was formed, emission tests were performed by cutting a 1.5-inch diameter and 1.0-inch height sample from each foam. These cylindrical samples were placed in a microchamber and equilibrated at 65°C for 20 minutes before sampling the effluent. Nitrogen humidified to 50% RH was flowed into the chamber at 50 mL / min. The effluent analytes were captured with Tenax® TA adsorbent resin and analyzed by gas chromatography / mass spectrometry. Identifiable emissions, such as triethylenediamine catalyst (TEDA) emissions, were quantified in toluene equivalent. The detected amounts of VOC and TEDA emissions are reported in Table 6 below. The "% decrease" values ​​reported in Table 6 below were calculated by comparing the emissions measured for the target foam with the emissions measured for the control foam.

[0052] [Table 6]

[0053]

[0047] The data in Table 6 show that the separate addition of zeolite and nitrogen-containing compound during foam formation (foam 5A) resulted in only an 8.1% reduction in total VOC emissions and an 11.5% reduction in TEDA emissions. In contrast, when the same amounts of zeolite and nitrogen-containing compound were added in the composite form described herein, the resulting foam (foam 5B) showed a 56.7% reduction in total VOC emissions and a 63.2% reduction in TEDA emissions. This dramatic reduction in emissions is remarkable considering that the only difference between the two foams is the form in which the zeolite and nitrogen-containing compound are added to the foam (i.e., composite vs. non-composite). These data suggest that foams produced with the additive composition of the present invention will exhibit dramatically reduced VOC emissions and amine emissions / odors compared to foams produced without the additive composition.

[0054]

[0048] All references, including publications, patent applications, and patents, cited herein are incorporated by reference to the same extent as they are described herein, with each reference being incorporated by reference individually and specifically.

[0055]

[0049] In the context describing the subject matter of this application (particularly in the context of the claims below), the terms “a,” “an,” and “the,” and similar references, should be interpreted as encompassing both singular and plural unless otherwise indicated herein or unless clearly inconsistent with the context. The terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., “including, but not limited to”) unless otherwise indicated herein. The enumeration of value ranges herein is intended solely as a concise way of referring individually to the individual values ​​contained within that range unless otherwise indicated herein, and the individual values ​​are incorporated herein as if they were individually enumerated. All methods described herein can be performed in any suitable order unless otherwise indicated herein or unless clearly inconsistent with the context. The use of any examples or illustrative language provided herein (e.g., “for example”) is intended solely to better illustrate the subject matter of this application and, unless otherwise requested, does not impose any limitation on the scope of the subject matter. Nothing in this specification should be construed as indicating that any element not claimed is essential to the practice of the subject matter described herein.

[0056]

[0050] Preferred embodiments of the subject matter of this application, including the best mode known to the inventors for carrying out the claimed subject matter, are described herein. Variations of such preferred embodiments may be apparent to those skilled in the art who have read the foregoing description. The inventors expect that those skilled in the art will appropriately utilize such variations, and the inventors intend that the subject matter described herein will be practiced in ways other than those specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter enumerated in the appended claims, as permitted by applicable law. Furthermore, any combination of the above elements in all of those possible variations is incorporated herein unless otherwise indicated herein or unless it is clearly inconsistent with the context. The invention described in the original claims of this application is listed below. [1] (a) polyols; (b) A zeolite composite dispersed in the polyol, (i) A zeolite substrate having a surface and a plurality of pores on the surface; and (ii) A nitrogen-containing compound adsorbed within at least a portion of the pores on the surface of the zeolite substrate, comprising (A) a first functional group containing a carbon atom double-bonded to a nitrogen atom and (B) a second functional group containing a hydrogen atom covalently bonded to a nitrogen atom. Zeolite complex containing An additive composition containing the following: [2] The additive composition according to [1], wherein the polyol has a molar mass of about 400 g / mol or more. [3] The additive composition according to [1] or [2], wherein the polyol is a polyether polyol. [4] The additive composition according to any one of [1] to [3], wherein the zeolite complex is present in the additive composition in an amount of about 5% to about 30% by weight, based on the total weight of the polyol and zeolite complex present in the additive composition. [5] The zeolite substrate is H + An additive composition according to any one of items [1] to [4], which is a cationic zeolite. [6] The additive composition according to any one of [1] to [5], wherein the nitrogen-containing compound is present in the zeolite composite in an amount of about 15% to about 50% by weight, based on the total weight of the zeolite substrate and the nitrogen-containing compound. [7] The additive composition according to any one of [1] to [6], wherein the nitrogen-containing compound comprises at least two second functional groups, each containing a hydrogen atom covalently bonded to a nitrogen atom. [8] The additive composition according to any one of [1] to [7], wherein the nitrogen-containing compound is selected from the group consisting of guanidine compounds, aminoguanidine compounds, biguanide compounds, guanamine compounds, and mixtures thereof. [9] A method for producing a polyurethane polymer, (a) A step of preparing the first polyol; (b) A step of preparing an isocyanate compound containing two or more isocyanate groups; (c) A step of preparing an additive composition, (i) Second polyol; and (ii) A zeolite complex dispersed in the second polyol, (A) A zeolite substrate having a surface and a plurality of pores on the surface; and (B) A process comprising a zeolite composite comprising a nitrogen-containing compound adsorbed in at least a portion of the pores on the surface of the zeolite substrate, the nitrogen-containing compound comprising (1) a first functional group comprising a carbon atom double-bonded to a nitrogen atom and (2) a second functional group comprising a hydrogen atom covalently bonded to a nitrogen atom; (d) A step of preparing a reaction mixture by combining the first polyol, the isocyanate compound, and the additive composition; and (e) A step of reacting the isocyanate compound with the first and second polyols to produce a polyurethane polymer, wherein the zeolite composite is dispersed in the polyurethane polymer. A method that includes this.

[10] The method according to [9], wherein the second polyol has a molar mass of about 400 g / mol or more.

[11] The method according to [9] or

[10] , wherein the second polyol is a polyether polyol.

[12] The method according to any one of [9] to

[11] , wherein the zeolite complex is present in the additive composition in an amount of about 5% to about 30% by weight, based on the total weight of the polyol and zeolite complex present in the additive composition.

[13] The zeolite substrate is H + The method described in any one of the items [9] to

[12] , wherein the material is a cationic zeolite.

[14] The method according to any one of [9] to

[13] , wherein the nitrogen-containing compound is present in the zeolite composite in an amount of about 15% to about 50% by weight, based on the total weight of the zeolite substrate and the nitrogen-containing compound.

[15] The method according to any one of [9] to

[14] , wherein the nitrogen-containing compound comprises at least two second functional groups, each containing a hydrogen atom covalently bonded to a nitrogen atom.

[16] The method according to any one of [9] to

[15] , wherein the nitrogen-containing compound is selected from the group consisting of aminoguanidine compounds, biguanide compounds, guanamine compounds, and mixtures thereof.

[17] The method according to any one of [9] to

[16] , wherein the reaction mixture contains about 0.1 parts by weight or more of zeolite composite per 100 parts by weight of polyol.

Claims

1. (a) Polyols; (b) A zeolite composite dispersed in the polyol, (i) A zeolite substrate having a surface and a plurality of pores on the surface; and (ii) A nitrogen-containing compound adsorbed within at least a portion of the pores on the surface of the zeolite substrate, wherein the nitrogen-containing compound comprises (A) a first functional group containing a carbon atom double-bonded to a nitrogen atom and (B) a second functional group containing a hydrogen atom covalently bonded to a nitrogen atom, and is present in the zeolite composite in an amount of about 15% to about 50% by weight, based on the total weight of the zeolite substrate and the nitrogen-containing compound. Zeolite complex containing An additive composition containing the following:

2. The additive composition according to claim 1, wherein the polyol has a molar mass of about 400 g / mol or more.

3. The additive composition according to claim 1, wherein the polyol is a polyether polyol.

4. The additive composition according to claim 1, wherein the zeolite complex is present in the additive composition in an amount of about 5% to about 30% by weight, based on the total weight of the polyol and zeolite complex present in the additive composition.

5. The zeolite substrate is H ＋ The additive composition according to claim 1, wherein the additive is a cationic zeolite.

6. The additive composition according to claim 1, wherein the nitrogen-containing compound comprises at least two second functional groups, each containing a hydrogen atom covalently bonded to a nitrogen atom.

7. The additive composition according to claim 1, wherein the nitrogen-containing compound is selected from the group consisting of guanidine compounds, aminoguanidine compounds, biguanide compounds, guanamine compounds, and mixtures thereof.

8. A method for producing polyurethane polymers, (a) A step of preparing the first polyol; (b) A step of preparing an isocyanate compound containing two or more isocyanate groups; (c) A step of preparing an additive composition, wherein the additive composition is (i) a second polyol; and (ii) A zeolite composite dispersed in the second polyol, (A) A zeolite substrate having a surface and a plurality of pores on the surface; and (B) A nitrogen-containing compound adsorbed within at least a portion of the pores on the surface of the zeolite substrate, wherein the nitrogen-containing compound comprises (1) a first functional group containing a carbon atom double-bonded to a nitrogen atom and (2) a second functional group containing a hydrogen atom covalently bonded to a nitrogen atom, and is present in the zeolite composite in an amount of about 15% to about 50% by weight, based on the total weight of the zeolite substrate and the nitrogen-containing compound. A process including a zeolite composite; (d) A step of generating a reaction mixture by combining the first polyol, the isocyanate compound, and the additive composition; and (e) A step of reacting the isocyanate compound with the first and second polyols to produce a polyurethane polymer, wherein the zeolite composite is dispersed in the polyurethane polymer. A method that includes this.

9. The method according to claim 8, wherein the second polyol has a molar mass of about 400 g / mol or more.

10. The method according to claim 8, wherein the second polyol is a polyether polyol.

11. The method according to claim 8, wherein the zeolite complex is present in the additive composition in an amount of about 5% to about 30% by weight, based on the total weight of the polyol and zeolite complex present in the additive composition.

12. The zeolite substrate is H ＋ The method according to claim 8, wherein the material is a cationic zeolite.

13. The method according to claim 8, wherein the nitrogen-containing compound comprises at least two second functional groups, each containing a hydrogen atom covalently bonded to a nitrogen atom.

14. The method according to claim 8, wherein the nitrogen-containing compound is selected from the group consisting of aminoguanidine compounds, biguanide compounds, guanamine compounds, and mixtures thereof.

15. The method according to claim 8, wherein the reaction mixture contains about 0.1 parts by weight or more of zeolite composite per 100 parts by weight of polyol.

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