Tertiary amino amide composition useful for the production of polyurethane polymers

Abstract

A catalyst composition comprising at least one compound represented by formula (I). TIFF2025524162000022.tif34150[wherein R1, R2, and R3 are each independently a straight-chain or branched C1-C3 alkyl group, or a straight-chain or branched C2-C6 alkenyl group; R4 is hydrogen, a straight-chain or branched C1-C3 alkyl group, or a straight-chain or branched C2-C6 alkenyl group.]

Description

Technical Field

[0001] The field of the present invention is novel compositions and uses of tertiary aminoamides as catalysts useful in the production of polyurethane foams.

[0002] Background of the Invention Polyurethane foam compositions are typically prepared by reacting an isocyanate with a premix consisting of isocyanate-reactive components such as polyols. The premix optionally includes other components such as water, flame retardants, blowing agents, foam stabilizing surfactants, and catalysts to promote the formation of urethanes by reaction of the isocyanate with the polyol, the formation of CO2 and urea by reaction with water, and the formation of isocyanurates (trimers) by reaction with excess isocyanate.

[0003] Blowing agents in the premix are usually classified as chemical blowing agents or physical blowing agents. Chemical blowing agents are typically substances that can generate gas when all the reactive components are mixed to produce polyurethane foam. Examples of chemical blowing agents include water and formic acid. Water is the most common chemical blowing agent that can react with isocyanate functional groups to produce carbon dioxide. Water is generally used in many types of polyurethane materials including rigid, semi-rigid and flexible polyurethane foams. Formic acid can also be used as a blowing agent, which produces a mixture of carbon dioxide and carbon monoxide. On the other hand, physical blowing agents are liquids or gases with a sufficiently low boiling point that they vaporize by the heat released during the polymerization reaction. Examples of blowing agents useful in the production of insulating polyurethane foams include, but are not limited to, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, hydrochlorofluorocarbons, formates, ketones such as acetone, and hydrocarbons such as pentane and cyclopentane.

[0004] Unlike simple hydrocarbons such as pentane, halogen-containing molecules such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs) are much less flammable and safe to use in foam production. However, they destroy the ozone layer or contribute to global warming in other ways. In contrast, hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) are very efficient and environmentally friendly blowing agents, with a much lower global warming potential (GWP) and a zero ozone depletion potential (ODP).

[0005] The proper selection and combination of components in the polyol premix and isocyanate can be useful in the production of any of soft, semi-soft, or rigid polyurethane foams. Polyurethane foam materials with various characteristics can be useful in a plurality of applications including soft molded foams useful for automotive interior applications, furniture, bedding, flooring, soft slabstock foams useful for the interior of transportation equipment, spray rigid materials, and on-site foams, for example, used in refrigerators, freezers, water heaters, insulation panels, garage doors, front doors, and various other applications where insulation is desired.

[0006] U.S. Patent No. 3,816,339 discloses a polyurethane catalyst consisting of a mixture of N,N-dimethylcyclohexylamine and N-methyl-dicyclohexylamine having unique properties. N,N-dimethylcyclohexylamine is a typical tertiary amine polyurethane catalyst that is widely used for the production of various types of polyurethane foam grades, especially rigid closed-cell polyurethane polymers.

[0007] U.S. Patent No. 6,737,446 discloses water as a blowing agent, a foam stabilizer, and an acid-blocked tertiary aminoalkylamide catalyst compound I (A = CH, N; R 1 = H, II; R 2 , R 3 = H, C 1-6 linear or branched alkyl; R 4 , R 5 = C 1-6Linear or branched alkyl, C 2-5 alkylene; R 6 =C 5-35 Disclosed is a method for preparing a polyurethane foam, which comprises reacting an organic polyisocyanate with a polyol in the presence of a linear or branched alkyl, alkenyl, aryl; n = 1 to 3).

Chemical formula

[0008] U.S. Patent No. 7,169,823 discloses a method for preparing a polyurethane foam, which comprises reacting an organic polyisocyanate with a polyol in the presence of water as a blowing agent, a foam stabilizer, and a tertiary amine amide catalyst composition represented by the following formula (wherein A, R 1 -R 6 , and n are defined in the specification, and the tertiary amino amide catalyst of Formula I is acid-blocked).

Chemical formula

[0009] The ability of a tertiary amine catalyst to selectively promote either foaming or gelation is an important consideration when selecting a catalyst for preparing a particular polyurethane foam. If the promotion of the foaming reaction by the catalyst is too rapid, a significant amount of CO2 will be generated before sufficient reaction between the isocyanate and the polyol occurs, causing the formulation to foam and resulting in foam collapse and the production of low-quality foam. On the other hand, if the promotion of the gelation reaction by the catalyst is too rapid, a significant amount of polymerization will occur before sufficient CO2 is generated, resulting in insufficient foaming action and the production of low-quality foam. Tertiary amine catalysts generally have a bad odor and are unpleasant, and many are highly volatile due to their low molecular weight. The release of tertiary amines during foam processing can pose safety and toxicity problems, and the release of residual amines during customer use is undesirable. On the other hand, low vapor pressure - high molecular weight amine catalysts require extremely high catalyst usage amounts due to their low N / C ratio, which is expected to significantly increase manufacturing costs.

[0010] Therefore, a tertiary amine catalyst with a low vapor pressure but a relatively high N / C ratio is required so that the catalytic activity can be maintained during the polymerization process while maintaining the good physical and mechanical properties of the completed polymer.

[0011] Summary of the Invention The present invention relates to a method for preparing a polyurethane foam, which includes reacting an organic polyisocyanate with a polyol in the presence of a polyurethane additive containing a catalyst composition including a blowing agent, a foam stabilizer, a crosslinking agent, and at least one compound represented by formula (I).

Chemical formula

[0012] The present invention enables the use of the catalyst of the present invention, thereby improving and reducing the odor of the completed foam, providing good catalytic activity, and giving a polyurethane foam product with excellent physical properties, thus solving the problems associated with conventional foam precursors.

[0013] The present invention provides a polyurethane catalyst and a polyol premix composition having the following advantages: a) providing a tertiary amine catalyst having an amide functional group capable of giving good foam kinetics and curing including surface curing; b) the odor quality is improved because the amide is not involved in the chain termination that brings about harmful physical properties of the foam; c) giving optimal catalytic activity and physical properties of the foam equivalent to existing standard products.

[0014] The catalyst composition is defined as at least one compound represented by formula (I):

Chemical formula

[0015] In an exemplary embodiment, the process comprises preparing a premix comprising at least one catalyst compound represented by formula (I), and contacting the premix with at least one physical blowing agent such as hydrofluorocarbon, hydrofluoroolefin, hydrochlorofluoroolefin, hydrochlorofluorocarbon, formate, ketones such as acetone, hydrocarbons such as pentane and cyclopentane, or a chemical blowing agent such as water or formic acid.

[0016] In another exemplary embodiment, the polyurethane composition comprises a polyol component, a catalyst composition, and an isocyanate component. The catalyst composition comprises at least one compound represented by formula (I).

[0017] In another exemplary embodiment, the polyurethane product comprises at least one catalyst compound represented by formula (I) and an isocyanate component.

[0018] In another exemplary embodiment, the catalyst composition comprises at least one catalyst compound represented by formula (I) and / or a tertiary amine catalyst containing an isocyanate-reactive group.

[0019] In another exemplary embodiment, the catalyst composition comprises at least one catalyst compound represented by formula (I) and / or a tertiary amine catalyst not containing an isocyanate-reactive group.

[0020] Other features and advantages of the present invention will become apparent upon interpreting the following more detailed description of the preferred embodiments in conjunction with the accompanying drawings that illustrate the principles of the invention.

[0021] Definitions The following definitions are provided to assist those skilled in the art in understanding the detailed description of the present invention. PUR: Polyurethane. Isocyanate index: The value obtained by dividing the amount of polyisocyanate actually used by the stoichiometric amount of polyisocyanate theoretically required to react with all the active hydrogens in the reaction mixture and multiplying by 100. Also known as (NCO equivalent / active hydrogen equivalent) × 100. pphp - Parts per hundred parts by weight of polyol. Polycat® - 5: A commercially available catalyst supplied by Evonik Corporation, the chemical name of which is pentamethyldiethylenetriamine. Polycat® - 8: A commercially available catalyst supplied by Evonik Corporation, the chemical name of which is dimethylaminocyclohexane.

[0022] Detailed Description of the Invention The present invention relates to a catalyst composition comprising at least one compound represented by formula (I).

Chemical formula

[0023] The present invention provides a polyurethane catalyst and a polyol premix composition having the following advantages: a) providing a tertiary amine catalyst having an amide functional group capable of giving good foam kinetics and curing including surface curing; b) since the amide is not involved in chain termination that results in harmful foam physical properties, the odor quality is improved; c) giving optimal catalytic activity and foam physical properties equivalent to existing standard products.

[0024] The present invention also provides a method for preparing a polyurethane foam, which includes contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of an effective amount of the catalyst composition defined by formula (I) above, combined with at least one foaming agent and a metal catalyst and / or a tertiary amine having or not having isocyanate-reactive groups.

[0025] Furthermore, the polyurethane foam can be produced by several methods known in the art using the novel catalyst system and novel composition of the present invention.

[0026] Preferably, any amount of the catalyst composition defined by the above formula (I) can be used in the composition of the present invention.

[0027] The present invention discloses several types of ranges. These include, but are not limited to, ranges of temperature, number of atoms, foam density, isocyanate index, foaming agent, water, surfactant, flame retardant, and ranges of pphp for the catalyst composition defined by formula (I) above.

[0028] The present invention discloses any type of range, which individually discloses each possible number that such a range can reasonably encompass, as well as any sub-range and combination of sub-ranges included therein. For example, when the present invention discloses a chemical moiety having a specific number of carbon atoms, the present invention individually discloses every possible number that such a range can encompass.

[0029] For example, R 1 and R 2 are each independently, C 1-3 The disclosure that the alkyl is a straight or branched chain, and the C2-C6 alkenyl is a straight or branched chain means, for example, that the alkyl group has a maximum of 3 carbon atoms. In other words, the C1-3 alkyl group as used herein is an alkyl group having 1, 2, or 3 carbon atoms, and can be independently selected from alkyl groups having 1, 2, or 3 carbon atoms, and the ranges between any two of these numbers, for example, C2-C3 alkyl groups, the "R 1 " or "R 2 " group.

[0030] Similarly, another representative example is given below for the parts by weight of the catalyst composition defined by formula (I) per 100 parts by weight of at least one active hydrogen-containing compound in the composition or in the foam formulation. When at least one active hydrogen-containing compound is at least one polyol, the parts by weight per 100 parts by weight of the polyol are abbreviated as pphp. Thus, for example, according to the disclosure that the catalyst composition defined by formula (I) is preferably present in an amount of about 0.05 to about 10 pphp, the pphp in the present invention can be selected from about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. Similarly, all other ranges disclosed herein should be interpreted in the same manner as these two examples.

[0031] If the applicant chooses to claim less than the full scope of the present disclosure, for example, to clarify references that the applicant may not have been aware of at the time of filing, the applicant reserves the right to exclude or disclaim any individual member of any such group (including any subrange or combination of subranges within the group) that can be claimed according to a range or in any similar manner. Further, if the applicant chooses to claim less than the full scope of the present disclosure, for example, to clarify references that the applicant may not have been aware of at the time of filing, the applicant reserves the right to exclude or disclaim any individual substituent, analog, compound, ligand, structure, or group thereof, or any member of the claimed group.

[0032] In another embodiment of the present invention, a catalyst composition is used to produce a rigid foam (a foam that cannot bend or lose its shape) having a density of from about 0.5 lb / ft 3 to about 5 lb / ft 3 , from about 1 lb / ft 3 to about 4 lb / ft 3 , and in some cases from about 2 lb / ft 3 to about 3 lb / ft 3 . The catalyst composition can be used to produce a closed-cell rigid foam, such as those typically used in spray foam insulation and appliances having desirable physical properties including dimensional stability, adhesion, crushability, thermal insulation, and compressive strength. In a further embodiment, a catalyst composition is used to produce a rigid foam having a density of from about 0.5 lb / ft 3 to about 5 lb / ft 3 , from about 1 lb / ft 3 to about 4 lb / ft 3 , and in some cases from about 2 lb / ft 3 to about 3 lb / ft 3 . The density can be measured according to ASTM D3574 Test A.

[0033] In another embodiment of the present invention, a catalyst composition can be used to produce flexible foams including flexible slabstock foam and flexible molded foam.

[0034] The flexible molded foam of the present invention is characterized by excellent physical properties and typically has a target density (ASTM 3574-A) in the range of about 28 to about 80 kg / m 3 3, an air flow (ASTM 3574-G) in the range of about 40 to about 120 L / M, an ILD (indentation load deflection method, ASTM 3574-B1) in the range of about 150 to about 600 N, a support factor (ASTM 3574-B1) in the range of about 2.5 to about 3.5, preferably about 3, and an elasticity (ASTM 3574-H) in the range of about 40 to about 80%. In one embodiment of the present invention, the desired foam has a tensile / HA tensile / elongation / HA elongation = DIN 53571 in the range of about 80 to about 200%, a 50% compression set = ASTM D3574-D in the range of about 1 to about 20%, an HA compression set = ASTM D3574-J1 and J2 in the range of about 5 to about 15%, and a tear = ASTM D3574-F in the range of about 150 to about 400.

[0035] In one embodiment of the present invention, the catalyst composition defined by formula (I) preferably comprises 2-[2-(dimethylamino)ethoxy]-N-methyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N,N-diethyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N,N-dipropyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N,N-dibutyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N,N-dipentyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N,N-dihexyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-ethyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-propyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-butyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-pentyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-hexyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-ethyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-propyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-butyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-pentyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-hexyl-acetamide, 2-[2-(diethylamino)ethoxy]-N,N-dimethyl-acetamide, 2-[2-(diethylamino)ethoxy]-N,N-diethyl-acetamide, 2-[2-(diethylamino)ethoxy]-N,N-dipropyl-acetamide, 2-[2-(diethylamino)ethoxy]-N,N-dibutyl-acetamide, 2-[2-(diethylamino)ethoxy]-N,N-dipentyl-acetamide, 2-[2-(diethylamino)ethoxy]-N,N-dihexyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-ethyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-propyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-butyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-pentyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-hexyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-ethyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-propyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-butyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-pentyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-hexyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-dimethyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-diethyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-dipropyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-dibutyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-dipentyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,It contains at least one member selected from the group consisting of N-dihexyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-ethyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-propyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-butyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-pentyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-hexyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-ethyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-propyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-butyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-pentyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-hexyl-acetamide, etc. Such compounds can be used individually or in any combination thereof.,

[0036] In one embodiment, the catalyst composition defined by formula (I) can be used as the sole catalyst or in combination with at least one tertiary amine catalyst. The tertiary amine catalyst can be a conventional tertiary amine catalyst having at least one isocyanate-reactive group or having no isocyanate-reactive group. Examples of isocyanate-reactive groups include primary hydroxyl groups, secondary hydroxyl groups, primary amine groups, secondary amine groups, urea groups or amide groups. Examples of tertiary amine catalysts having isocyanate-reactive groups preferably include N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-2-hydroxy(propyl)-1,3-propylenediamine, dimethylaminopropylamine, (N,N-dimethylaminoethoxy)ethanol, methyl-hydroxy-ethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine, N,N-dimethylaminopropylurea, diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, N,N'-bis(3-diethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole, and N-(2-hydroxyethyl)imidazole, N,N-bis(dimethylaminopropyl)-N-(3-aminopropyl)amine;N,N-bis(3-dimethylaminopropyl)-N-{3-[bis(2-hydroxypropyl)]propylamine}, N,N-bis(3-dimethylaminopropyl)-N-{3-[bis(2-hydroxyethyl)]propylamine}, N,N'-bis[bis-N'',N''-(3-dimethylaminopropyl)-N''-(3-aminopropyl)]urea, N,N-bis(3-dimethylaminopropyl)-N-(3-aminopropyl)]urea, N,N-bis(3-dimethylaminopropyl)-N-(bis(2-hydroxypropyl)-3-aminopropyl)]amine, N,N-bis(3-dimethylaminopropyl)-N-[N',N'-bis(2-hydroxypropyl)-3-aminopropyl]amine, N,N-bis(3-dimethylaminopropyl)-N-[(2-hydroxypropyl)-3-aminopropyl]amine; 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl)ether, or combinations thereof, including but not limited to. The weight ratio of the suitable tertiary amine to the catalyst of the present invention can be in the range of about 0 to about 100, about 0.1 to about 50, and in some cases about 1 to about 10.;

[0037] In one embodiment, the tertiary amine catalyst component is highly volatile and not isocyanate-reactive. For example, in one embodiment, the tertiary amine catalyst component is a volatile gelling catalyst, preferably diazabicyclooctane (triethylenediamine), 1,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl)amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, or a combination thereof, or includes them. In addition to or instead of the above, in one embodiment, the tertiary amine catalyst component is a volatile foaming catalyst or includes it, preferably bis(dimethylaminoethyl)ether, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine and related compositions, and further polyvalent permethylated polyamines or includes it. In addition to or instead of the above, in another embodiment, the tertiary amine catalyst component is preferably a foaming catalyst having an isocyanate-reactive group, such as 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol and related structures, alkoxylated polyamines, imidazole-boron compositions, aminopropyl-bis(amino-ethyl)ether compositions, or a combination thereof, or includes it.

[0038] In another embodiment, the catalyst of the present invention can preferably be acid-blocked with an acid, such as a carboxylic acid (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acid or any other organic or inorganic acid. Examples of preferred carboxylic acids include monoacids, diacids or polyacids, with or without isocyanate-reactive groups. Examples of preferred carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid, and the like. The acid-blocked catalyst can be obtained by known methods using conventional equipment.

[0039] In another embodiment, the tertiary amine catalyst component is preferably used in combination with a transition metal catalyst. For example, in one embodiment, the tertiary amine catalyst component is preferably used in combination with an organotin compound, a tin(II) carboxylate, a bismuth(III) carboxylate, or a combination thereof. Examples of preferred transition metal catalysts such as organotin compounds or bismuth carboxylates include dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilauryl mercaptide, dibutyltin dilauryl mercaptide, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, dimethyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(2-ethylhexyl mercaptoacetate), stannous octate, other suitable organotin catalysts, or at least one member selected from the group consisting of combinations thereof. Other metals, such as bismuth (Bi), etc., can also be included. Suitable bismuth carboxylates preferably include salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids. Other salts of transition metals, lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids can also be included.

[0040] The catalyst composition defined by formula (I) can be produced, for example in the case of 2-[2-(dimethylamino)ethoxy]-N-methyl-acetamide, by following the steps below: An 8.8 g of a CuO / ZnO / Al2O3 catalyst with a typical composition of 61% CuO, 28% ZnO and 10% Al2O3, sold by Siid Chemie under the name of T-4581 material, was charged into a fixed bed tubular reactor equipped with a 10 cc quartz preheating bed. The reactor was pressurized with nitrogen up to 20.7 bar (300 psig) and then vented to the ambient. The pressure of the reactor was maintained by a back pressure controller. The nitrogen purge was repeated for 2 more cycles, followed by 3 hydrogen purges. Next, hydrogen was fed to the reactor at 500 scc / m and 20.7 bar (300 psig). The reactor was heated to 250 °C at 1 °C / min using a resistance heater and held at that temperature for 4 hours to reduce the catalyst. The hydrogen flow rate measured by a mass flow controller was adjusted so that the molar ratio of hydrogen / dimethylaminoethoxyethanol (DMAEE) was 4 / 1. DMAEE was fed to the pressurized reactor by a constant flow syringe pump. MMA was co-fed to the pressurized reactor by a constant flow syringe pump at a 2 / 1 MMA / DMAEE molar ratio. The effluent from the reactor was analyzed by GC to obtain approximately 12% of 2-[2-(dimethylamino)ethoxy]-N-methyl-acetamide, which was separated and purified by distillation.

[0041] In another embodiment, the catalyst system or composition of the present invention can further preferably contain other catalyst materials, such as carboxylates, in any amount. Preferably, the other catalyst materials are selected from alkali metal salts, alkaline earth metal salts, and quaternary ammonium carboxylates, such as, but not limited to, potassium formate, potassium acetate, potassium propionate, potassium butyrate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octanoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octanoate, lithium stearate, sodium caprioate, lithium octanoate, 2-hydroxypropyltrimethylammonium octanoate solution, etc., or combinations thereof.

[0042] Preferably, the amounts of the other catalyst materials and salts can be in the range of about 0 pphp to about 20 pphp, about 0.1 pphp to about 15 pphp, and in some cases about 0.5 pphp to about 10 pphp.

[0043] The catalyst composition of the present invention also encompasses mixtures or combinations of two or more catalyst compounds defined by formula (I). Further, in another embodiment, the catalyst composition of the present invention can further preferably contain at least one urethane catalyst that does not have isocyanate-reactive groups.

[0044] The term "contacting substances" is used herein to describe compositions in which the components are contacted with one another at any time, in any order, and by any means. For example, the components can be contacted by blending or mixing. Further, the contacting of any components can be carried out in the presence or absence of any other components of the compositions or foam formulations described herein. Further combinations of catalyst components can be carried out by any method known to those skilled in the art. For example, in one embodiment of the invention, the catalyst composition can be prepared by combining or contacting a catalyst composition defined by formula (I) with at least one tertiary amine, with or without at least one isocyanate-reactive group, and optionally an alkali metal carboxylate. This is usually done in the form of a solution.

[0045] Compositions and methods are described using the term "comprising" various components or steps, but the compositions and methods can also "consist essentially of" or "consist of" various components or steps.

[0046] Polyisocyanate Polyisocyanates useful in the PIR / PUR foam forming process preferably include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate (TDI), multiple isomers of diphenylmethane diisocyanate (MDI), hydrated MDI, and 1,5-naphthalene diisocyanate. In the present invention, for example, 2,4-TDI, 2,6-TDI, and mixtures thereof can be easily used. Other suitable mixtures of diisocyanates include, but are not limited to, those known in the art as crude MDI or PAPI, which contain 4,4'-diphenylmethane diisocyanate together with other isomers and similar higher polyisocyanates. In another embodiment of the present invention, prepolymers of polyisocyanates containing a partially pre-reacted mixture of polyisocyanates and polyether or polyester polyols are suitable. In yet another embodiment, the polyisocyanate contains MDI or consists essentially of MDI or a mixture of MDI.

[0047] The catalyst system, composition, and method for producing PIR / PUR foams of the present invention can be used to produce many types of foams. This catalyst system is useful, for example, in the formation of foam products for rigid and flame-retardant applications that typically require a high isocyanate index. As defined above, the isocyanate index is the value obtained by dividing the amount of polyisocyanate actually used by the stoichiometric amount of polyisocyanate theoretically required to react with all the active hydrogens in the reaction mixture and multiplying by 100. In the present invention, the isocyanate index is represented by the formula: Isocyanate index = (NCO equivalents / equivalents of active hydrogen) × 100 [where NCO equivalents is the number of NCO functional groups in the polyisocyanate and equivalents of active hydrogen is the number of active hydrogen atom equivalents].

[0048] Foam products produced with an isocyanate index of from about 10 to about 800 are within the scope of the present invention. According to another embodiment of the present invention, the isocyanate index ranges from about 20 to about 700, from about 30 to about 650, from about 50 to about 600, or from about 70 to about 500.

[0049] Polyol The active hydrogen-containing compound for use with the aforementioned polyisocyanate in the formation of the polyisocyanurate / polyurethane foam of the present invention can be any organic compound having at least two hydroxyl groups, such as, for example, a polyol. Polyols typically used in the PIR / PUR foam forming process include polyalkylene ethers and polyester polyols. Polyalkylene ether polyols include poly(alkylene oxide) polymers, such as poly(ethylene oxide) and poly(propylene oxide) polymers, and copolymers having terminal hydroxyl groups derived from polyhydric alcohol compounds including diols and triols. These diols and triols preferably include, but are not limited to, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylolpropane, cyclohexanediol, and saccharides such as sucrose and similar low molecular weight polyols.

[0050] Amine polyether polyols can be used in the present invention. These can be prepared by reacting amines such as, for example, ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine or triethanolamine with ethylene oxide or propylene oxide.

[0051] In another embodiment of the present invention, a single high molecular weight polyether polyol, or a mixture of high molecular weight polyether polyols, such as a mixture of different polyfunctional materials and / or materials of different molecular weights or different chemical compositions, can be used.

[0052] In yet another embodiment of the present invention, polyester polyols can be used, including those produced when a dicarboxylic acid is reacted with an excess of diol. Non-limiting examples include adipic acid, phthalic acid, or phthalic anhydride reacted with ethylene glycol or butanediol. Polyols useful in the present invention can be produced by reacting a lactone with an excess of diol, for example, by reacting caprolactone with propylene glycol. In a further embodiment, active hydrogen-containing compounds such as polyester polyols and polyether polyols, and combinations thereof, are useful in the present invention.

[0053] Preferably, the polyol may have an OH number of about 5 to about 600, about 100 to about 600, and in some cases about 50 to about 100, and a functionality of about 2 to about 8, about 3 to about 6, and in some cases about 4 to about 6.

[0054] Preferably, the amount of polyol may be in the range of about 0 pphp to about 100 pphp, about 10 pphp to about 90 pphp, and in some cases about 20 pphp to about 80 pphp.

[0055] Blowing agent According to the compositions, foam formulations, and PIR / PUR foam production methods within the scope of the present invention, suitable blowing agents that can be used alone or in combination preferably include, but are not limited to, water, methylene chloride, acetone, hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCCs), hydrofluoroolefins (HFOs), chlorofluoroolefins (CFOs), hydrochloroolefins (HCOs), hydrofluorochloroolefins (HFCOs), hydrochlorofluorocarbons (HCFCs), chloroolefins, formates, and hydrocarbons. Examples of HFCs include, but are not limited to, HFC-245fa, HFC-134a, and HFC-365. Specific examples of HCFCs include, but are not limited to, HCFC-141b, HCFC-22, and HCFC-123. Exemplary hydrocarbons include, but are not limited to, n-pentane, iso-pentane, cyclopentane, etc., or any combination thereof. In one embodiment of the present invention, the blowing agent or mixture of blowing agents includes at least one hydrocarbon. In another embodiment, the blowing agent includes n-pentane. Further, in another embodiment of the present invention, the blowing agent consists essentially of n-pentane or consists essentially of a mixture of n-pentane and one or more blowing agents. Examples of hydrohaloolefin blowing agents are, among numerous HFOs, in particular, HFO-1234ze (trans-1,3,3,3-tetrafluoroprop-1-ene), HFO-1234yf (2,3,3,3-tetrafluoropropene), and HFCO-1233zd (1-propene,1-chloro-3,3,3-trifluoro).

[0056] In one embodiment, the blowing agent component includes a hydrohaloolefin (preferably one containing at least one of trans-HFO-1234ze and HFCO-1233zd), and optionally a hydrocarbon, fluorocarbon, chlorocarbon, fluorochlorocarbon, halogenated hydrocarbon, ether, fluorinated ether, ester, aldehyde, ketone, carbon dioxide generating material, or a combination thereof. The hydrohaloolefin preferably includes at least one haloalkene, such as a fluoroalkene or chloroalkene containing 3 to 4 carbon atoms and at least one carbon-carbon double bond. Preferred hydrohaloolefins include, but are not limited to, trifluoropropene, tetrafluoropropene, such as (HFO-1234), pentafluoropropene, such as (HFO-1225), chlorotrifluoropropene, such as (HFO-1233), chlorodifluoropropene, chlorotrifluoropropene, chlorotetrafluoropropene, and combinations thereof. Other preferred blowing agents include tetrafluoropropene, pentafluoropropene, and chlorotrifluoropropene compounds having one or fewer fluorine or chlorine substituents at the unsaturated terminal carbon. 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO1225zc), 1,1,1,3,3,3-hexafluorobut-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd), 1,1,1,4,4,4-hexafluorobut-2-ene or combinations thereof, as well as all possible structural isomers, geometric isomers or stereoisomers of each of these.Preferred optional blowing agents include, without limitation, water, formic acid, organic acids that produce carbon dioxide when reacting with isocyanate, hydrocarbons, ethers, halogenated ethers, pentafluorobutane, pentafluoropropane, hexafluoropropane, heptafluoropropane, trans-1,2 dichloro-ethylene, methyl formate, 1-chloro-1,2,2,2-tetrafluoroethane, 1,1-dichloro-1-fluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1-chloro-1,1-difluoroethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,3,3,3-heptafluoropropane, trichlorofluoromethane, dichlorodifluoromethane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,3,3-hexafluoropropane, difluoromethane, difluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1-difluoroethane, isobutane, normal pentane, isopentane, cyclopentane, or combinations thereof. The blowing agent component is typically present in the polyol premix composition in an amount of about 1 wt% to about 30 wt%, preferably about 3 wt% to about 25 wt%, more preferably about 5 wt% to about 25 wt% by weight of the polyol premix composition. When both a hydrohaloolefin and an optional blowing agent are present, the hydrohaloolefin component is typically present in the blowing agent component in an amount of about 5 wt% to about 90 wt%, preferably about 7 wt% to about 80 wt%, more preferably about 10 wt% to about 70 wt% by weight of the blowing agent component, and the optional blowing agent is typically present in the blowing agent component in an amount of about 95 wt% to about 10 wt%, preferably about 93 wt% to about 20 wt%, more preferably about 90 wt% to about 30 wt% by weight of the blowing agent component.

[0057] It has been found that chlorofluorocarbons (CFCs) can deplete stratospheric ozone, so the use of this type of blowing agent is not desirable. Chlorofluorocarbons (CFCs) are alkanes in which all hydrogen atoms are replaced by chlorine and fluorine atoms. Examples of CFCs include trichlorofluoromethane and dichlorodifluoromethane.

[0058] The amount of blowing agent used can vary, for example, based on the intended method of use and application of the foam product and the desired rigidity and density of the foam. In the compositions, foam formulations and methods for preparing the polyisocyanurate / polyurethane foams of the present invention, the blowing agent is present in an amount of from about 5 to about 80 parts by weight per 100 parts by weight of at least one active hydrogen-containing compound. In another embodiment, the blowing agent is present in an amount of from about 10 to about 60, from about 15 to about 50, or from about 20 to about 40 parts by weight per 100 parts by weight of at least one active hydrogen-containing compound. When at least one active hydrogen-containing compound is at least one polyol, the blowing agent is present in an amount of from about 5 to about 80 parts per hundred parts of polyol (pphp), from about 10 to about 60 pphp, from about 15 to about 50 pphp, or from about 20 to about 40 pphp.

[0059] If water is present in the formulation for use as a blowing agent or otherwise, the water is present in an amount of up to about 60 parts by weight per 100 parts by weight of at least one active hydrogen-containing compound. Similarly, when at least one active hydrogen-containing compound is at least one polyol, the water can range from 0 to about 15 pphp. In another embodiment, the water can be in the range of 0 to about 10 pphp, 0 to about 8 pphp, 0 to about 6 pphp, or 0 to about 4 pphp.

[0060] Urethane catalyst In one embodiment, in order to accelerate the reaction for forming polyurethane, a conventional urethane catalyst having no isocyanate-reactive group can preferably be used, and this can be used as a further component of the catalyst system and composition of the present invention for producing polyisocyanurate / polyurethane foam. Suitable urethane catalysts for use herein preferably include metal salt catalysts such as organotin compounds, and amine compounds such as triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethyl-imidazole, N-methylmorpholine (commercially available as DABCO® NMM catalyst), N-ethylmorpholine (commercially available as DABCO® NEM catalyst), triethylamine (commercially available as DABCO® TETN catalyst), N,N'-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (commercially available as Polycat® 41 catalyst), 2,4,6-tris(dimethylaminomethyl)phenol (commercially available as DABCO TMR® 30 catalyst), N-methyldicyclohexylamine (commercially available as Polycat® 12 catalyst), pentamethyldipropylenetriamine (commercially available as Polycat® 77 catalyst), N-methyl-N'-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyldiethylenetriamine (commercially available as Polycat® 5 catalyst), hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine (commercially available as Polycat® 8 catalyst), pentamethyldipropylene-triamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether (commercially available as DABCO® BL19 catalyst), tris(3-dimethylamino)-propylamine (commercially available as Polycat® 9 catalyst), 1,8-diazabicyclo[5.4.0]undecene (commercially available as DABCO® DBU catalyst) or its acid-block derivatives, etc., and any mixtures thereof, but are not limited thereto.

[0061] In another embodiment, the present invention can be used with a tertiary amine catalyst having an isocyanate-reactive group. Preferably, the isocyanate-reactive groups present in the tertiary amine gelation co-catalyst consist essentially of primary amines, secondary amines, secondary hydroxyl groups, amides, and ureas.Examples of gelling catalysts preferably include N,N-bis(3-dimethylamino-propyl)-N-(2-hydroxypropyl)amine, N,N-dimethyl-N’,N’-bis(2-hydroxypropyl)-1,3-propylenediamine, dimethylaminopropylamine (DMAPA), N-methyl-N-2-hydroxypropyl-piperazine, bis(dimethylaminopropyl)amine (POLYCAT® 15), dimethylaminopropylurea and N,N’-bis(3-dimethylaminopropyl)urea (DABCO® NE1060, DABCO® NE1070, DABCO® NE1080 and DABCO® NE1082), 1,3-bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole, N,N’-bis(2-hydroxypropyl)piperazine, N-(2-hydroxypropyl)-morpholine, N-(2-hydroxyethylimidazole), N,N-bis(3-dimethylaminopropyl)-N-{3-[bis(2-hydroxypropyl)]propylamine}, N,N-bis(3-dimethylaminopropyl)-N-{3-[bis(2-hydroxyethyl)]propylamine}; N,N-bis(dimethylaminopropyl)-N-(3-aminopropyl)-amine; N,N’-bis[bis-N’’,N’’-(3-dimethylaminopropyl)-N’’-(3-aminopropyl)]urea; N,N-bis(3-dimethylaminopropyl)-N-(3-aminopropyl)]urea; N,N-bis(3-dimethylaminopropyl)-N-(bis(2-hydroxypropyl)-3-aminopropyl)]amine; N,N-bis(3-dimethylaminopropyl)-N-[N’,N’-bis(2-hydroxypropyl)-3-aminopropyl]amine; and N,N-bis(3-dimethylaminopropyl)-N-[(2-hydroxypropyl)-3-aminopropyl]amine.Examples of the blowing co - catalysts containing isocyanate - reactive groups that can be used together with the above - mentioned gelling catalysts preferably include 2 - [N - (dimethylaminoethoxyethyl) - N - methylamino] ethanol (DABCO® NE200), N,N,N’ - trimethyl - N’ - 3 - aminopropyl - bis(aminoethyl) ether (DABCO® NE300).

[0062] Suitable urethane catalysts that can be used in combination with the catalyst in the present invention preferably include acid - blocked tertiary amines containing carboxylic acid (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acid or any other organic or inorganic acid. Examples of carboxylic acids preferably include mono - acids, di - acids or poly - acids with or without isocyanate - reactive groups. Examples of preferred carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2 - ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid, etc. The acid - blocked catalysts can be obtained by known methods using conventional equipment.

[0063] In another embodiment, the tertiary amine catalyst component can preferably also be used together with a metal catalyst. For example, in certain embodiments, the tertiary amine catalyst component is preferably used together with an organotin compound, a tin(II) carboxylate, a bismuth(III) carboxylate, or a combination thereof. Preferred examples of metal catalysts such as organotin compounds or bismuth carboxylates include dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilauryl mercaptide, dibutyltin dilauryl mercaptide, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, dimethyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(2-ethylhexyl mercaptoacetate), stannous octoate, other suitable organotin catalysts, or at least one member selected from the group consisting of combinations thereof. Other metals, such as bismuth (Bi), etc., can also be included. Suitable bismuth carboxylates preferably include salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids. Other salts of metals, lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids can also be included.

[0064] In another embodiment, the present invention can preferably further comprise other catalyst materials, such as any amount of carboxylate salts. Preferred examples of alkali metal, alkaline earth metal and quaternary ammonium carboxylate salts include potassium formate, potassium acetate, potassium propionate, potassium butyrate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octanoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octanoate, lithium stearate, sodium caprioate, lithium octanoate, 2-hydroxypropyltrimethylammonium octanoate solution, tetramethylammonium carboxylate, tetraalkylammonium carboxylate, such as tetramethylammonium pivalate (supplied by Evonik Corporation as DABCO® TMR7), or combinations thereof, but are not limited thereto.

[0065] To prepare the polyisocyanurate / polyurethane foam of the present invention, the formulation can contain from 0 to about 10 pphp, 0 to about 8 pphp, 0 to about 6 pphp, 0 to about 4 pphp, 0 to about 2 pphp, or 0 to about 1 pphp of urethane catalyst. In another embodiment, from 0 to about 0.8 pphp, 0 to about 0.6 pphp, 0 to about 0.4 pphp, or 0 to about 0.2 pphp of urethane catalyst is present.

[0066] Other additives Depending on the requirements during foam production or the end-use requirements of the foam product, various additives for adapting to specific properties can preferably be used in the PIR / PUR foam formulation. These additives preferably include, but are not limited to, foam stabilizers, flame retardants, chain extenders, epoxy resins, acrylic resins, fillers, pigments, or any combination thereof. Other mixtures or materials known in the art can also be included in the foam formulation, and it goes without saying that they are within the scope of the present invention.

[0067] The foam stabilizers include surfactants such as organopolysiloxanes. The silicone surfactant can be present in the foam formulation in an amount of about 0.5 to about 10 pphp, about 0.6 to about 9 pphp, about 0.7 to about 8 pphp, about 0.8 to about 7 pphp, about 0.9 to about 6 pphp, about 1 to about 5 pphp, or about 1.1 to about 4 pphp. Useful flame retardants include halogenated organic phosphorus compounds and non-halogenated compounds. A non-limiting example of a halogenated flame retardant is trichloropropyl phosphate (TCPP). For example, triethyl phosphate ester (TEP) and DMMP are non-halogenated flame retardants. Depending on the end use of the final foam, the flame retardant can be present in the foam formulation in an amount of 0 to about 50 pphp, 0 to about 40 pphp, 0 to about 30 pphp, or 0 to about 20 pphp. In another embodiment, there is a flame retardant in an amount of 0 to about 15 pphp, 0 to about 10 pphp, 0 to about 7 pphp, or 0 to about 5 pphp. Chain extenders such as ethylene glycol and butanediol can also be used in the present invention. For example, ethylene glycol can also be present in the formulation as a diluent or solvent for the carboxylate catalyst of the present invention.

[0068] Polyurethane Foam Formulations and Processes One preferred embodiment of the present invention provides a polyurethane composition comprising a contact product of at least one active hydrogen-containing compound, at least one blowing agent, and at least one catalyst composition defined above by formula (I).

[0069] Another preferred embodiment provides a composition comprising a contact product of at least one polyisocyanate, at least one blowing agent, and at least one catalyst composition defined above by formula (I), used in combination with at least one tertiary amine having at least one isocyanate-reactive group.

[0070] Another preferred embodiment provides a composition comprising a contact product of at least one polyisocyanate, at least one blowing agent, and at least one catalyst composition as defined above by formula (I), which is used in combination with at least one tertiary amine having no isocyanate-reactive groups.

[0071] In another preferred embodiment, the composition can further comprise the catalyst composition as defined above by formula (I) together with at least one urethane catalyst having no isocyanate-reactive groups and at least one urethane catalyst having isocyanate-reactive groups. Similarly, the composition can preferably further comprise at least one additive selected from at least one foam stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.

[0072] In another preferred embodiment, the present invention provides a method for preparing polyurethane foams and polyisocyanurate / polyurethane (PIR / PUR) foams, which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and an effective amount of the catalyst composition as defined above by formula (I). According to the method of the present invention, PUR and PIR / PUR foams having a density of about 8 Kg / m 3 to about 250 Kg / m 3 (about 0.5 lb / ft 3 to about 15.5 lb / ft 3 ) or about 24 Kg / m 3 to about 60 Kg / m 3 (about 1.5 lb / ft 3 to about 3.75 lb / ft 3 ) can be produced.

[0073] Another preferred embodiment provides a method for preparing a polyurethane foam comprising contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and an effective amount of the catalyst composition as defined above by formula (I), wherein the catalyst composition is present in a tertiary amine with or without isocyanate-reactive groups.

[0074] Another preferred embodiment provides a method for preparing a polyurethane foam comprising contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and an effective amount of the catalyst composition as defined above by formula (I), wherein the catalyst composition is present in combination with a metal catalyst, a tertiary amine with or without isocyanate-reactive groups, or a combination thereof.

[0075] The present invention can be used in a wide range of methods for making rigid closed-cell foams, rigid open-cell foams, flexible foams including flexible slabstock foams and flexible molded foams, as well as semi-flexible foams and microcellular foams. Examples of suitable methods include, among other rigid foam production methods, injection, molding, spraying. In one embodiment, the method of the present invention relates to a method for making laminated foams. The foams of the present invention can be laminated to a wide range of substrates including wood, steel, paper and plastics.

[0076] The present method for preparing PUR and PIR / PUR foams can also provide a polyol premix with less ammonia odor when compared to other commercially available catalyst systems.

[0077] The catalyst composition defined by formula (I) above is preferably present in a catalytically effective amount in the foam formulation. In the PUR and PIR / PUR foam formulations of the present invention, the catalyst composition is present in an amount of about 0.05 to about 20 parts by weight per 100 parts by weight of at least one active hydrogen-containing compound, excluding the weight contribution of the catalyst system diluent. In another embodiment, the catalyst composition is present in an amount of about 0.4 to about 10 parts by weight, or about 0.8 to about 8 parts by weight per 100 parts by weight of at least one active hydrogen-containing compound. When at least one active hydrogen-containing compound is at least one polyol, the catalyst composition is present in an amount of about 0.05 to about 10 parts by weight per 100 parts by weight of the polyol (pphp). In another embodiment, the catalyst composition is present in an amount of about 0.2 to about 9.5 pphp, about 0.4 to about 9 pphp, about 0.6 to about 8.5 pphp, or about 0.8 to about 8 pphp.

[0078] According to one embodiment of the method of the present invention, the components of the foam formulation are contacted substantially simultaneously. For example, at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent, and an effective amount of the catalyst composition defined by formula (I) above are contacted with each other. Considering the number of components involved in PUR and PIR / PUR formulations, there are numerous different orders in which the components can be combined, and it will be understood by those skilled in the art that changes in the order of addition of the components are within the scope of the present invention. Similarly, for each of the different orders in which the aforementioned components of the foam formulation are combined, the foam formulation of the present invention can further comprise at least one urethane catalyst. Further, the method for producing a PIR / PUR foam preferably further comprises the presence of at least one additive selected from at least one surfactant, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof. In one embodiment of the present invention, all components, including optional components, are contacted substantially simultaneously.

[0079] In another embodiment of the present invention, a premix of components other than at least one polyisocyanate is first contacted, and then at least one polyisocyanate is added. For example, at least one active hydrogen-containing compound, at least one blowing agent, at least one foam stabilizer, and the catalyst composition of the present invention are first contacted to form a premix. Next, the premix is contacted with at least one polyisocyanate to produce a PUR or PIR / PUR foam according to the method of the present invention. In a further embodiment of the present invention, the same method can be used, and the premix preferably further contains at least one urethane catalyst. Similarly, the premix preferably further contains at least one additive selected from at least one foam stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.

[0080] One embodiment of the present invention provides a method for preparing polyurethane, polyisocyanurate, polyisocyanurate / polyurethane foam, comprising the following steps:

[0081] (a) i) at least one polyol, ii) a blowing agent in an amount of about 1 to about 80 parts by weight per 100 parts by weight of polyol (pphp), iii) a silicone surfactant in an amount of about 0.5 to about 10 pphp, iv) water in an amount of 0 to about 60 pphp, v) a flame retardant in an amount of 0 to about 50 pphp, vi) a urethane catalyst in an amount of 0 to about 10 pphp, and vii) a catalyst composition as defined in formula (I) above in an amount of about 0.05 to about 20 pphp to form a premix, and (b) contacting the premix with at least one polyisocyanate at an isocyanate index of about 10 to about 800.

[0082] The following is a list of preferred items of the present invention. Item 1. A catalyst composition comprising at least one compound represented by formula (I):

Chemical formula

Examples

[0083] These examples are provided to demonstrate specific embodiments of the present invention and are not intended to limit the scope of the appended claims.

[0084] [Example 1 (of the present invention)] This example describes the synthesis of 2-[2-(dimethylamino)ethoxy]-N-methyl-acetamide (DMAEMAc). An 8.8 g of CuO / ZnO / Al₂O₃ catalyst with a typical composition of 61% CuO, 28% ZnO and 10% Al₂O₃, sold by Siid Chemie under the name of T-4581 material, was charged into a fixed-bed tubular reactor equipped with a 10 cc quartz preheating bed. The reactor was pressurized with nitrogen up to 20.7 bar (300 psig) and then vented to the ambient. The pressure of the reactor was maintained by a back-pressure controller. The nitrogen purge was repeated for an additional 2 cycles, followed by 3 hydrogen purges. Next, hydrogen was supplied to the reactor at 500 scc / m and 20.7 bar (300 psig). The reactor was heated to 250 °C at 1 °C / min using a resistance heater and held at that temperature for 4 hours to reduce the catalyst. The hydrogen flow rate measured by a mass flow controller was adjusted so that the molar ratio of hydrogen / dimethylaminoethoxyethanol (DMAEE) was 4 / 1. DMAEE was supplied to the pressurized reactor by a constant flow syringe pump. MMA was co-fed to the pressurized reactor by a constant flow syringe pump at a 2 / 1 MMA / DMAEE molar ratio. The effluent from the reactor was analyzed by GC to obtain approximately 12% of 2-[2-(dimethylamino)ethoxy]-N-methyl-acetamide (DMAEMAc), which was separated and purified by distillation.

[0085] [Example 2 (the present invention)] This example describes the synthesis of crude 2-[2-(dimethylamino)ethoxy]-N-methyl-acetamide (crude DMAEMAc). A crude sample of DMAEMAc was prepared using the same procedure as described in Example 1. This sample was produced by distillation and after removal of N,N,N’-trimethyl-aminoethyl ether (TMAEE) as well as excess starting materials (DMAEE) and a small amount of BDMAEE (bis-dimethylaminoethyl ether), 25% crude DMAEMAc was obtained. The crude DMAEMAc composition mainly consists of 50 - 60% DMAEMAc, 10 - 20% N-methyl-N,N-bis(dimethylaminoethoxyethyl)amine, 4 - 8% N,N-bis(dimethylaminoethoxyethyl)amine and about 4 - 6% 2-[2-(dimethylamino)ethoxy]-N-methyl-N-(dimethylaminoethoxyethyl)-acetamide. [Chemical formula]

[0086] [Example 3 (of the present invention)] This example describes the synthesis of pure 2-[2-(dimethylamino)ethoxy]-N-methyl-acetamide (pure DMAEMAc). The crude sample of DMAEMAc described in Example 2 was distilled off under nitrogen to obtain a transparent liquid consisting of DMAEMAc. The sample was produced by distillation after removal of N-methyl-N,N-bis(dimethylaminoethoxyethyl)amine, N,N-bis(dimethylaminoethoxyethyl)amine, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-(dimethylaminoethoxyethyl)-acetamide and other heavy impurities.

[0087] [Example 4 (of the present invention)] This example describes the comparison of the foam rising rate kinetics and usage levels for 2-[2-(dimethylamino)ethoxy]-N-methyl-acetamide (DMAEMAc). The forming performance can be evaluated by comparing the foam height versus time for the standard and new amine catalysts. The foam height profile can be measured by an automated rising rate device that uses a free-rise cup foam sample with a FOMAT sonar rising rate device (hereinafter referred to as "ROR"). The FOMAT device is equipped with a sonar sensor that measures and records the height of the rising foam sample (in millimeters (mm)) versus time (in seconds (s)) immediately after all components of the formulation are mixed. The FOMAT standard software generates both a height-versus-time plot and a rate-versus-time plot. These plots are useful for comparing the relative reactivity of different catalyst formulations. The flexible foam can be prepared by admixing the components in Table 1 other than isocyanate, with a total weight of about 300 g, in a 32-ounce (951 ml) paper cup. Next, this premix formulation is mixed at about 6,000 rpm for about 10 seconds using an overhead stirrer equipped with a 2-inch (5.1 cm) diameter stirring paddle. Next, sufficient toluene diisocyanate is added to achieve a desired isocyanate index of about 100, and the formulation is further mixed well at about 6,000 rpm for about 6 seconds using the same stirrer. Next, the cup is placed under the FOMAT sensor. The start time of the ROR measurement is automated for FOMAT and starts immediately after the end of the final mixing. When the cup is placed under the ROR, the chemical mixture begins to polymerize. Since the walls of the cup limit expansion in all directions except vertically, this expansion appears in this experiment as an increase in height over time.

Table 1

[0088] This increase in height can also be expressed as the rate of change of height with respect to time (velocity). By recording the time required for the foam to reach the standard height (TOC = upper end of the cup) after mixing, the maximum foam rise velocity, the time required to achieve the maximum velocity after mixing, and the string gelation time (SGT) (which is the time at which the polymer mass can form polymer strings when touched with a wooden tongue depressor), a useful comparison can be made regarding the speed of the forming reaction. [Table 2]

[0089] [Example 5 (the present invention)] This example compares the physical properties of polyurethane foams made using the catalysts "pure DMAEMAc", "crude DMAEMAc", and a standard catalyst used in the polyurethane industry.

[0090] The foam pads were prepared by adding a tertiary amine catalyst to approximately 302 g of premix (prepared as in Table 1) in 32-ounce (951 ml) paper cups. This formulation was mixed for approximately 10 seconds at approximately 6,000 RPM using an overhead stirrer equipped with a 2-inch (5.1 cm) diameter stirring paddle. Next, toluene diisocyanate was added, and the formulation was further mixed well for approximately 6 seconds at approximately 6,000 RPM using the same stirrer. Then, it was poured into a preheated mold at 70 °C and demolded after 4 minutes. The foam pads were removed from the mold, crushed by hand, weighed, and mechanically crushed at 75% of the pad thickness. The foam pads were stored under constant temperature and humidity conditions for 48 hours, then cut and tested. [Table 3] [Table 4]

[0091] Table 4 shows the physical properties of a soft molded polyurethane pad made using the standard reactive gelation / foaming amine catalysts Dabco® 33LV / DABCO® BL11 during environmental aging and wet aging, and compares them with the new gelation catalysts DMAEMAc (Example 3) and "crude DMAEMAc" (Example 2) (using the foaming catalyst DABCO® NE300 in both cases). Table 4 shows that the environmental physical properties are very similar and give a foam pad with excellent physical properties. Table 4 also shows the physical properties after wet aging using the Volkswagen aging procedure. The evaluation shows the new gelation catalysts, pure DMAEMAc and crude DMAEMAc, which were carried out in the same way as the standard reactive catalyst DABCO® 33LV, and the foams made using the catalysts of the present invention have overall better performance under wet aging.

[0092] [Example 6 (the present invention)] This example compares the physical properties of polyurethane foams made using the catalysts "pure DMAEMAc", "crude DMAEMAc" and standard catalysts used by the industry.

[0093] The foam pads were prepared by adding a tertiary amine catalyst to approximately 302 g of premix (prepared as in Table 1) in a 32 ounce (951 ml) paper cup. This formulation was mixed at approximately 6,000 RPM for approximately 10 seconds using an overhead stirrer equipped with a 2 inch (5.1 cm) diameter stirring paddle. Toluene diisocyanate was then added and the formulation was further mixed well at approximately 6,000 RPM for approximately 6 seconds using the same stirrer, then poured into a preheated mold at 70 °C and demolded after 4 minutes. The foam pads were removed from the mold, crushed by hand, weighed, and mechanically crushed at 75% pad thickness. The foam pads were stored under constant temperature and humidity conditions for 48 hours, then cut and tested.

Table 5

Table 6

[0094] Table 6 shows the physical properties of soft molded polyurethane pads made using the standard reactive gelation / foaming amine catalysts Dabco® NE1070 / DABCO® NE300 during environmental aging and wet aging, and compares them with the new gelation catalysts, pure DMAEMAc and crude DMAEMAc (using the foaming catalyst DABCO® NE300 in both cases). Table 6 shows that the environmental physical properties are very similar and give foam pads with excellent physical properties. Table 6 also shows the physical properties after wet aging using the Volkswagen aging procedure. The evaluation shows the new gelation catalysts, pure DMAEMAc and crude DMAEMAc, which were carried out in the same manner as the standard reactive catalyst DABCO® NE1070, and the foams made using the catalysts of the present invention have overall better performance under wet aging.

[0095] [Example 7 (the present invention)] This example describes the performance of DMAEMAc in a typical closed-cell rigid foam formulation.

[0096] The evaluation of catalyst reactivity in the rigid polyurethane system was carried out using free-rise cup foam samples with a FOMAT sonication rate of rise (ROR) device. The FOMAT standard software generates both a height vs. time plot and a rate vs. time plot. These plots are useful for comparing the relative reactivity of different catalyst formulations. MDI polyurethane foams were prepared in a conventional hand-mix manner. Polyurethane formulation (parts by weight):

Table 7

[0097] The following table shows the amount of catalyst required to match the string gel time in a standard rigid formulation when using distilled (pure) DMAEMAc and non-distilled (crude) DMAEMAc as the sole catalyst.

Table 8

[0098] Alternatively, as shown in the following table, DMAEMAc and non-distilled (crude) DMAEMAc can be used in rigid formulations in combination with blowing catalysts such as Polycat® 5 commercially available from Evonik Corporation.

Table 9

[0099] The following table shows the physical properties of the foams made with DMAEMAc.

Table 10

Table 11

Table 12

[0100] Therefore, pure DMAEMAc and crude DMAEMAc are useful catalysts in the preparation of various types of polyurethane foams, including rigid and flexible foams.

Claims

1. A catalyst composition comprising at least one compound represented by formula (I). 【Chemistry 1】 [wherein, R １ , R ２ , and R ３ are each independently a linear or branched C １ -C ３ alkyl group, or a linear or branched C ２ -C ６ alkenyl group; R ４ is hydrogen, a linear or branched C １ -C ３ alkyl group, or a linear or branched C ２ -C ６ alkenyl group.]

2. R １ , R ２ , and R ３ Each of these is independently a methyl group, R ４ The catalyst composition according to claim 1, wherein is hydrogen.

3. The at least one compound represented by formula (I) is 2-[2-(dimethylamino)ethoxy]-N-methyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N,N-diethyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N,N-dipropyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N,N-dibutyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N,N-dipentyl-acetamide Mido, 2-[2-(dimethylamino)ethoxy]-N,N-dihexyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-ethyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-propyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-butyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-pentyl-acetamide, 2-[2- (dimethylamino)ethoxy]-N-methyl-N-hexyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-ethyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-propyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-butyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-pentyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-hexyl-acetamide, 2-[2-(diethylamino)ethoxy]-N,N-dimethylacetamide, 2-[2-(diethylamino)ethoxy]-N,N-diethylacetamide, 2-[2-(diethylamino)ethoxy]-N,N-dipropylacetamide, 2-[2-(diethylamino)ethoxy]-N,N-dibutylacetamide, 2-[2-(diethylamino)ethoxy]-N,N-dipentylacetamide, 2-[2-(diethylamino)ethoxy]-N,N-dihexyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-ethyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-propyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-butyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-pentyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-N-hexyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-methyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-ethyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-propyl-acetamide, 2-[2-(diethylamino)ethoxy]- N-butyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-pentyl-acetamide, 2-[2-(diethylamino)ethoxy]-N-hexyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-dimethyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-diethyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-dipropyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-dibutyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-dipentyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N,N-dihexyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-ethyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-propyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-butyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-pentyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-methyl-N-hexyl-acetamide, 2-[2-(N-methyl- A catalyst composition according to claim 1, selected from the group consisting of N-ethyl-amino)ethoxy]-N-methyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-ethyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-propyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-butyl-acetamide, 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-pentyl-acetamide, and 2-[2-(N-methyl-N-ethyl-amino)ethoxy]-N-hexyl-acetamide.

4. The catalyst composition according to claim 1, further comprising a tertiary amine catalyst having or not having an isocyanate reactive group.

5. The catalyst composition according to claim 4, wherein the tertiary amine catalyst has at least one isocyanate-reactive group comprising a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group, or an amide group.

6. The tertiary amine catalyst is N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-2-hydroxy(propyl)-1,3-propylenediamine, dimethylaminopropylamine, (N,N-dimethylaminoethoxy)ethanol, methyl-hydroxy-ethyl-propyl Perazine, bis(N,N-dimethyl-3-aminopropyl)amine, N,N-dimethylaminopropylurea, diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, N,N'-bis(3-diethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole, N-(2-hydroxyethyl)imidazole, N,N-bis(dimethylaminopropyl)- N-(3-aminopropyl)amine, N,N-bis(3-dimethylaminopropyl)-N-{3-[bis(2-hydroxypropyl)]propylamine}, N,N-bis(3-dimethylaminopropyl)-N-{3-[bis(2-hydroxyethyl)]propylamine}, N,N'-bis[bis-N'',N''-(3-dimethylaminopropyl)-N''-(3-aminopropyl)]urea, N,N-bis(3-dimethylaminopropyl)-N-(3-aminopropyl)urea, N,N-bis(3-dimethylaminopropyl)- N-(bis(2-hydroxypropyl)-3-aminopropyl)amine, N,N-bis(3-dimethylaminopropyl)-N-[N',N'-bis(2-hydroxypropyl)-3-aminopropyl]amine, N,N-bis(3-dimethylaminopropyl)-N-[(2-hydroxypropyl)-3-aminopropyl]amine, 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,The catalyst composition according to claim 4 or 5, selected from the group consisting of N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl) ether or a combination thereof.

7. The catalyst composition according to any one of claims 1 to 5, wherein the catalyst composition is acid-blocked with a carboxylic acid or a sulfonic acid.

8. The catalyst composition according to claim 7, wherein the catalyst composition is acid-blocked with an acid selected from the group consisting of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, and salicylic acid.

9. A catalyst composition according to any one of claims 1 to 5, further comprising a transition metal catalyst.

10. The catalyst composition according to claim 9, wherein the transition metal catalyst is an organotin compound, a tin(II) carboxylate, a bismuth(III) carboxylate, or a combination thereof.

11. A catalyst composition according to any one of claims 1 to 5, further comprising a catalyst material selected from the group consisting of potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octanoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octanoate, lithium stearate, sodium caprioate, lithium octanoate, a solution of 2-hydroxypropyltrimethylammonium octanoate, or a combination thereof.

12. A polyurethane composition comprising a contact between at least one active hydrogen-containing compound, at least one blowing agent, and the catalyst composition according to any one of claims 1 to 3.

13. The polyurethane composition according to claim 12, further comprising a tertiary amine having or not having an isocyanate-reactive group.

14. The polyurethane composition according to claim 12, further comprising at least one foam stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or at least one additive selected from any combination thereof.

15. A method for preparing a polyurethane foam, comprising contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of at least one blowing agent and a catalyst composition according to any one of claims 1 to 3.

16. The method according to claim 15, wherein the catalyst composition is present in combination with a metal catalyst, a tertiary amine having or not having an isocyanate reactive group, or a combination thereof.

Images