Method for adjusting flexible slabstock polyurethane foam

Abstract

At least one polyurethane additive selected from the group consisting of a blowing agent, a foam stabilizer, and a crosslinking agent, and formula (I): TIFF2025524171000017.tif23150[wherein R1, R2, R 3、 R4 and R5 are each independently a linear or branched C1-C3 alkyl or C2-C6 alkenyl], in the presence of a catalyst composition comprising at least one compound represented by the formula, contacting at least one polyisocyanate with at least one polyol, a method for preparing a flexible slabstock polyurethane foam.

Description

Technical Field

[0001] The field of the invention is a method for preparing flexible slabstock polyurethane foam and the use of tertiary amines as catalysts for the production of flexible slabstock polyurethane foam.

[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 for promoting the formation of urethane by reaction of isocyanate with polyol, the formation of CO2 and urea by reaction of water, and the formation of isocyanurate (trimer) by reaction of 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 are vaporized by the heat released during the polymerization reaction. Examples of blowing agents useful for the production of insulating polyurethane foams include, but are not limited to, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluorocarbons, 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, HFOs and HCFs 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. It can produce polyurethane foam materials with various characteristics useful for many 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, on-site foams, and various applications where insulation is desired, such as refrigerators, freezers, water heaters, insulation panels, garage doors, front doors, and others.

[0006] U.S. Patent No. 8,664,445 and U.S. Patent No. 8,822,729 disclose methods for secondary or tertiary amines having the formula (R 1 R 2 NR 3 )2NR 4 [wherein each of R 1 and R 2 is independently selected from the group consisting of methyl, ethyl, isopropyl, and n-propyl groups, R 3 is an alkoxyalkyl group selected from the group consisting of -CH2CH2OCH2CH2-, -CH2CH2OCH2CH2CH2-, and -CH2CH2CH2OCH2CH2CH2-, R 4 is hydrogen, methyl, ethyl, isopropyl, n-propyl, or a group having the formula R 1 R 2 NR 3 . This method provides for R 1 R2 NR 3 (OH) is reacted with ammonia to obtain a mixture containing (R 1 R 2 NR 3 )2NR 4 and separating (R 1 R 2 NR 3 )2NR 4 from the mixture.

[0007] U.S. Patent No. 9,382,397 discloses a primary amine component corresponding to the formula (R 1 R 2 NR 3 )2NR 4 [wherein each of R 1 and R 2 is selected from the group consisting of a methyl group, an ethyl group, an isopropyl group, and an n-propyl group, R 3 is an alkoxyalkyl group selected from the group consisting of -CH2CH2OCH2CH2-, -CH2-CH2OCH2CH2CH2-, and -CH2CH2CH2OCH2CH2CH2-, and R 4 is selected from the group consisting of hydrogen and -CH2CH2CH2NH2] and a catalytic system in the reaction of at least one polyisocyanate component and at least one isocyanate-reactive component (this catalytic system further includes at least one gelling catalyst different from those included in (R 1 R 2 NR 3 )2NR 4 , formula (R 1 R 2 NR 3 )2NR 4 ). The use of the primary amine component corresponding to (R 1 R 2 NR 3 )2NR 4 as a foaming catalyst is disclosed.

[0008] The ability of a tertiary amine catalyst to selectively promote either foaming or gelling 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 foaming from the formulation and resulting in foam collapse and the production of low-quality foam. On the other hand, if the promotion of the gelling 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 due to their low N / C ratio, which is expected to significantly increase manufacturing costs.

[0009] Therefore, there is a need for a tertiary amine catalyst with a low vapor pressure but a relatively high N / C ratio so that the catalytic activity can be maintained during the polymerization process while maintaining good physical and mechanical properties of the finished polymer. There is also a need for a tertiary amine with a low vapor pressure that can provide an improvement in physical properties compared to standard amine catalysts commonly used in the industry.

[0010] Summary of the Invention The present invention relates to at least one polyurethane additive selected from the group consisting of a blowing agent, a foam stabilizer, and a crosslinking agent, and a compound of formula (I):

[0011]

Chemical formula

[0012] The present invention uses at least one catalyst compound represented by formula (I), thus improving and reducing the odor of the finished foam, providing good catalytic activity, and giving a flexible slabstock polyurethane foam with excellent physical properties, thereby solving the problems associated with conventional foam precursors.

[0013] The present invention provides a flexible slabstock polyurethane foam and a polyol premix composition having the following advantages: a) giving a polyurethane foam having good foam kinetics and curing including surface curing; b) improving the odor quality because amides are not involved in chain termination resulting in harmful physical properties of the foam; c) providing a flexible slabstock foam having optimal catalytic activity and physical properties of the foam equivalent to existing standards, in particular improved physical properties compared to those made using conventional tertiary amine catalysts.

[0014] In an exemplary embodiment, the process comprises preparing a premix comprising at least one catalyst compound represented by formula (I), and contacting the premix containing the catalyst composition with at least one physical blowing agent such as a hydrofluorocarbon, hydrofluoroolefin, hydrofluorochloroolefin, hydrochlorofluorocarbon, formate, a ketone such as acetone, a hydrocarbon such as pentane and cyclopentane, or a chemical blowing agent such as water or formic acid.

[0015] In another exemplary embodiment, the flexible slabstock polyurethane foam comprises a contact product of at least one polyol, at least one isocyanate, and a catalyst composition comprising at least one compound represented by formula (I).

[0016] In another exemplary embodiment of the present invention, the catalyst composition comprises at least one catalyst component represented by formula (I) and / or a tertiary amine catalyst containing an isocyanate-reactive group.

[0017] In another exemplary embodiment of the present invention, the catalyst composition comprises at least one catalyst component represented by formula (I) and / or a tertiary amine catalyst not containing an isocyanate-reactive group.

[0018] 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 present invention.

[0019] 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 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. DABCO® 33LV - A commercially available catalyst supplied by Evonik Corporation. This is a 33% dipropylene glycol solution of triethylenediamine. DABCO® BL11 - A commercially available catalyst supplied by Evonik Corporation, and its chemical name is pentamethyldiethylenetriamine. HFO - Hydrofluoroolefin

[0020] Detailed Description of the Invention The present invention relates to a method for preparing a flexible slabstock polyurethane foam, which comprises reacting at least one polyisocyanate with at least one polyol in the presence of a catalyst composition comprising at least one polyurethane additive selected from the group consisting of a blowing agent, a foam stabilizer and a crosslinking agent, and at least one compound represented by formula (I): [Chemical formula] [wherein, R1, R2, R 3、 R4 and R5 are each independently a linear or branched C1-C3 alkyl or C2-C6 alkenyl group]. Preferably, in one embodiment, R1, R2, R3, R4 and R5 are each independently a methyl group.

[0021] The present invention provides flexible slabstock polyurethane foams and polyol premix compositions having the following advantages: a) giving a polyurethane foam having good foam kinetics and curing including surface curing; b) improving the odor quality because the amide is not involved in chain termination which results in harmful foam physical properties; c) providing a flexible slabstock foam having optimal catalytic activity and foam physical properties equivalent to existing standard products, especially improved physical properties compared to those made using conventional tertiary amine catalysts.

[0022] The present invention also provides a method for preparing a flexible slabstock polyurethane foam, which comprises contacting at least one polyisocyanate with at least one polyol in the presence of an effective amount of the catalyst composition defined by formula (I) above, combined with at least one blowing agent and a metal catalyst and / or a tertiary amine having or not having isocyanate-reactive groups.

[0023] Furthermore, the flexible slabstock polyurethane foam can be produced by several methods known in the art using the catalyst systems and compositions of the present invention.

[0024] 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, blowing agents, water, surfactants, flame retardants, and ranges of pphp for the catalyst composition defined in the above formula (I).

[0025] The present invention discloses any type of range, and each possible number that such a range can reasonably encompass, as well as any sub - ranges and combinations of sub - ranges included therein, are disclosed individually. For example, if the present invention discloses a chemical moiety having a specific number of carbon atoms, the present invention discloses each possible number that such a range can encompass, individually.

[0026] For example, the disclosure that R1, R2, R3, R4 and R5 are independently a straight - chain or branched C1 - C3 alkyl or C2 - C6 alkenyl group means, for example, that the alkyl group has a maximum of 3 carbon atoms. In other words, the C 1~3 alkyl group referred to herein can be independently selected from an alkyl group having 1, 2 or 3 carbon atoms, as well as the ranges between two of these numbers, for example a C2 - C3 alkyl group, the "R 1 " or "R 2 " or "R 3 " or "R 4 " or "R 5 " groups.

[0027] 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 the at least one polyol in the composition or in the foam formulation. Parts by weight per 100 parts by weight of polyol are abbreviated as pphp. Thus, for example, by 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. In a preferred embodiment, the catalyst composition defined by formula (I) is present in an amount of about 0.05 to about 1 pphp. In another preferred embodiment, the catalyst composition defined by formula (I) is present in an amount of about 0.05 to about 0.5 pphp. In another preferred embodiment, the catalyst composition defined by formula (I) is present in an amount of about 0.05 to about 0.2 pphp. In another preferred embodiment, the catalyst composition defined by formula (I) is present in an amount of about 0.05 to about 0.1 pphp. Similarly, all other ranges disclosed herein should be interpreted in the same manner as these two examples.

[0028] If the applicant, for any reason, chooses to claim less than the full amount 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 sub-range or combination of sub-ranges within that group) that can be claimed according to a range or in any similar manner. Further, if the applicant, for any reason, chooses to claim less than the full amount 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.

[0029] In one embodiment of the method of the present invention, the catalyst composition defined by formula (I) comprises at least one member selected from the group consisting of bis(N,N-2-dimethylaminoethoxyethyl)methylamine, bis(N,N-2-dimethylaminoethoxyethyl)ethylamine, bis(N,N-2-dimethylaminoethoxyethyl)propylamine, bis(N,N-2-dimethylaminoethoxyethyl)isopropylamine, bis(N,N-2-diethylaminoethoxyethyl)methylamine, bis(N,N-2-diethylaminoethoxyethyl)ethylamine, bis(N,N-2-diethylaminoethoxyethyl)propylamine, bis(N,N-2-diethylaminoethoxyethyl)isopropylamine, bis(N,N-2-dipropylaminoethoxyethyl)methylamine, bis(N,N-2-dipropylaminoethoxyethyl)ethylamine, bis(N,N-2-dipropylaminoethoxyethyl)propylamine, bis(N,N-2-dipropylaminoethoxyethyl)isopropylamine, and the like. Such compounds can be used individually or in any combination thereof.

[0030] In one embodiment of the method of the present invention, 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.

[0031] In one embodiment of the method of the present invention, 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 alternative tertiary amine catalyst can be a conventional tertiary amine catalyst having at least one isocyanate-reactive group or having no isocyanate-reactive group. Preferred examples of isocyanate-reactive groups include primary hydroxyl groups, secondary hydroxyl groups, primary amine groups, secondary amine groups, urea groups or amide groups. Preferred examples of tertiary amine catalysts having isocyanate-reactive groups 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, 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, 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,NN-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, N,N-dimethylaminoethyl-N’-methyl-N’-ethanol, dimethylaminoethoxyethanol, N,N,N’-trimethyl-N’-3-aminopropyl-bis(aminoethyl)ether, or combinations thereof, but not limited thereto. 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.,

[0032] In one embodiment of the method of the present invention, 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 and is diazabicyclooctane (triethylenediamine), 1,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl)amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, or combinations 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, such as bis(dimethylaminoethyl)ether, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine and related compositions, and furthermore polyvalent permethylated polyamines. In addition to or instead of the above, in another embodiment, the tertiary amine catalyst component is 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 combinations thereof, or includes them.,

[0033] In one embodiment of the method of the present invention, the catalyst composition 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. In a preferred embodiment of the method of the present invention, the catalyst composition is acid-blocked with a carboxylic acid or a sulfonic acid. Examples of carboxylic acids include monoacids, diacids or polyacids, with or without isocyanate-reactive groups. Preferred examples of 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 catalyst can be obtained by known methods using conventional equipment.

[0034] In one embodiment of the method of the present invention, the tertiary amine catalyst component is preferably used together with a transition metal catalyst. For example, in certain embodiments, the tertiary amine catalyst component is used with an organotin compound, a tin(II) carboxylate, a bismuth(III) carboxylate, or a combination thereof. Examples of 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) can also be included. Suitable bismuth carboxylates include salts of 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, and other suitable carboxylic acids. Other salts of transition metals, lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids can also be included.

[0035] The catalyst composition defined by formula (I) can be produced, for example in the case of bis(N,N-2-dimethylaminoethoxyethyl)methylamine, by following the procedure below: A fixed-bed tubular reactor equipped with a 10 cc quartz preheating bed was charged with 8.8 g of a CuO / ZnO / Al2O3 catalyst having a typical composition of 61% CuO, 28% ZnO and 10% Al2O3, sold by Siid Chemie under the name of T-4581 material. The reactor was pressurized with nitrogen up to 20.7 bar (300 psig) and then vented to the atmosphere. The pressure of the reactor was maintained by a backpressure controller. The nitrogen purge was repeated for 2 more 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. Analysis of the effluent from the reactor by GC showed that about 5 - 10% of bis(N,N-2-dimethylaminoethoxyethyl)methylamine was obtained, which was separated and purified by distillation.

[0036] In another embodiment of the method of the present invention, 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 alkali metals, alkaline earth metals, 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 a combination thereof.

[0037] 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.

[0038] It is also within the scope of the method of the present invention to include a mixture or combination of two or more catalyst compositions defined by formula (I). Furthermore, the method of the present invention can further include at least one urethane catalyst having no isocyanate-reactive groups.

[0039] The term "contacting substances" is used herein to describe compositions in which the components are brought into contact with each other in any order and by any means over any period of time. 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 typically done in the form of a solution.

[0040] 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.

[0041] Polyisocyanate Polyisocyanates useful in the PIR / PUR foam forming process include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate isomers (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.

[0042] The PIR / PUR foam production method of the present invention can be used to produce foam products for flame retardant applications, which usually 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 equivalent / equivalent of active hydrogen) × 100 [wherein the NCO equivalent is the number of NCO functional groups in the polyisocyanate, and the equivalent of active hydrogen is the number of active hydrogen atom equivalents].

[0043] Foam products produced with an isocyanate index of about 10 to about 800 are within the scope of the present invention. According to another embodiment of the present invention, the isocyanate index is in the range of about 20 to about 700, about 30 to about 650, about 50 to about 600, or about 700 to about 500.

[0044] Polyol The active hydrogen-containing compounds for use with the aforementioned polyisocyanates in the formation of the polyisocyanurate / polyurethane foams of the present invention can be any organic compounds having at least two hydroxyl groups, such as polyols. Polyols typically used in the PIR / PUR foam formation 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 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 sugars such as sucrose and similar low molecular weight polyols.

[0045] In the present invention, amine polyether polyols can be used. These can be prepared by reacting amines such as ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine or triethanolamine with ethylene oxide or propylene oxide.

[0046] 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.

[0047] In yet another embodiment of the present invention, a polyester polyol can be used that includes what is produced when a dicarboxylic acid is reacted with an excess of diol. Non-limiting examples include adipic acid or phthalic acid or phthalic anhydride that react 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, polyols such as polyester polyols and polyether polyols, and combinations thereof, are useful in the present invention.

[0048] The polyol can 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.

[0049] The amount of polyol can 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.

[0050] Blowing agent According to the PIR / PUR foam production method included in the scope of the present invention, suitable blowing agents that can be used alone or in combination 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, 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).

[0051] 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, a fluorocarbon, a chlorocarbon, a fluorochlorocarbon, a halogenated hydrocarbon, an ether, a fluorinated ether, an ester, an aldehyde, a ketone, a carbon dioxide generating material, or a combination thereof. The hydrohaloolefin preferably includes at least one haloalkene, such as a fluoroalkene or a chloroalkene containing 3 to 4 carbon atoms and at least one carbon-carbon double bond. Preferred hydrohaloolefins include, without limitation, 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 on 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, and all possible structural isomers, geometric isomers, or stereoisomers thereof are included.Preferred optional blowing agents include, but are not limited to, water, formic acid, organic acids that produce carbon dioxide when reacting with isocyanate, hydrocarbons, ethers, halogenated ethers, pentafluorobutane, pentafluoropropane, hexafluoropropane, heptafluoropropane, trans-1,2-dichloroethylene, 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 usually 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 usually 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 usually 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.

[0052] Since chlorofluorocarbons (CFCs) have been found to be able to deplete stratospheric ozone, 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.

[0053] The amount of blowing agent used can vary, for example, based on the intended use and application of the foam product and the desired rigidity and density of the foam. In a method for preparing the polyisocyanurate / polyurethane foam of the present invention, the blowing agent is present in an amount of about 5 to about 80 parts by weight per 100 parts by weight of the at least one polyol. In another embodiment, the blowing agent is present in an amount of about 5 to about 80 parts per hundred parts by weight (pphp), about 10 to about 60 pphp, about 15 to about 50 pphp, or about 20 to about 40 pphp of the polyol.

[0054] When water is present in the formulation for use as a blowing agent or otherwise, the water is present in an amount in the range of 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.

[0055] Urethane catalyst In one embodiment, in order to accelerate the reaction for forming polyurethane, a conventional urethane catalyst having no isocyanate-reactive group can be used, and this can be used as a further component of the catalyst system and composition of the present invention for producing a polyisocyanurate / polyurethane foam. Examples of urethane catalysts suitable for use herein 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), pentamethyldipropylenetriamine, 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, and the like, and any mixtures thereof, but are not limited thereto.

[0056] 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 alternative tertiary amine gelation co-catalyst consist essentially of primary amines, secondary amines, secondary hydroxyl groups, amides and ureas. Examples of gelation catalysts 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}. Examples of blowing co-catalysts containing isocyanate-reactive groups that can be used with the above-described gelation catalysts include 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol (DABCO® NE200), N,N,N’-trimethyl-N’-3-aminopropyl-bis(aminoethyl)ether (DABCO® NE300).

[0057] Suitable urethane catalysts that can be used in combination with a catalyst in the process of the present invention preferably include tertiary amines acid-blocked with a carboxylic acid (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acid or any other organic or inorganic acid. Examples of carboxylic acids include monoacids, diacids or polyacids, with or without isocyanate-reactive groups. Examples of 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.

[0058] 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 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 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.

[0059] In another embodiment, the present invention can further include 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.

[0060] To prepare the polyisocyanurate / polyurethane foam of the present invention, the formulation can contain 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 a urethane catalyst. In another embodiment, 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 a urethane catalyst is present.

[0061] Other additives Depending on the requirements during foam manufacture or the end-use requirements of the foam product, various additives can be used in the PIR / PUR foam formulation to adapt to specific properties. These additives preferably include, but are not limited to, cell 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 are, of course, within the scope of the present invention.

[0062] The foam stabilizer includes 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.

[0063] Polyurethane Foam Formulation and Process The present invention provides a method for preparing a flexible slabstock polyurethane foam and a flexible slabstock polyisocyanurate / polyurethane (PIR / PUR) foam, which includes contacting at least one polyisocyanate with at least one polyol in the presence of a catalyst composition containing at least one polyurethane additive selected from the group consisting of a blowing agent, a foam stabilizer, and a crosslinking agent, and an effective amount of at least one compound represented by formula (I). According to the method of the present invention, about 8 Kg / m 3 ~ about 250 Kg / m 3 (about 0.5 lb / ft 3 ~ about 15.5 lb / ft 3 ) or about 24 Kg / m 3 ~ about 60 Kg / m 3 (about 1.5 lb / ft 3 ~ about 3.75 lb / ft 3) PUR and PIR / PUR foams having the density of can be manufactured.

[0064] The present invention can be used in a wide range of methods for producing flexible slabstock foams and flexible molded foams. Examples of suitable methods include, among numerous foam production methods, injection, molding, spraying.

[0065] The present method for preparing PUR and PIR / PUR foams can also provide a polyol premix with less ammonia odor when compared with other commercially available catalyst systems.

[0066] The catalyst composition defined by formula (I) above is preferably present in a catalytically effective amount in the foam formulation. Preferably, the catalyst composition is present in an amount of about 0.05 to about 10 parts per hundred parts by weight (pphp) of polyol. In another embodiment, the catalyst composition is present in an amount of 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. In a preferred embodiment, the catalyst composition defined by formula (I) is present in an amount of about 0.05 to about 1 pphp. In another preferred embodiment, the catalyst composition defined by formula (I) is present in an amount of about 0.05 to about 0.5 pphp. In another preferred embodiment, the catalyst composition defined by formula (I) is present in an amount of about 0.05 to about 0.2 pphp. In another preferred embodiment, the catalyst composition defined by formula (I) is present in an amount of about 0.05 to about 0.1 pphp.

[0067] 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 polyol, 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 changing the order of addition of the components is within the scope of the present invention. Similarly, for each of the different orders in which the 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 can further comprise the presence of 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. In one embodiment of the present invention, all components including optional components are contacted substantially simultaneously.

[0068] In another embodiment of the present invention, a premix of the components other than the at least one polyisocyanate is first contacted, and then the at least one polyisocyanate is added. For example, the at least one active hydrogen-containing compound, the at least one blowing agent, the at least one foam stabilizer, and the catalyst composition of the present invention are first contacted to form a premix. Then, the premix is contacted with the 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, where the premix further comprises at least one urethane catalyst. Similarly, the premix can 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.

[0069] In another embodiment of the present invention, the flexible slabstock polyurethane foam comprises a contact product of at least one polyol, at least one isocyanate, and a catalyst composition comprising at least one compound represented by formula (I). In a preferred embodiment, the contact product further comprises a tertiary amine having or not having isocyanate-reactive groups. In another preferred embodiment, the contact product further comprises 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.

[0070] One embodiment of the present invention provides a method for preparing polyurethane, polyisocyanurate, polyisocyanurate / polyurethane foam, comprising the following steps:

[0071] (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 above by formula (I) in an amount of about 0.05 to about 10 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.

[0072] In another embodiment of the present invention, there is provided a method for preparing bis(N,N-2-dimethylaminoethoxyethyl)methylamine (BDMAEEN), the method comprising the following steps: (a) Reacting dimethylaminoethoxyethanol (DMAEE) with methylamine (MMA), thereby preparing a mixture containing bis(N,N-2-dimethylaminoethoxyethyl)methylamine (BDMAEEN), N,N,N'-trimethylbis(aminoethyl)ether (TMAEE) and other components, and (b) Separating bis(N,N-2-dimethylaminoethoxyethyl)methylamine (BDMAEEN) from the mixture.

[0073] The following is a list of preferred items of the present invention. Item 1. At least one polyurethane additive selected from the group consisting of a blowing agent, a foam stabilizer and a crosslinking agent, and at least one polyisocyanate is contacted with at least one polyol in the presence of a catalyst composition containing at least one compound represented by formula (I):

Chemical formula

Examples

[0074] These examples are provided to demonstrate specific embodiments of the present invention and are not intended to limit the scope of the appended claims.

[0075] Example 1 (of the present invention) Describe the synthesis of bis(N,N-2-dimethylaminoethoxyethyl)methylamine.

[0076] 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 2 more 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, and approximately 5 - 10% of bis(N,N-2-dimethylaminoethoxyethyl)methylamine (BDMAEEN) was obtained mainly together with TMAEE (N,N,N'-trimethylbis(aminoethyl)ether) and other components separated by distillation.

[0077] Example 2 (the present invention) This example describes the synthesis of crude bis(N,N-2-dimethylaminoethoxyethyl)methylamine (crude BDMAEEN).

[0078] The crude sample of BDMAEEN was prepared using the same procedure as described in Example 1. This sample was produced by distillation of the effluent obtained in Example 1, and 25% of "crude BDMAEEN" was obtained after removal of N,N,N'-trimethyl-aminoethyl ether (TMAEE) as well as excess starting material (DMAEE) and a small amount of BDMAEE (bis-dimethylaminoethyl ether). The composition of the crude BDMAEEN was approximately 50 - 60% 2-[2-(dimethylamino)ethoxy]-N,N-dimethyl-acetamide, 10 - 20% bis(N,N-2-dimethylaminoethoxyethyl)methylamine (BDMAEEN), 4 - 8% N,N-bis(dimethylaminoethoxyethyl)amine, and approximately 4 - 6% 2-[2-(dimethylamino)ethoxy]-N-methyl-N-(dimethylaminoethoxyethyl)-acetamide.

[0079] Example 3 (the present invention) This example describes the purification of bis(N,N-2-dimethylaminoethoxyethyl)methylamine (pure BDMAEEN).

[0080] The crude sample of BDMAEEN described in Example 2 was distilled off under nitrogen to obtain a clear liquid composed of BDMAEEN and a small amount of N,N-bis(dimethylaminoethoxyethyl)amine. This sample was produced by distillation after removing 2-[2-(dimethylamino)ethoxy]-N,N-dimethyl-acetamide, 2-[2-(dimethylamino)ethoxy]-N-methyl-N-(dimethylaminoethoxyethyl)-acetamide, and other heavy impurities. The distillation fraction contained N,N-bis(dimethylaminoethoxyethyl)amine together with the desired compound bis(N,N-2-dimethylaminoethoxyethyl)methylamine (BDMAEEN). N,N-bis(dimethylaminoethoxyethyl)amine was converted to bis(N,N-2-dimethylaminoethoxyethyl)methylamine (BDMAEEN) by reductive alkylation using a standard procedure with formaldehyde, hydrogen, and a 5% Pd / C catalyst.

[0081] Example 4 (the present invention) In this example, the form rise rate kinetics and usage levels of bis(N,N-2-dimethylaminoethoxyethyl)methylamine (BDMAEEN) are described.

[0082] The foaming performance can be evaluated by comparing the foam height versus time for standard and new amine catalysts. The foam height profile can be measured by an automated rise rate device that uses a free-rise cup foam sample with a FOMAT sonar rise rate device (hereinafter referred to as "ROR"). The FOMAT device is equipped with a sonar sensor that measures and records the height (in millimeters (mm)) of the rising foam sample versus time (in seconds (s)) immediately after all the 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 mixing the components in Table 2 other than isocyanate in a 32 ounce (951 ml) paper cup with a total weight of approximately 300 g. Next, this premix formulation is 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. Next, sufficient toluene diisocyanate is added to achieve a desired isocyanate index of approximately 100, and the formulation is further mixed well at approximately 6,000 rpm for approximately 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 restrict expansion in all directions except the vertical direction, this expansion appears as an increase in height over time in this experiment. [Table 1]

[0083] 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 = top 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 rate of the forming reaction. [Table 2]

[0084] Example 5 (the present invention) In this example, the physical properties of a polyurethane foam prepared using BDMAEEN as a blowing catalyst are compared with those of a comparative BDMAEE standard catalyst.

[0085] The foam samples 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 poured into a 5-gallon bucket and subsequently allowed to rise freely. The bucket containing the foam samples was stored under constant temperature and humidity conditions for 48 hours, then cut and tested. [Table 3] [Table 4]

[0086] Table 4 shows that the environmental physical properties are extremely similar and that using BDMAEEN gives a foam with excellent physical properties. Table 4 also shows that the foam produced using BDMAEEN has significantly better compression set and better air permeability than the foam sample produced under the same conditions using Dabco® BL11 (70% dipropylene glycol solution of BDMAEE).

[0087] Example 6 (the present invention) In this example, the foam rise rate kinetics and usage level comparison of bis(N,N-2-dimethylaminoethoxyethyl)methylamine (BDMAEEN) are described.

[0088] 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 rise rate device that uses a free-rise cup foam sample with a FOMAT sonar rise rate device (hereinafter referred to as "ROR"). The FOMAT device is equipped with a sonar sensor that measures and records the height (in millimeters (mm)) of the rising foam sample versus time (in seconds (s)) immediately after mixing all the components of the formulation. 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 mixing the components in Table 5 other than isocyanate, with a total weight of approximately 300 g, in a 32 ounce (951 ml) paper cup. Next, this premix formulation is 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. Next, sufficient toluene diisocyanate is added to achieve a desired isocyanate index of approximately 100, and the formulation is further mixed well at approximately 6,000 rpm for approximately 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 the expansion in all directions except vertically, this expansion appears in this experiment as an increase in height over time.

Table 5

[0089] 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), useful comparisons can be made regarding the speed of the forming reaction.

Table 6

[0090] Example 7 (the present invention) In this example, the physical properties of polyurethane foams prepared using pure BDMAEEN and the standard catalyst DABCO® BL11 (BDMAEE) used in the polyurethane industry are compared.

[0091] The foam pads were prepared by adding a tertiary amine catalyst to approximately 302 g of premix (prepared as in Table 2) 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 mixed well for an additional approximately 6 seconds at approximately 6,000 RPM 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 7

Table 8

[0092] Table 8 shows the physical properties of soft molded polyurethane pads prepared using combinations of the standard gelling / foaming reactive amine catalysts Dabco® 33LV / Dabco® BL11, the standard gelling / foaming reactive amine catalysts Dabco® NE1070 / Dabco® NE300, and the combination when Dabco® BL11 and Dabco® NE300 are replaced with BDMAEEN during environmental aging and humid aging. Table 8 shows that the environmental physical properties are very similar when BDMAEE is used instead of BL11. Table 8 also shows that foams made using BDMAEEN generally have better physical properties than Dabco® NE300.

[0093] Example 8 (the present invention) In this example, the physical properties of polyurethane foams prepared using the catalyst, pure BDMAEEN, and the standard catalyst Dabco® NE300 used in the polyurethane industry are compared.

[0094] Using the following formulations with MDI, foam pads were prepared as described above.

Table 9

[0095] This formulation was 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, toluene diisocyanate was added, and the formulation was further mixed well at about 6,000 RPM for about 6 seconds using the same stirrer, then poured into a preheated mold at 70 °C and demolded after 4 minutes. The foam pad was removed from the mold, crushed by hand, weighed, and mechanically crushed at 75% of the pad thickness. The foam pad was stored under constant temperature and humidity conditions for 48 hours, then cut and tested.

Table 10

Table 11

[0096] Table 11 shows that the MDI form prepared using BDMAEEN has better physical properties than the form prepared using DABCO® NE300.

Claims

**Claim 1** A method for preparing a flexible slabstock polyurethane foam, comprising contacting at least one polyisocyanate with at least one polyol in the presence of a catalyst composition comprising at least one polyurethane additive selected from the group consisting of a blowing agent, a foam stabilizer, and a crosslinking agent, and at least one compound represented by formula (I). 【Chemical 1】 [wherein, R １ , R ２ , R ３、 R ４ and R ５ are each independently a linear or branched C １ -C ３ alkyl or C ２ -C ６ alkenyl]] **Claim 2** The method according to claim 1, wherein the catalyst composition is present in an amount of about 0.05 to about 0.5 pp hp. **Claim 3** R １ 、 R ２ 、 R ３ 、 R ４ and R ５ is, independently, a methyl group, the method according to claim 1 or 2. **Claim 4** The at least one compound of general formula I is selected from the group consisting of bis(N,N-2-dimethylaminoethoxyethyl)methylamine, bis(N,N-2-dimethylaminoethoxyethyl)ethylamine, bis(N,N-2-dimethylaminoethoxyethyl)propylamine, bis(N,N-2-dimethylaminoethoxyethyl)isopropylamine, bis(N,N-2-diethylaminoethoxyethyl)methylamine, bis(N,N-2-diethylaminoethoxyethyl)ethylamine, bis(N,N-2-diethylaminoethoxyethyl)propylamine, bis(N,N-2-diethylaminoethoxyethyl)isopropylamine, bis(N,N-2-dipropylaminoethoxyethyl)methylamine, bis(N,N-2-dipropylaminoethoxyethyl)ethylamine, bis(N,N-2-dipropylaminoethoxyethyl)propylamine, bis(N,N-2-dipropylaminoethoxyethyl)isopropylamine, and combinations thereof. The method according to claim 1 or 2. **Claim 5** The method according to any one of claims 1 to 4, wherein the catalyst composition is present in combination with a transition metal catalyst, a tertiary amine with or without an isocyanate-reactive group, or a combination thereof. **Claim 6** The method according to claim 5, wherein the tertiary amine 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. **Claim 7** The tertiary amine 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-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, 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 method according to claim 5 or 6, selected from the group consisting of N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl) ether, or combinations thereof. **Claim 8** The method according to claim 5, wherein the transition metal catalyst is an organotin compound, a tin(II) carboxylate, a bismuth(III) carboxylate, or a combination thereof. **Claim 9** The method according to any one of claims 1 to 8, wherein the catalyst composition is acid-blocked with a carboxylic acid or a sulfonic acid.

10. The method according to claim 9, wherein the 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-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, and salicylic acid.

11. The method according to any one of claims 1 to 10, 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, 2-hydroxypropyltrimethylammonium octanoate solution, or a combination thereof.

12. A flexible slabstock polyurethane foam prepared by the method according to any one of claims 1 to 11.

13. A method for preparing bis(N,N-2-dimethylaminoethoxyethyl)methylamine, the method comprising the following steps: (a) reacting dimethylaminoethoxyethanol with methylamine to thereby prepare a mixture containing bis(N,N-2-dimethylaminoethoxyethyl)methylamine, N,N,N'-trimethylbis(aminoethyl)ether, and other components; and (b) separating bis(N,N-2-dimethylaminoethoxyethyl)methylamine from the mixture.

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