Foam-forming composition containing metal carboxylate catalyst, related foam and method for production thereof

Abstract

To provide polyurethane foam-forming compositions, methods of producing polyurethane foams, polyurethane foams produced from compositions made by such methods, as well as isocyanate-reactive compositions.SOLUTION: A polyurethane foam-forming composition includes (a) a polyol, (b) a catalyst composition comprising a tertiary amine and a metal carboxylate, (c) a blowing agent composition comprising a physical blowing agent and water, (d) a β-dicarbonyl compound, and (e) a polyisocyanate.SELECTED DRAWING: None

Description

[Technical field]

[0001] This disclosure generally relates to polyurethane foam-forming compositions comprising (a) a polyol, (b) a catalyst composition comprising a tertiary amine and a metal carboxylate, (c) a blowing agent composition comprising a physical blowing agent and water, (d) a β-dicarbonyl compound, and (e) a polyisocyanate. This disclosure also relates to methods of producing polyurethane foams using such polyurethane foam-forming compositions, and to polyurethane foams produced from such foam-forming compositions. [Background technology]

[0002] Rigid polyurethane foams are used in a variety of applications. They are produced by reacting a polyisocyanate with an isocyanate-reactive compound, usually a polyol, in the presence of a blowing agent. One use of such foams is as an insulating medium in the construction of refrigerated storage equipment, including refrigeration appliances and trailer trucks.

[0003] There are several physical properties that are important for such foams. Specifically, the foam must be dimensionally stable and exhibit good compressive strength, as well as exhibit good thermal insulation properties (as determined by K-factor measurements). To achieve this, the flow profile of the foam-forming composition must be optimized to minimize cell elongation. Cell elongation is often the result of an imbalance between the cure and flow profiles, which causes the foam-forming composition to begin to gel, i.e., increase in viscosity, before the foam-forming composition has finished flowing (rise time). Foam formulators often achieve an optimal flow profile by carefully selecting a specific catalyst package, often including a combination of a blow catalyst (a catalyst that promotes the isocyanate-water reaction) and a gel catalyst (a catalyst that promotes the isocyanate-polyol reaction). However, a drawback of this solution is that it can severely limit the foam formulator's flexibility in terms of catalyst selection and amount.

[0004] It would therefore be desirable to provide a means to easily tailor and optimize the flow profile of insulating rigid polyurethane foam formulations, thus offering the foam formulator greater formulation flexibility. Summary of the Invention

[0005] In certain aspects, the present disclosure relates to polyurethane foam-forming compositions. These polyurethane foam-forming compositions include a polyol, a catalyst composition, a blowing agent composition, a β-dicarbonyl compound, and a polyisocyanate. The catalyst composition comprises a tertiary amine and a β-dicarbonyl compound having the structure: [ka] and a metal carboxylate having the formula: wherein each R may be the same or different, is a saturated or unsaturated, optionally substituted (cyclo)alkyl group having 2 to 25 carbon atoms, x is 2 or 3, and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium. The blowing agent composition comprises a physical blowing agent and water. The β-dicarbonyl compound has the structure: [ka] (In the formula, (i) each R 1 may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, or halogen atoms such as fluorine, and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R2 is hydrogen or R 1 )

[0006] In another aspect, the present disclosure relates to a method for producing a polyurethane foam. The method comprises reacting a polyurethane foam-forming composition comprising a polyol, a polyisocyanate, a catalyst composition, a blowing agent composition, and a β-dicarbonyl compound at an Isocyanate Index of 0.90 to 1.50. The catalyst composition comprises a tertiary amine and a β-dicarbonyl compound having the structure: [ka] and a metal carboxylate having the formula: wherein each R may be the same or different, is a saturated or unsaturated, optionally substituted (cyclo)alkyl group having 2 to 25 carbon atoms, x is 2 or 3, and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium. The blowing agent composition comprises a physical blowing agent and water. The β-dicarbonyl compound has the structure: [ka] (In the formula, (i) each R 1 may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, or halogen atoms such as fluorine, and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R 2 is hydrogen or R 1 )

[0007] In yet another aspect, the present disclosure relates to isocyanate-reactive compositions. These isocyanate-reactive compositions include a polyol, a catalyst composition, a blowing agent composition, and a β-dicarbonyl compound. The catalyst composition includes a tertiary amine and a β-dicarbonyl compound having the structure: [ka] and a metal carboxylate having the formula: wherein each R may be the same or different, is a saturated or unsaturated, optionally substituted (cyclo)alkyl group having 1 to 20 carbon atoms, x is 2 or 3, and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), cobalt(III), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium. The blowing agent composition comprises a physical blowing agent and water. The β-dicarbonyl compound has the structure: [ka] (In the formula, (i) each R 1 may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, or halogen atoms such as fluorine, and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R 2 is hydrogen or R 1 )

[0008] This specification also relates to rigid polyurethane foams produced from such foam-forming compositions and by such processes, and to composite articles comprising such rigid foams, and to panel insulation comprising such rigid foams. [Brief description of the drawings]

[0009] [Figure 1(a)] FIG. 13 shows a graph of the rise rate profile of an example foam. [Figure 1(b)] FIG. 13 shows a graph of the rise rate profile of an example foam. [Figure 1(c)] FIG. 13 shows a graph of the rise rate profile of an example foam. [Figure 1(d)] FIG. 13 shows a graph of the rise rate profile of an example foam. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Various embodiments are described and discussed herein to provide a thorough understanding of the structure, function, properties, and use of the disclosed invention. It is understood that the various embodiments described and discussed herein are non-limiting and non-exhaustive. Thus, the present invention is not limited by the description of the various non-limiting and non-exhaustive embodiments disclosed herein. Features and characteristics described in connection with various embodiments may be combined with features and characteristics of other embodiments. Such modifications and variations are intended to be included within the scope of the present specification. Accordingly, the claims may be amended to recite any feature or characteristic that is explicitly or inherently described or explicitly or inherently supported herein. Furthermore, the applicant(s) reserve the right to amend the claims to affirmatively disclaim any feature or characteristic that may exist in the prior art. Any such amendment is therefore in compliance with the requirements of 35 U.S.C. 112 and 35 U.S.C. 132(a). The various embodiments disclosed and described herein may comprise, consist of, or consist essentially of the features and characteristics as variously described herein.

[0011] Any patent, publication, or other disclosure material identified herein is incorporated herein by reference in its entirety unless otherwise stated, but only to the extent that the incorporated material does not contradict existing definitions, descriptions, or other disclosure material expressly set forth herein. Thus, to the extent necessary, the express disclosure set forth herein supersedes any conflicting material made part of this specification by reference. Any material, or portion thereof, that is said to be made part of this specification by reference but that contradicts existing definitions, descriptions, or other disclosure material set forth herein, is incorporated only to the extent that no conflict occurs between the incorporated material and the existing disclosure material. The applicant(s) reserve the right to amend this specification to explicitly recite any subject matter, or portion thereof, made part of this specification by reference.

[0012] As used herein, unless otherwise expressly indicated, all numerical parameters are to be understood as being prefaced and modified in all instances by the term "about," having the inherent variability characteristic of the underlying measuring technique used to determine the numerical value of the parameter. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter set forth herein should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0013] Also, any numerical range recited herein is intended to include all subranges of the same numerical precision subsumed within the recited range. For example, the range "1.0 to 10.0" is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, i.e., subranges having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein, and any minimum numerical limitation recited herein is intended to include all higher numerical limitations subsumed therein. Accordingly, the applicant(s) reserve the right to amend this specification, including the claims, to expressly recite any subranges subsumed within the ranges expressly recited herein. Any such ranges are intended to be essentially described herein, such that amendment to expressly recite any such subranges complies with the requirements of 35 U.S.C. § 112 and 35 U.S.C. § 132(a).

[0014] As used herein, the grammatical articles "one", "a", "an", and "the" are intended to include "at least one" or "one or more" unless otherwise specified. Thus, the articles are used herein to refer to one or more than one (i.e., "at least one") of the grammatical object of the article. By way of example, "a β-dicarbonyl compound" means one or more β-dicarbonyl compounds, and thus, more than one β-dicarbonyl compound is contemplated, may be employed, or may be used. Furthermore, unless otherwise specified in the context of the usage, the use of the singular noun includes the plural and the use of the plural noun includes the singular.

[0015] As used herein, the term "functionality" refers to the average number of reactive hydroxyl groups -OH present per molecule of the -OH functional material described, and in the case of the polyether polyols described herein, is calculated by the functionality of the starting compound used to make the polyether polyol. In the production of polyurethane foam, the hydroxyl groups react with the isocyanate groups -NCO attached to the isocyanate compound. The term "hydroxyl number" refers to the number of reactive hydroxyl groups available for reaction, expressed as the number of milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of polyol (ASTM D4274-16). The term "equivalent weight" refers to the weight of a compound divided by its atomic valence. In the case of a polyol, the equivalent weight is the weight of the polyol that combines with the isocyanate groups and can be calculated by dividing the molecular weight of the polyol by its functionality. The equivalent weight of a polyol can also be calculated by dividing 56100 by the hydroxyl number of the polyol. Equivalent weight (g / eq) = (56.1 x 1000) / OH number.

[0016] As indicated, certain embodiments herein relate to polyurethane foam-forming compositions useful for producing rigid foams, characterized by a compressive strength to tensile strength ratio of at least 0.5:1, an elongation of less than 10%, and a low recovery from strain and a low elastic limit, as described in "Polyurethanes: Chemistry and Technology, Part II Technology," J.H. Saunders & K.C. Frisch, Interscience Publishers, 1964, page 239.

[0017] The polyurethane foam-forming compositions herein include a polyisocyanate. As used herein, the term "polyisocyanate" encompasses not only diisocyanates but also polyisocyanates with a functionality greater than 2.0.

[0018] Any of the known organic isocyanates, modified isocyanates, or isocyanate-terminated prepolymers made from any of the known organic isocyanates can be used. Suitable organic isocyanates include aromatic, aliphatic, and cycloaliphatic polyisocyanates, and combinations thereof. Useful isocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isomers of hexahydrotoluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenyl diisocyanate, 5,5'-diphenyl diisocyanate, 6,5'-diphenyl diisocyanate, 7,5'-diphenyl diisocyanate, 8,5'-diphenyl diisocyanate, 9,5'-diphenyl diisocyanate, 10,5'-diphenyl diisocyanate, 11,5'-diphenyl diisocyanate, 12,5'-diphenyl diisocyanate, 13,5'-diphenyl diisocyanate, 14,5'-diphenyl diisocyanate, 15,5'-diphenyl diisocyanate, 16,5'-diphenyl diisocyanate, 17,5'-diphenyl diisocyanate, 18,5'-diphenyl diisocyanate, 19,6 ... Examples of the isocyanate include diisocyanates such as diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, and 3,3'-dimethyldiphenylpropane-4,4'-diisocyanate, triisocyanates such as 2,4,6-toluene triisocyanate, and polyisocyanates such as 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate and polymethylene polyphenyl-polyisocyanate.

[0019] Undistilled or crude polyisocyanates can also be used. Crude toluene diisocyanate obtained by phosgenating a mixture of toluene diamine and crude diphenylmethane diisocyanate (polymeric MDI) obtained by phosgenating crude diphenylmethane diamine are examples of suitable crude polyisocyanates. Suitable undistilled or crude polyisocyanates are disclosed in U.S. Pat. No. 3,215,652.

[0020] Modified isocyanates are obtained by chemical reaction of diisocyanates and / or polyisocyanates. Useful modified isocyanates include, but are not limited to, isocyanates containing ester groups, urea groups, biuret groups, allophanate groups, carbodiimide groups, isocyanurate groups, uretdione groups, urethane groups, or any combination of two or more thereof. Examples of modified isocyanates include those based on prepolymers, such as polyether polyols or polyester polyols, and diphenylmethane diisocyanate, that contain NCO groups and have an NCO content of 25% to 35% by weight, for example 29% to 34% by weight.

[0021] In certain embodiments, the polyisocyanate comprises a methylene bridged polyphenyl polyisocyanate and / or a prepolymer of a methylene bridged polyphenyl polyisocyanate having an average functionality of 1.8 to 3.5, e.g., 2.0 to 3.1, isocyanate moieties per molecule and an NCO content of 25% to 32% by weight.

[0022] The polyurethane foam-forming compositions herein include a polyol, such as a polyether polyol. In some embodiments, the polyol comprises a blend of two or more different polyether polyols. Suitable polyether polyols include, but are not limited to, those prepared by adding an alkylene oxide, often in the presence of a catalyst such as a base catalyst or a double metal cyanide (DMC) compound, to a starter compound having an isocyanate-reactive hydrogen atom. These starter compounds often have a functionality of 2 to 8, e.g., 2 to 6, or 2 to 4, and in some embodiments are amine-functional and / or hydroxyl-functional. Specific examples of suitable starting material compounds include (i) polyhydroxy compounds such as water, ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, and any combination of two or more thereof, (ii) organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid, terephthalic acid, and any combination of two or more thereof, (iii) amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, butylenediamine, hexamethylenediamine, toluenediamine, and any combination of two or more thereof, and (iv) any combination of two or more of the starting materials listed in (i) to (iii). Suitable alkylene oxides include, for example, ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and any combination of two or more thereof. In some embodiments, propylene oxide and ethylene oxide are introduced to the reaction mixture alone, in admixture, or sequentially. When the alkylene oxides are added sequentially, the resulting product contains polyether chains having a block structure.

[0023] In some embodiments, the polyol blend comprises an aromatic amine-initiated polyether polyol. As used herein, "aromatic amine-initiated polyether polyol" refers to a polyether polyol that is the reaction product of an H-functional starter material that includes an aromatic amine, such as toluene diamine ("TDA"), with an alkylene oxide.

[0024] In certain embodiments, the aromatic amine used has an amine functionality of at least 1, for example 1-3 or 1-2.Specific examples of suitable aromatic amines that can be used include crude TDA obtained by nitrating toluene and then reducing; 2,3-TDA, 3,4-TDA, 2,4-TDA, 2,6-TDA or mixtures thereof; aniline; 4,4'-methylenedianiline; methylenedianiline isomers prepared by reacting aniline with formaldehyde by methods known in the art, and methylene-bridged polyphenyl polyamines composed of higher molecular weight triamines or polyamines.In some embodiments, a mixture composed of 2,3-TDA and 3,4-TDA (commonly referred to as "o-TDA") is used.

[0025] In addition to aromatic amine, other H-functional starting materials may be used to prepare aromatic amine-initiated polyether polyol. These other H-functional starting materials include, for example, water, propylene glycol, glycerin, ethylene glycol, ethanolamine, diethylene glycol, or any mixture of two or more thereof. As can be understood, various individual starting materials can be used in combination with each other. However, in some embodiments, aromatic amine is the main or essentially the only H-functional starting material used to prepare aromatic amine-initiated polyether polyol. That is, in these embodiments, aromatic amine is present in an amount of more than 50 wt%, for example at least 80 wt%, at least 90 wt%, or even 100 wt%, based on the total weight of H-functional starting materials used to prepare aromatic amine-initiated polyether polyol.

[0026] Various alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and mixtures thereof, may be used to prepare the aromatic amine-initiated polyether polyol. The alkylene oxides may be added individually, one after the other to form blocks, or as a mixture to form heteric polyethers. The aromatic amine-initiated polyether polyol may have primary hydroxyl end groups or secondary hydroxyl end groups. In some embodiments, propylene oxide is the predominant or essentially the only alkylene oxide used to prepare the aromatic amine-initiated polyether polyol. That is, in these embodiments, propylene oxide is used in an amount of more than 50 wt%, or at least 60 wt%, for example 60 wt% to 70 wt%, based on the total weight of alkylene oxide used to prepare the aromatic amine-initiated polyether polyol. In some embodiments, ethylene oxide is used in a relatively small amount. In these embodiments, ethylene oxide is used in an amount of 50% by weight or less, or 40% by weight or less, for example, 30% to 40% by weight, based on the total weight of alkylene oxide used to prepare the aromatic amine-initiated polyether polyol.

[0027] In some embodiments, the aromatic amine-initiated polyether polyol has an OH number of 200 mg KOH / g to 600 mg KOH / g and a functionality of at least 2.5. In some embodiments, the aromatic amine-initiated polyether polyol has an OH number of 300 mg KOH / g to 500 mg KOH / g, e.g., 380 mg KOH / g to 420 mg KOH / g, and an average functionality of 3.5 to 4.5, 3.8 to 4.2, or 4.0.

[0028] In some embodiments, the aromatic amine-initiated polyether polyol is present in an amount of at least 10 wt%, based on the total weight of polyols present. More specifically, in some embodiments, the aromatic amine-initiated polyol is present in an amount of 10 wt% to 40 wt%, e.g., 10 wt% to 30 wt%, or in some cases 10 wt% to 25 wt%, or 15 wt% to 25 wt%, based on the total weight of the polyol blend.

[0029] In some embodiments, the polyol blend also includes a sugar-initiated polyether polyol. As used herein, "sugar-initiated polyether polyol" refers to a polyether polyol that is a reaction product of an H-functional starting material, including a sugar such as sucrose, with an alkylene oxide. Examples of suitable alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, or a mixture of any two or more thereof. Some examples of suitable sugar initiators are sucrose, sorbitol, and maltitol, as well as other monosaccharides, disaccharides, trisaccharides, and polysaccharides. Other initiator compounds are often used in combination with the sugar initiator to prepare the sugar-initiated polyether polyol. Sugars can be co-initiated with compounds such as water, propylene glycol, glycerin, ethylene glycol, ethanolamine, diethylene glycol, or a mixture of any two or more thereof. As will be appreciated, it is possible to use a variety of individual initiator compounds in combination with the sugar initiator.

[0030] In some embodiments, the sugar is the predominant H-functional starting material used to make the sugar-initiated polyether polyol, i.e., in these embodiments, the sugar is present in an amount greater than 50 wt%, such as at least 70 wt%, or at least 80 wt%, based on the total weight of the H-functional starting materials used to make the sugar-initiated polyether polyol.

[0031] In some embodiments, propylene oxide is the main or essentially the only alkylene oxide used to prepare the sugar-initiated polyether polyol. That is, in these embodiments, propylene oxide is used in an amount of more than 50 wt%, for example at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt%, based on the total weight of alkylene oxide used to prepare the sugar-initiated polyether polyol. In some embodiments, ethylene oxide is used in a relatively small amount. Thus, in these embodiments, ethylene oxide is present in an amount of 50 wt% or less, for example 20 wt% or less, or in some cases 10 wt% or less, based on the total weight of alkylene oxide used to prepare the sugar-initiated polyether polyol.

[0032] In some embodiments, the sugar-initiated polyether polyols have an OH number from 200 mg KOH / g to 600 mg KOH / g, e.g., from 300 mg KOH / g to 550 mg KOH / g, from 300 mg KOH / g to 400 mg KOH / g, or in some cases from 350 mg KOH / g to 400 mg KOH / g, and a functionality from 4 to 6, e.g., from 5 to 6 or from 5.5 to 6.

[0033] In some embodiments, the sugar-initiated polyether polyol is present in an amount of at least 10% by weight, based on the total weight of polyols present. More specifically, in some embodiments, the sugar-initiated polyether polyol is present in an amount of from 10% to 50% by weight, such as from 20% to 40% by weight, or in some cases from 25% to 35% by weight, based on the total weight of the polyol blend.

[0034] In some embodiments, the polyol blend comprises a triol-initiated polyether polyol. As used herein, "triol-initiated polyether polyol" refers to a polyether polyol prepared by reacting an alkylene oxide with a starting material in the presence of a suitable catalyst, the starting material including a triol such as glycerin, trimethylolpropane, trimethylolethane, 2-methylpropane-1,2,3-triol, 1,2,6-hexanetriol, or a mixture of any two or more thereof. Examples of suitable alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and epichlorohydrin, and a mixture of any two or more thereof. Other initiators may be used in combination with the triol to prepare the triol-initiated polyether polyol. The triol may be co-initiated with, for example, water, propylene glycol, ethylene glycol, ethanolamine, or diethylene glycol, and a mixture of any two or more thereof. However, in some embodiments, a triol such as glycerin is the predominant starting material used to prepare the triol-initiated polyether polyols, such that in some embodiments, the triol such as glycerin is present in an amount greater than 50% by weight, such as at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, or in some embodiments, at least 98% by weight or 100% by weight, based on the total weight of the starting materials used.

[0035] In some embodiments, propylene oxide is the main or essentially the only alkylene oxide used to prepare the triol-initiated polyether polyol. That is, in these embodiments, propylene oxide is used in an amount of more than 50 wt%, for example at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or even 100 wt%, based on the total weight of alkylene oxide used to prepare the triol-initiated polyether polyol. In some embodiments, ethylene oxide is used in a relatively small amount. Thus, in these embodiments, ethylene oxide is present in an amount of 50 wt% or less, for example 20 wt% or less, or in some cases 10 wt% or less, based on the total weight of alkylene oxide used to prepare the triol-initiated polyether polyol.

[0036] In some embodiments, the triol-initiated polyether polyol has an OH number of 300 mg KOH / g to 600 mg KOH / g and a functionality of at least 2.5. In some embodiments, the triol-initiated polyether polyol has an OH number of 400 mg KOH / g to 500 mg KOH / g, e.g., 450 mg KOH / g to 500 mg KOH / g, and a functionality of 2.5 to 3.5, 2.8 to 3.2, or 3.0.

[0037] In some embodiments, the triol-initiated polyether polyol is present in an amount of at least 30% by weight, based on the total weight of polyols present. More specifically, in some embodiments, the triol-initiated polyether polyol is present in an amount of from 30% to 70% by weight, such as from 40% to 60% by weight, or in some cases from 45% to 55% by weight, based on the total weight of the polyol blend.

[0038] In certain embodiments, the sugar-initiated polyether polyol and the aromatic amine-initiated polyether polyol are present in a weight ratio of at least 1:1, such as from 1:1 to 3:1, from 1:1 to 2:1, or in some cases from 1.2:1 to 1.8:1. In certain embodiments, the triol-initiated polyether polyol and the aromatic amine-initiated polyether polyol are present in a weight ratio of at least 1:1, such as from 1:1 to 5:1, from 2:1 to 4:1, or from 2.0:1 to 3.0:1. In certain embodiments, the triol-initiated polyether polyol and the sugar-initiated polyether polyol are present in a weight ratio of 1:1, such as from 1:1 to 3:1, from 1:1 to 2:1, or in some cases from 1.2:1 to 1.8:1.

[0039] Optionally, the polyol blend may include additional compounds containing isocyanate-reactive groups, such as chain extenders and / or crosslinkers, as well as higher molecular weight polyether and polyester polyols not listed above, including, for example, ethylene glycol, propylene glycol, butylene glycol, glycerol, diethylene glycol, dipropylene glycol, dibutylene glycol, trimethylolpropane, pentaerythritol, ethylenediamine, and diethyltoluenediamine.

[0040] In certain embodiments, the polyol blend has a weighted average functionality of 3 to 5, e.g., 3.5 to 4.5 or 3.8 to 4.2, and / or a weighted average hydroxyl number of 300 mg KOH / g to 500 mg KOH / g, e.g., 350 mg KOH / g to 450 mg KOH / g. In certain embodiments, the polyol blend is present in the polyurethane foam-forming composition in an amount of at least 50% by weight, e.g., 50% to 90% by weight or 60% to 80% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0041] In some embodiments, the sum of the amounts of aromatic amine-initiated polyether polyol, sugar-initiated polyether polyol, and triol-initiated polyether polyol is at least 90% by weight, such as at least 95% by weight, at least 98% by weight, or in some cases 100% by weight, based on the total weight of the polyol blend.

[0042] As indicated, the polyurethane foam-forming compositions herein further comprise a physical blowing agent composition. As will be understood, the term "physical blowing agent" refers to a compound that is used in liquid or gas form and does not chemically react with isocyanates, but is dissolved or emulsified in the input materials used to make the polyurethane, and that vaporizes under normal reaction conditions. Suitable physical blowing agents include, for example, hydrocarbons such as cyclopentane, isopentane, n-pentane, butane, and propane, halogenated hydrocarbons, and other compounds such as perfluorinated alkanes such as perfluorohexane, perfluorinated alkenes such as 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene, 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)-2-pentene or cis-1,1,1,4,4,4-hexafluoro-2-butene, chlorofluoroalkenes such as trans-1-chloro-3,3,3-trifluoropropene, and ethers, esters, ketones, and / or acetals.

[0043] In some embodiments, the physical blowing agent, such as a hydrocarbon blowing agent, is present in an amount of at least 5% by weight, e.g., from 5% to 30% by weight, or from 5% to 20% by weight, or from 5% to 15% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0044] The polyurethane foam-forming compositions herein also include water, which acts as a carbon dioxide generating chemical blowing agent. Specifically, in some embodiments, water is used in an amount of at least 1.0 wt.%, e.g., 1.0 wt.% to 5.0 wt.%, 1.0 wt.% to 4.0 wt.%, 1.0 wt.% to 3.0 wt.%, or 1.0 wt.% to 2.0 wt.%, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0045] In certain embodiments, the physical blowing agent composition and water are present in a relative weight ratio of at least 5:1, such as from 5:1 to 50:1, from 5:1 to 20:1, or in some cases from 5:1 to 9:1 or from 5:1 to 7:1.

[0046] The polyurethane foam-forming compositions herein also include a catalyst composition. More specifically, the catalyst composition includes a tertiary amine. Specific examples of suitable tertiary amine catalysts include, for example, trialkylamines, and heterocyclic amines. Specific examples of suitable tertiary amines include, but are not limited to, trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, dimethylbenzylamine, dibutylcyclohexylamine, dimethylethanolamine, triethanolamine, diethylethanolamine, ethyldiethanolamine, dimethylisopropanolamine, dimethyloctylamine, triisopropanolamine, triethylenediamine, tetramethyl-1,3-butanediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexane-1,6-diamine, N,N,N',N',N''-pentamethyldiethylenetriamine, bis(2- dimethylaminoethoxy)methane, N,N,N'-trimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N',N'-(2-hydroxyethyl)ethylenediamine, tetramethylguanidine, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, 1,4-dimethylpiperidine, 1,2,4-trimethylpiperidine, N-(2-dimethylaminoethyl)morpholine, 1-methyl-4-(2-dimethylamino)piperidine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]-5-nonane, or any combination of two or more thereof. In some embodiments, the tertiary amine comprises a chemically blocked tertiary amine (including any of the tertiary amines described above). Chemical blocking can be achieved by protonation of tertiary amines with acids such as formic acid, acetic acid, 2-ethylhexanoic acid, oleic acid, phenol, or with boron trichloride.

[0047] In some embodiments, the tertiary amine is present in an amount of 0.01 wt% to 3.0 wt%, or 0.3 wt% to 2.5 wt%, or 1.0 wt% to 2.0 wt%, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate. More specifically, in some embodiments, the tertiary amine comprises an unblocked tertiary amine and a chemically blocked tertiary amine, for example, the unblocked tertiary amine and the chemically blocked tertiary amine are present in a weight ratio of 1:5 to 5:1, 1:3 to 3:1, 1:2 to 2:1, or 1.1:1 to 1:1.1. Further, in some embodiments, the unblocked tertiary amine and the chemically blocked tertiary amine are each present in an amount of 0.1 wt% to 1 wt%, 0.1 wt% to 0.5 wt%, or 0.3 wt% to 0.5 wt%, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0048] The catalyst composition has the structure: [ka] wherein each R may be the same or different, is saturated or unsaturated, and is a (cyclo)alkyl group having 2 to 25, for example 5 to 15, 5 to 10, or 7 to 9 carbon atoms, optionally substituted with a heteroatom (oxygen, nitrogen, sulfur, phosphorus, etc., or a halogen atom such as fluorine); x is 2 or 3; and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium.

[0049] Specific examples of suitable metal carboxylates include metal salts of aliphatic monocarboxylic acids having 2 to 25 carbon atoms. Specific examples of such acids include saturated and unsaturated aliphatic monocarboxylic acids, including mixtures thereof. Specific examples of such acids include, but are not limited to, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, naphthenic acid, 9-hexadecenoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid, cis,cis-9,12-octadecenoic acid, cis,cis-9,12-octadecenoic acid, cis,cis-1,1 ... These include tadecadienoic acid, 9,12,15-octadecatrienoic acid, 6,9,12-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, 5,8,11,14-eicosatetraenoic acid, tung oil acid, linseed oil acid, soybean oil acid, resin acid, tall oil fatty acid, rosin acid, abietic acid, neoabietic acid, palustric acid, pimaric acid, dehydroabietic acid, and mixtures of any two or more thereof. In certain embodiments, the metal is iron(III), bismuth, zinc, or a combination of any two or more thereof.

[0050] In some embodiments, the metal carboxylate is present in an amount of from 0.01% to 1.0% by weight, or from 0.02% to 0.5% by weight, or from 0.05% to 0.15% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0051] As noted above, the polyurethane foam-forming compositions herein include a β-dicarbonyl compound. The β-dicarbonyl compound has the structure: [ka] (In the formula, (i) each R 1may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, or halogen atoms such as fluorine, and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R 2 is hydrogen or R 1 As used herein, (cyclo)alkyl includes linear and branched alkyl and cycloalkyl, e.g., any linear or branched alkyl and cycloalkyl containing from 1 to 25 carbon atoms, and (cyclo)alkoxy includes linear and branched alkoxy and cycloalkoxy, e.g., any linear or branched alkoxy and cycloalkoxy containing from 1 to 25 carbon atoms. In some embodiments, each R 1 may be the same or different and are saturated or unsaturated, linear, branched or cyclic alkyl groups having 1 to 25 carbon atoms, for example, 1 to 10 carbon atoms (e.g., each R 1 may be the same or different and are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, dodecanyl, octadecanyl, vinyl, allyl, prenyl, crotyl, cyclopentadienyl, phenyl, tolyl, xylyl, or a substituted aryl group. 2 is hydrogen or a saturated or unsaturated linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, for example 1 to 10 carbon atoms (e.g., each R 2may be the same or different and are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, dodecanyl, octadecanyl, vinyl, allyl, prenyl, crotyl, cyclopentadienyl, phenyl, tolyl, xylyl, or a substituted aryl group. Specific examples of suitable β-dicarbonyl compounds include, but are not limited to, 2,4-pentanedione, 3-chloro-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 3-(1-hydroxyethylidene)-2,4-pentanedione, 3-nitro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 2,4-hexanedione, 5-chloro-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 3-(1-hydroxyethylidene)-2,4-pentanedione, 5-nitro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 5-hexanedione, 5-chloro-2,4-pentanedione, 5-ethyl-2,4-pentanedione, 5-butyl-2,4-pentanedione, 5-(1-hydroxyethylidene)-2,4-pentanedione, 5-nitro-2,4-pentanedione, 5-chloro-2,4-pentanedione, 5-methyl ... -Methyl-2,4-hexanedione, 5,5-dimethyl-2,4-hexanedione, 3-ethyl-2,4-pentanedione, 2,4-octanedione, 2,4-decanedione, 2,2-dimethyl-3,5-nonanedione, 2,4-tridecanedione, 1-cyclohexyl-1,3-butanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-cyclohexanedione, 1-phenyl-1,3-butanedione dione, 1-phenyl-1,3-pentanedione, 1-(4-biphenyl)-1,3-butanedione, 3-benzyl-2,4-pentanedione, 1-phenyl-5,5-dimethyl-2,4-hexanedione, 1-phenyl-2-butyl-1,3-butanedione, and 1-phenyl-3,3-(2-methoxyphenyl)-1,3-propanedione, 3-oxobutanamide, methylenediformamide, methyl-3-oxobutan ... xobutanoate, N-(2-methyloxyethyl)-3-oxobutanamide, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 3-methyl-2,4-pentanedione, or a combination of any two or more thereof.

[0052] In some embodiments, the β-dicarbonyl compound and the metal carboxylate are present in the polyurethane foam-forming composition in a relative weight ratio of at least 0.5:1, such as from 0.5:1 to 10:1, from 1:1 to 10:1, from 1:1 to 5:1, or from 1:1 to 3:1.

[0053] Polyurethane foam-forming compositions typically also include a surfactant. Suitable surfactants include organosilicon compounds such as polysiloxane-polyalkylene-block copolymers, such as polyether-modified polysiloxanes. Other possible surfactants include polyethylene glycol ethers of long-chain alcohols, tertiary amine or alkanolamine salts of long-chain alkyl acid sulfates, alkyl sulfonates, or alkylaryl sulfonic acids. Such surfactants are used in an amount sufficient to stabilize the foaming reaction mixture and prevent collapse and the formation of large, non-uniform cells. In some embodiments, the surfactant is used in an amount of 0.2% to 5.0% by weight, for example 1% to 3% by weight, based on the total weight of the polyurethane foam-forming composition, excluding the weight of the polyisocyanate.

[0054] Additional materials that may optionally be included in the foam-forming composition include pigments, colorants, fillers, antioxidants, flame retardants, and stabilizers. Exemplary flame retardants useful in the foam-forming composition include, but are not limited to, reactive bromine-based compounds and chlorinated phosphate esters known for use in polyurethane chemistry, including, but not limited to, tri(2-chloroethyl)phosphate (TECP), tri(1,3-dichloro-2-propyl)phosphate, tri(1-chloro-2-propyl)phosphate (TCPP), and dimethylpropyl phosphate (DMPP).

[0055] The present specification also relates to a method for producing rigid polyurethane foams, in which a polyisocyanate is reacted with a polyol, such as the polyol blends described herein, having an Isocyanate Index of 0.9 to 1.5, 1.0 to 1.5, 1.1 to 1.2, or 1.1 to 1.15, in the presence of a catalyst composition, a blowing agent composition, and a β-dicarbonyl compound.

[0056] Rigid foams can be prepared by blending all polyurethane foam-forming composition components together in a phase-stable mixture, except for the polyisocyanate, and then mixing this mixture with the polyisocyanate in the appropriate ratio. Alternatively, one or more components, such as a surfactant, may be combined with the polyisocyanate prior to mixing with the polyol blend. Other possible embodiments may include adding one or more components as a separate stream along with the polyol blend and polyisocyanate. As used herein, the term phase-stable means that the composition does not visibly separate upon storage at about 70°F (or 21°C) for 7 days.

[0057] Many foaming machines are designed to mix only two components in the appropriate ratio. To use these foaming machines, a premix of all components except the polyisocyanate may be used. According to the two-component method (component A: polyisocyanate and component B: isocyanate-reactive composition, typically including polyol blend, blowing agent, water, catalyst, β-dicarbonyl compound, and surfactant), these components can be mixed in the appropriate ratio at a temperature of 5°C to 50°C, for example 15°C to 35°C, and injected or poured into a mold having a controlled temperature within the range of 20°C to 70°C, for example 35°C to 60°C. The mixture then expands and a rigid polyurethane foam fills the cavity. This simplifies the metering and mixing of the reactive components that form the foam-forming mixture, but requires that the isocyanate-reactive composition be phase stable.

[0058] Alternatively, rigid polyurethane foams can also be prepared by the so-called "quasi-prepolymer" method. In this method, a portion of the polyol component is reacted with the polyisocyanate component in a ratio that results in 10% to 35% free isocyanate groups relative to the prepolymer in the reaction product in the absence of a urethane-forming catalyst. To prepare the foam, the remaining portion of the polyol is added and these components are reacted together in the presence of a blowing agent and other suitable additives such as catalysts and surfactants. After other additives are added to either the isocyanate prepolymer or the remaining polyol or both, the components are mixed, thereby obtaining a rigid foam at the end of the reaction.

[0059] Additionally, rigid foams may be prepared in a batch or continuous process by one-shot or pseudo-prepolymer processes using any well-known foaming equipment. Rigid foams may be produced in the form of slabstock, moldings, cavity fills, spray foams, frothed foams, or laminates having other materials such as hardboard, gypsum board, plastic, paper, or metal as the facing substrate.

[0060] This specification also relates to the use of the rigid foams described herein for thermal insulation. That is, the rigid foams herein can be used as thermal insulation materials in refrigeration equipment. These rigid foams can be used, for example, as intermediate layers in composite elements or to fill hollow spaces in refrigerators, freezers, water heaters, or refrigerated trailers. These foams can also be used in the construction industry or for insulation of long-distance heating piping and vessels.

[0061] Thus, the present disclosure also provides a composite article comprising the rigid foam disclosed herein sandwiched between one or more surfacing substrates. In certain embodiments, the surfacing substrates can be plastic (e.g., polypropylene resin reinforced with continuous bidirectional glass fiber or fiberglass reinforced polyester copolymer), paper, wood, or metal. For example, in certain embodiments, the composite article can be a refrigeration device, such as a refrigerator, freezer, or cooler, with an outer metal skin and an inner plastic liner. In certain embodiments, the refrigeration device can be a trailer, and the composite article can include the foam in a sandwich composite for the trailer floor or wall.

[0062] Surprisingly, it was observed that different metal carboxylate catalysts responded differently to the presence of β-dicarbonyl compounds. In the case of iron octoate, the catalyst showed a delay in gelation that correlated with increasing amounts of β-dicarbonyl compounds, and the flow data demonstrated a dramatic shift in the magnitude and timing of foam pressure (lower pressure and later maximum). The results also suggest a synergistic interaction between the iron octoate catalyst and the amine catalyst with respect to the foaming reaction, as observed by the increase / spike in rise rate (flow) observed around the time when the catalyst is likely to be in the "unblocked" form. This overall behavior allows the dynamics of the system to be carefully tuned to maximize flow performance and foam quality. On the other hand, when a metal carboxylate catalyst based on a bismuth neodecanoate / zinc neodecanoate blend was evaluated, the impact of β-dicarbonyl compounds was different. Although no change in gelation was observed, it was also found that the presence of β-dicarbonyl compounds resulted in an overall rise rate boost and a shift in flow to an earlier and narrower window. This can be an unexpected advantage since more foam flow occurs prior to foam gelation and viscosity build (compared to the control, which had longer flow).

[0063] Various aspects of the subject matter described herein are set forth in the following numbered sections:

[0064] Item 1. A polyurethane foam-forming composition comprising: (a) a polyol; and (b) a catalyst composition comprising: (i) a tertiary amine; and (ii) a catalyst composition having the structure: [ka] wherein each R may be the same or different and is a saturated or unsaturated, optionally substituted, (cyclo)alkyl group having 2 to 25 carbon atoms; x is 2 or 3; and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium; (c) a blowing agent composition comprising: (i) a physical blowing agent, and (ii) water; and (d) a metal carboxylate having the structure: [ka] (In the formula, (i) each R 1 may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with a heteroatom such as oxygen, nitrogen, sulfur, phosphorus, or a halogen atom such as fluorine, and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R 2 is hydrogen or R 1 and (e) a polyisocyanate.

[0065] Item 2. The polyurethane foam-forming composition according to Item 1, wherein the polyisocyanate comprises a methylene-bridged polyphenyl polyisocyanate and / or a prepolymer of a methylene-bridged polyphenyl polyisocyanate having an average functionality of 1.8 to 3.5, for example 2.0 to 3.1, isocyanate moieties per molecule and an NCO content of 25% to 32% by weight.

[0066] Item 3. The polyurethane foam-forming composition according to item 1 or 2, wherein the polyol comprises a polyether polyol, such as a polyol blend comprising two or more different polyether polyols, such as those prepared by adding an alkylene oxide to a starter compound having an isocyanate-reactive hydrogen atom, optionally in the presence of a base catalyst or a catalyst such as a double metal cyanide (DMC) compound.

[0067] Item 4. The polyurethane foam-forming composition according to item 3, wherein the polyol blend comprises an aromatic amine-initiated polyether polyol that is the reaction product of an H-functional starter material containing an aromatic amine, such as TDA (e.g., o-TDA), with an alkylene oxide.

[0068] Item 5. The polyurethane foam-forming composition of item 4, wherein the aromatic amine is present in an amount of greater than 50 weight percent, at least 80 weight percent, at least 90 weight percent, or 100 weight percent, based on the total weight of H-functional starting materials used to make the aromatic amine-initiated polyether polyol.

[0069] Item 6. The polyurethane foam-forming composition according to item 4 or 5, wherein the alkylene oxide used to prepare the aromatic amine-initiated polyether polyol comprises ethylene oxide, propylene oxide, butylene oxide, amylene oxide, or a mixture of any two or more thereof, and for example, propylene oxide is used in an amount of more than 50 wt%, at least 60 wt%, or from 60 wt% to 70 wt%, based on the total weight of alkylene oxide used to prepare the aromatic amine-initiated polyether polyol, and ethylene oxide is used in an amount of 50 wt% or less, 40 wt% or less, or from 30 wt% to 40 wt%, based on the total weight of alkylene oxide used to prepare the aromatic amine-initiated polyether polyol.

[0070] Item 7. The polyurethane foam-forming composition of any one of Items 4 to 6, wherein the aromatic amine-initiated polyether polyol has an OH number of 200 mg KOH / g to 600 mg KOH / g, 300 mg KOH / g to 500 mg KOH / g, or 380 mg KOH / g to 420 mg KOH / g, and a functionality of at least 2.5, 3.5 to 4.5, 3.8 to 4.2, or 4.0.

[0071] Item 8. The polyurethane foam-forming composition of any one of Items 4 to 7, wherein the aromatic amine-initiated polyether polyol is present in an amount of at least 10% by weight, 10% to 40% by weight, 10% to 30% by weight, 10% to 25% by weight, or 15% to 25% by weight, based on the total weight of the polyol blend.

[0072] Item 9. The polyurethane foam-forming composition according to any one of items 3 to 8, wherein the polyol blend also includes a sugar-initiated polyether polyol that is the reaction product of an H-functional starting material, including a sugar such as sucrose, with an alkylene oxide.

[0073] Item 10. The polyurethane foam-forming composition of item 9, wherein the sugar is present in an amount of greater than 50 weight percent, at least 70 weight percent, or at least 80 weight percent, based on the total weight of H-functional starting materials used to make the sugar-initiated polyether polyol.

[0074] Item 11. The polyurethane foam-forming composition of item 9 or 10, wherein the propylene oxide is used in an amount greater than 50 weight percent, at least 80 weight percent, at least 90 weight percent, at least 95 weight percent, at least 99 weight percent, or 100 weight percent, based on the total weight of alkylene oxide used to prepare the sugar-initiated polyether polyol, and ethylene oxide is present in an amount of 50 weight percent or less, 20 weight percent or less, or 10 weight percent or less, based on the total weight of alkylene oxide used to prepare the sugar-initiated polyether polyol.

[0075] Item 12. The polyurethane foam-forming composition according to any one of Items 9 to 11, wherein the sugar-initiated polyether polyol has an OH number of 200 mg KOH / g to 600 mg KOH / g, 300 mg KOH / g to 550 mg KOH / g, 300 mg KOH / g to 400 mg KOH / g, or 350 mg KOH / g to 400 mg KOH / g, and a functionality of 4 to 6, 5 to 6, or 5.5 to 6.

[0076] Item 13. The polyurethane foam-forming composition of any one of items 9 to 12, wherein the sugar-initiated polyether polyol is present in an amount of at least 10% by weight, 10% to 50% by weight, 20% to 40% by weight, or 25% to 35% by weight, based on the total weight of the polyol blend.

[0077] Item 14. The polyurethane foam-forming composition according to any one of Items 3 to 13, wherein the polyol blend comprises a triol-initiated polyether polyol that is the reaction product of an alkylene oxide and a starting material in the presence of a suitable catalyst, the starting material comprising a triol such as glycerin, trimethylolpropane, trimethylolethane, 2-methylpropane-1,2,3-triol, 1,2,6-hexanetriol, or a mixture of any two or more thereof.

[0078] Item 15. The polyurethane foam-forming composition of item 14, wherein the triol, such as glycerin, is present in an amount of greater than 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 98% by weight, or 100% by weight, based on the total weight of starting materials used to make the triol-initiated polyether polyol.

[0079] Item 16. The polyurethane foam-forming composition of item 14 or 15, wherein propylene oxide is present in an amount greater than 50 weight percent, at least 80 weight percent, at least 90 weight percent, at least 95 weight percent, at least 99 weight percent, or 100 weight percent, based on the total weight of alkylene oxide used to prepare the triol-initiated polyether polyol, and ethylene oxide is present in an amount no greater than 50 weight percent, no greater than 20 weight percent, or no greater than 10 weight percent, based on the total weight of alkylene oxide used to prepare the triol-initiated polyether polyol.

[0080] Item 17. The polyurethane foam-forming composition of any one of Items 14 to 16, wherein the triol-initiated polyether polyol has an OH number of 300 mg KOH / g to 600 mg KOH / g, 400 mg KOH / g to 500 mg KOH / g, or 450 mg KOH / g to 500 mg KOH / g, a functionality of at least 2.5, 2.5 to 3.5, 2.8 to 3.2, or 3.0, and is present in an amount of at least 30 wt%, 30 wt% to 70 wt%, 40 wt% to 60 wt%, or 45 wt% to 55 wt%, based on the total weight of the polyol blend.

[0081] Item 18. The polyurethane foam-forming composition according to any one of items 9 to 17, wherein the sugar-initiated polyether polyol and the aromatic amine-initiated polyether polyol are present in a weight ratio of at least 1:1, 1:1 to 3:1, 1:1 to 2:1, or 1.2:1 to 1.8:1.

[0082] Item 19. The polyurethane foam-forming composition according to any one of items 14 to 18, wherein the triol-initiated polyether polyol and the aromatic amine-initiated polyether polyol are present in a weight ratio of at least 1:1, 1:1 to 5:1, 2:1 to 4:1, or 2.0:1 to 3.0:1.

[0083] Item 20. The polyurethane foam-forming composition of any one of Items 14 to 19, wherein the triol-initiated polyether polyol and the sugar-initiated polyether polyol are present in a weight ratio of 1:1, 1:1 to 3:1, 1:1 to 2:1, or 1.2:1 to 1.8:1.

[0084] Item 21. The polyurethane foam-forming composition according to any one of items 3 to 20, wherein the polyol blend has a weighted average functionality of 3 to 5, 3.5 to 4.5, or 3.8 to 4.2.

[0085] Item 22. The polyurethane foam-forming composition according to any one of Items 3 to 21, wherein the polyol blend has a weighted average hydroxyl number of 300 mg KOH / g to 500 mg KOH / g or 350 mg KOH / g to 450 mg KOH / g.

[0086] Item 23. The polyurethane foam-forming composition according to any one of Items 3 to 22, wherein the polyol blend is present in the polyurethane foam-forming composition in an amount of at least 50% by weight, 50% to 90% by weight, or 80% to 90% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0087] Item 24. The polyurethane foam-forming composition according to any one of items 14 to 23, wherein the sum of the amounts of the aromatic amine-initiated polyether polyol, the sugar-initiated polyether polyol, and the triol-initiated polyether polyol is at least 90% by weight, at least 95% by weight, at least 98% by weight, or 100% by weight, based on the total weight of the polyol blend.

[0088] Item 25. The polyurethane foam-forming composition according to any one of items 1 to 24, wherein the physical blowing agent comprises a hydrocarbon such as cyclopentane, isopentane, n-pentane, butane, or propane; a perfluorinated alkene such as 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene, 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)-2-pentene or cis-1,1,1,4,4,4-hexafluoro-2-butene; a chlorofluoroalkene such as trans-1-chloro-3,3,3-trifluoropropene; or a mixture of any two or more thereof.

[0089] Item 26. The polyurethane foam-forming composition according to any one of items 1 to 25, wherein the physical blowing agent is present in an amount of at least 5% by weight, 5% to 30% by weight, 5% to 20% by weight, or 5% to 15% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0090] Item 26. The polyurethane foam-forming composition according to any one of Items 1 to 26, wherein the water is present in an amount of at least 1.0% by weight, 1.0 to 5.0% by weight, 1.0 to 4.0% by weight, 1.0 to 3.0% by weight, or 1.0 to 2.0% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0091] Item 27. The polyurethane foam-forming composition according to any one of items 1 to 26, wherein the physical blowing agent composition and water are present in a relative weight ratio of at least 5:1, 5:1 to 50:1, 5:1 to 20:1, 5:1 to 9:1, or 5:1 to 7:1.

[0092] Item 28. The tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, dimethylbenzylamine, dibutylcyclohexylamine, dimethylethanolamine, triethanolamine, diethylethanolamine, ethyldiethanolamine, dimethylisopropanolamine, dimethyloctylamine, triisopropanolamine, triethylenediamine, tetramethyl-1,3-butanediamine, and N,N,N',N'-tetramethyl-1,3-butanediamine. Methylethylenediamine, N,N,N',N'-tetramethylhexane-1,6-diamine, N,N,N',N',N''-pentamethyldiethylenetriamine, bis(2-dimethylaminoethoxy)methane, N,N,N'-trimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N',N'-(2-hydroxyethyl)ethylenediamine, tetramethylguanidine, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, 1,4-dimethyl tertiary amines include unblocked tertiary amines and chemically blocked tertiary amines, for example, the unblocked tertiary amines include ethyl piperidine, 1,2,4-trimethylpiperidine, N-(2-dimethylaminoethyl)morpholine, 1-methyl-4-(2-dimethylamino)piperidine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]-5-nonane, or a combination of any two or more thereof, for example, the ... 28. The polyurethane foam-forming composition according to any one of items 1 to 27, wherein the tertiary amine and the chemically blocked tertiary amine are present in a weight ratio of 1:5 to 5:1, 1:3 to 3:1, 1:2 to 2:1, or 1.1:1 to 1:1.1, and / or the unblocked tertiary amine and the chemically blocked tertiary amine are each present in an amount of 0.1 to 1 wt %, 0.1 to 0.5 wt %, or 0.3 to 0.5 wt %, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0093] Item 29. The polyurethane foam-forming composition according to any one of items 1 to 28, wherein the tertiary amine is present in an amount of 0.01% by weight to 3.0% by weight, 0.3% by weight to 2.5% by weight, or 1.0% by weight to 2.0% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0094] Item 30. The polyurethane foam-forming composition according to any one of items 1 to 29, wherein each R, which may be the same or different, has 5 to 15, 5 to 10, or 7 to 9 carbon atoms.

[0095] Item 31. The metal carboxylate includes a metal salt of an aliphatic monocarboxylic acid having 2 to 25 carbon atoms. For example, the aliphatic monocarboxylic acid includes a saturated aliphatic monocarboxylic acid, an unsaturated aliphatic monocarboxylic acid, or a mixture thereof. For example, the aliphatic monocarboxylic acid includes ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, naphthenic acid, 9-hexadecenoic acid, Item 31. The polyurethane foam-forming composition according to any one of items 1 to 30, comprising cis-9-octadecenoic acid, 11-octadecenoic acid, cis,cis-9,12-octadecadienoic acid, 9,12,15-octadecatrienoic acid, 6,9,12-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, 5,8,11,14-eicosatetraenoic acid, tung oil acid, linseed oil acid, soybean oil acid, resin acid, tall oil fatty acid, rosin acid, abietic acid, neoabietic acid, palustric acid, pimaric acid, dehydroabietic acid, or a mixture of any two or more thereof.

[0096] Item 32. The polyurethane foam-forming composition according to any one of Items 1 to 31, wherein the metal carboxylate is present in an amount of 0.01% by weight to 1.0% by weight, 0.02% by weight to 0.5% by weight, or 0.05% by weight to 0.15% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0097] Section 33. Each R 1 may be the same or different and are saturated or unsaturated linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, for example, each R 1 may be the same or different and are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, dodecanyl, octadecanyl, vinyl, allyl, prenyl, crotyl, cyclopentadienyl, phenyl, tolyl, xylyl, or a substituted aryl group; and / or R 2 is a saturated or unsaturated linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, R 2 33. The polyurethane foam-forming composition according to any one of items 1 to 32, wherein x may be the same or different and is a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, dodecanyl, octadecanyl, vinyl, allyl, prenyl, crotyl, cyclopentadienyl, phenyl, tolyl, xylyl, or substituted aryl group.

[0098] Item 34. The β-dicarbonyl compound is 2,4-pentanedione, 3-chloro-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 3-(1-hydroxyethylidene)-2,4-pentanedione, 3-nitro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 2,4-hexanedione, 5-methyl-2,4-hexanedione, 5, 5-Dimethyl-2,4-hexanedione, 3-Ethyl-2,4-pentanedione, 2,4-Octanedione, 2,4-Decanedione, 2,2-Dimethyl-3,5-nonanedione, 2,4-Tridecanedione, 1-Cyclohexyl-1,3-butanedione, 5,5-Dimethyl-1,3-cyclohexanedione, 1,3-Cyclohexanedione, 1-Phenyl-1,3-butanedione, 1-Phenyl-1,3-pentanedione 1-(4-biphenyl)-1,3-butanedione, 3-benzyl-2,4-pentanedione, 1-phenyl-5,5-dimethyl-2,4-hexanedione, 1-phenyl-2-butyl-1,3-butanedione, and 1-phenyl-3,3-(2-methoxyphenyl)-1,3-propanedione, 3-oxobutanamide, methylenediformamide, methyl-3-oxobutanoate, N-(2-methyloxyethyl)-1,3-propanedione, 34. The polyurethane foam-forming composition according to any one of items 1 to 33, comprising 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 3-methyl-2,4-pentanedione, or a combination of any two or more thereof.

[0099] Item 35. The polyurethane foam-forming composition according to any one of items 1 to 34, wherein the β-dicarbonyl compound and the metal carboxylate are present in a relative weight ratio of at least 0.5:1, for example, 0.5:1 to 10:1, 1:1 to 10:1, 1:1 to 5:1, or 1:1 to 3:1.

[0100] Item 36. A method for producing a polyurethane foam, comprising reacting a polyurethane foam with an isocyanate index of 0.90 to 1.50, wherein the polyurethane foam-forming composition comprises (a) a polyol, (b) a polyisocyanate, (c) a catalyst composition, (d) a blowing agent composition, and (e) a β-dicarbonyl compound, (1) wherein the catalyst composition comprises (i) a tertiary amine, and (ii) a tertiary amine having the structure: [ka] wherein each R may be the same or different, is a saturated or unsaturated, optionally substituted (cyclo)alkyl group having 2 to 25 carbon atoms; x is 2 or 3; and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium; (2) the blowing agent composition comprises a physical blowing agent, and water; and (3) the β-dicarbonyl compound comprises a metal carboxylate having the structure: [ka] (In the formula, (i) each R 1 may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with a heteroatom such as oxygen, nitrogen, sulfur, phosphorus, or a halogen atom such as fluorine, and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R 2 is hydrogen or R 1 (wherein

[0101] Item 37. The method according to item 36, wherein the isocyanate index is 1.0 to 1.5, 1.1 to 1.2, or 1.1 to 1.15.

[0102] Item 38. The method according to item 36 or 37, wherein the polyisocyanate comprises a methylene-bridged polyphenyl polyisocyanate and / or a prepolymer of a methylene-bridged polyphenyl polyisocyanate having an average functionality of 1.8 to 3.5, for example 2.0 to 3.1, isocyanate moieties per molecule and an NCO content of 25% by weight to 32% by weight.

[0103] Item 39. The method according to any one of items 36 to 38, wherein the polyol comprises a polyether polyol, such as a polyol blend comprising two or more different polyether polyols, such as one prepared by adding an alkylene oxide to a starter compound having an isocyanate-reactive hydrogen atom in the presence of a base catalyst or a catalyst such as a double metal cyanide (DMC) compound.

[0104] Item 40. The method of item 39, wherein the polyol blend comprises an aromatic amine-initiated polyether polyol that is the reaction product of an H-functional starting material, such as an aromatic amine, such as TDA (e.g., o-TDA), with an alkylene oxide.

[0105] Item 41. The method of item 40, wherein the aromatic amine is present in an amount of more than 50 wt%, at least 80 wt%, at least 90 wt%, or 100 wt%, based on the total weight of the H-functional starting materials used to prepare the aromatic amine-initiated polyether polyol.

[0106] Item 42. The method according to item 40 or 41, wherein the alkylene oxide used to prepare the aromatic amine-initiated polyether polyol comprises ethylene oxide, propylene oxide, butylene oxide, amylene oxide, or a mixture of any two or more thereof, and for example, propylene oxide is used in an amount of more than 50 wt%, at least 60 wt%, or from 60 wt% to 70 wt%, based on the total weight of alkylene oxide used to prepare the aromatic amine-initiated polyether polyol, and ethylene oxide is used in an amount of 50 wt% or less, 40 wt% or less, or from 30 wt% to 40 wt%, based on the total weight of alkylene oxide used to prepare the aromatic amine-initiated polyether polyol.

[0107] Item 43. The method according to any one of items 40 to 42, wherein the aromatic amine-initiated polyether polyol has an OH number of 200 mg KOH / g to 600 mg KOH / g, 300 mg KOH / g to 500 mg KOH / g, or 380 mg KOH / g to 420 mg KOH / g, and a functionality of at least 2.5, 3.5 to 4.5, 3.8 to 4.2, or 4.0.

[0108] Item 44. The method according to any one of items 40 to 43, wherein the aromatic amine-initiated polyether polyol is present in an amount of at least 10% by weight, 10% to 40% by weight, 10% to 30% by weight, 10% to 25% by weight, or 15% to 25% by weight, based on the total weight of the polyol blend.

[0109] Item 45. The method according to any one of items 39 to 44, wherein the polyol blend also comprises a sugar-initiated polyether polyol, which is the reaction product of an H-functional starting material, including a sugar such as sucrose, with an alkylene oxide.

[0110] Item 46. The method of item 45, wherein the sugar is present in an amount of greater than 50 wt%, at least 70 wt%, or at least 80 wt%, based on the total weight of H-functional starting materials used to produce the sugar-initiated polyether polyol.

[0111] Item 47. The method of item 45 or 46, wherein the propylene oxide is used in an amount greater than 50 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt%, based on the total weight of alkylene oxide used to prepare the sugar-initiated polyether polyol, and ethylene oxide is present in an amount of 50 wt% or less, 20 wt% or less, or 10 wt% or less, based on the total weight of alkylene oxide used to prepare the sugar-initiated polyether polyol.

[0112] Item 48. The method according to any one of items 45 to 47, wherein the sugar-initiated polyether polyol has an OH number of 200 mg KOH / g to 600 mg KOH / g, 300 mg KOH / g to 550 mg KOH / g, 300 mg KOH / g to 400 mg KOH / g, or 350 mg KOH / g to 400 mg KOH / g, and a functionality of 4 to 6, 5 to 6, or 5.5 to 6.

[0113] Item 49. The method of any one of items 45 to 48, wherein the sugar-initiated polyether polyol is present in an amount of at least 10% by weight, 10% to 50% by weight, 20% to 40% by weight, or 25% to 35% by weight, based on the total weight of the polyol blend.

[0114] Item 50. The method according to any one of items 39 to 49, wherein the polyol blend comprises a triol-initiated polyether polyol that is a reaction product of an alkylene oxide and a starting material in the presence of a suitable catalyst, and the starting material comprises a triol such as glycerin, trimethylolpropane, trimethylolethane, 2-methylpropane-1,2,3-triol, 1,2,6-hexanetriol, or a mixture of any two or more thereof.

[0115] Item 51. The method of item 50, wherein the triol, such as glycerin, is present in an amount of more than 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 98% by weight, or 100% by weight, based on the total weight of starting materials used to produce the triol-initiated polyether polyol.

[0116] Item 52. The method of item 50 or 51, wherein propylene oxide is present in an amount greater than 50 weight percent, at least 80 weight percent, at least 90 weight percent, at least 95 weight percent, at least 99 weight percent, or 100 weight percent, based on the total weight of alkylene oxide used to prepare the triol-initiated polyether polyol, and ethylene oxide is present in an amount of 50 weight percent or less, 20 weight percent or less, or 10 weight percent or less, based on the total weight of alkylene oxide used to prepare the triol-initiated polyether polyol.

[0117] Item 53. The method according to any one of items 50 to 52, wherein the triol-initiated polyether polyol has an OH number of 300 mg KOH / g to 600 mg KOH / g, 400 mg KOH / g to 500 mg KOH / g, or 450 mg KOH / g to 500 mg KOH / g, a functionality of at least 2.5, 2.5 to 3.5, 2.8 to 3.2, or 3.0, and is present in an amount of at least 30 wt%, 30 wt% to 70 wt%, 40 wt% to 60 wt%, or 45 wt% to 55 wt%, based on the total weight of the polyol blend.

[0118] Item 54. The method of any one of items 39 to 53, wherein the sugar-initiated polyether polyol and the aromatic amine-initiated polyether polyol are present in a weight ratio of at least 1:1, 1:1 to 3:1, 1:1 to 2:1, or 1.2:1 to 1.8:1.

[0119] Item 55. The method according to any one of items 50 to 54, wherein the triol-initiated polyether polyol and the aromatic amine-initiated polyether polyol are present in a weight ratio of at least 1:1, 1:1 to 5:1, 2:1 to 4:1, or 2.0:1 to 3.0:1.

[0120] Item 56. The method of any one of items 50 to 55, wherein the triol-initiated polyether polyol and the sugar-initiated polyether polyol are present in a weight ratio of 1:1, 1:1 to 3:1, 1:1 to 2:1, or 1.2:1 to 1.8:1.

[0121] Item 57. The method according to any one of items 39 to 56, wherein the polyol blend has a weighted average functionality of 3 to 5, 3.5 to 4.5, or 3.8 to 4.2.

[0122] Item 58. The method according to any one of items 39 to 57, wherein the polyol blend has a weighted average hydroxyl number of 300 mg KOH / g to 500 mg KOH / g or 350 mg KOH / g to 450 mg KOH / g.

[0123] Item 59. The method of any one of items 39 to 58, wherein the polyol blend is present in the polyurethane foam-forming composition in an amount of at least 50% by weight, 50% to 90% by weight, or 80% to 90% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0124] Item 60. The method according to any one of items 50 to 59, wherein the sum of the amounts of the aromatic amine-initiated polyether polyol, the sugar-initiated polyether polyol, and the triol-initiated polyether polyol is at least 90% by weight, at least 95% by weight, at least 98% by weight, or 100% by weight, based on the total weight of the polyol blend.

[0125] Item 61. The method according to any one of items 36 to 60, wherein the physical blowing agent is a hydrocarbon such as cyclopentane, isopentane, n-pentane, butane, and propane, 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene, 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)-2-pentene or cis-1,1,1,4,4,4-hexafluoro-2-butene, or other perfluorinated alkene, trans-1-chloro-3,3,3-trifluoropropene, or other chlorofluoroalkene, or a mixture of two or more thereof.

[0126] Item 62. The method according to any one of items 36 to 61, wherein the physical blowing agent is present in an amount of at least 5% by weight, 5% to 30% by weight, 5% to 20% by weight, or 5% to 15% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0127] Item 63. The method according to any one of items 36 to 62, wherein the water is present in an amount of at least 1.0% by weight, 1.0% to 5.0% by weight, 1.0% to 4.0% by weight, 1.0% to 3.0% by weight, or 1.0% to 2.0% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0128] Item 64. The method according to any one of items 36 to 63, wherein the physical blowing agent composition and water are present in a relative weight ratio of at least 5:1, 5:1 to 50:1, 5:1 to 20:1, 5:1 to 9:1, or 5:1 to 7:1.

[0129] Item 65. The tertiary amine is trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, dimethylbenzylamine, dibutylcyclohexylamine, dimethylethanolamine, triethanolamine, diethylethanolamine, ethyldiethanolamine, dimethylisopropanolamine, dimethyloctylamine, triisopropanolamine, triethylenediamine, tetramethyl-1,3-butanediamine, N,N,N',N'- Tetramethylethylenediamine, N,N,N',N'-tetramethylhexane-1,6-diamine, N,N,N',N',N''-pentamethyldiethylenetriamine, bis(2-dimethylaminoethoxy)methane, N,N,N'-trimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N',N'-(2-hydroxyethyl)ethylenediamine, tetramethylguanidine, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, 1,4-dimethylpiperidine, 1,2,4-trimethylpiperidine, N-(2-dimethylaminoethyl)morpholine, 1-methyl-4-(2-dimethylamino)piperidine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]-5-nonane, or a combination of any two or more thereof, for example, the tertiary amines include unblocked tertiary amines and chemically blocked tertiary amines, for example: 65. The method of any one of claims 36 to 64, wherein the unblocked tertiary amine and the chemically blocked tertiary amine are present in a weight ratio of 1:5 to 5:1, 1:3 to 3:1, 1:2 to 2:1, or 1.1:1 to 1:1.1, and / or the unblocked tertiary amine and the chemically blocked tertiary amine are each present in an amount of 0.1 wt % to 1 wt %, 0.1 wt % to 0.5 wt %, or 0.3 wt % to 0.5 wt %, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0130] Item 66. The method according to any one of items 36 to 65, wherein the tertiary amine is present in an amount of 0.01% by weight to 3.0% by weight, 0.3% by weight to 2.5% by weight, or 1.0% by weight to 2.0% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0131] Item 67. The method according to any one of items 36 to 66, wherein each R may be the same or different and has 5 to 15, 5 to 10, or 7 to 9 carbon atoms.

[0132] Item 68. The metal carboxylate includes a metal salt of an aliphatic monocarboxylic acid having 2 to 25 carbon atoms, and for example, the aliphatic monocarboxylic acid includes a saturated aliphatic monocarboxylic acid, an unsaturated aliphatic monocarboxylic acid, or a mixture thereof, and for example, the aliphatic monocarboxylic acid includes ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, naphthenic acid, 9-hexanoic acid, 1 ... Item 36 to Item 67, comprising cis-9-octadecenoic acid, cis-9,12-octadecadienoic acid, cis-9,12,15-octadecatrienoic acid, 6,9,12-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, 5,8,11,14-eicosatetraenoic acid, tung oil acid, linseed oil acid, soybean oil acid, resin acid, tall oil fatty acid, rosin acid, abietic acid, neoabietic acid, palustric acid, pimaric acid, dehydroabietic acid, or a mixture of any two or more thereof.

[0133] Item 69. The method according to any one of items 36 to 68, wherein the metal carboxylate is present in an amount of 0.01% by weight to 1.0% by weight, 0.02% by weight to 0.5% by weight, or 0.05% by weight to 0.15% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

[0134] Section 70.Each R 1 may be the same or different and are saturated or unsaturated linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, for example, each R 1 may be the same or different and are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, dodecanyl, octadecanyl, vinyl, allyl, prenyl, crotyl, cyclopentadienyl, phenyl, tolyl, xylyl, or a substituted aryl group; and / or R 2 is a saturated or unsaturated linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, R 2 may be the same or different and are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, dodecanyl, octadecanyl, vinyl, allyl, prenyl, crotyl, cyclopentadienyl, phenyl, tolyl, xylyl, or a substituted aryl group.

[0135] Item 71. The β-dicarbonyl compound is 2,4-pentanedione, 3-chloro-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 3-(1-hydroxyethylidene)-2,4-pentanedione, 3-nitro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 2,4-hexanedione, 5-methyl-2,4-hexanedione. , 5,5-dimethyl-2,4-hexanedione, 3-ethyl-2,4-pentanedione, 2,4-octanedione, 2,4-decanedione, 2,2-dimethyl-3,5-nonanedione, 2,4-tridecanedione, 1-cyclohexyl-1,3-butanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-cyclohexanedione, 1-phenyl-1,3-butanedione, 1-phenyl-1,3- Pentanedione, 1-(4-biphenyl)-1,3-butanedione, 3-benzyl-2,4-pentanedione, 1-phenyl-5,5-dimethyl-2,4-hexanedione, 1-phenyl-2-butyl-1,3-butanedione, and 1-phenyl-3,3-(2-methoxyphenyl)-1,3-propanedione, 3-oxobutanamide, methylenediformamide, methyl-3-oxobutanoate, N-(2- Item 71. The method according to any one of items 36 to 70, comprising a fluorophenyl ether ester (methyloxyethyl)-3-oxobutanamide, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 3-methyl-2,4-pentanedione, or a combination of any two or more thereof.

[0136] Item 72. The method according to any one of Items 36 to 71, wherein the β-dicarbonyl compound and the metal carboxylate are present in a relative weight ratio of at least 0.5:1, for example, 0.5:1 to 10:1, 1:1 to 10:1, 1:1 to 5:1, or 1:1 to 3:1.

[0137] Item 73. The rigid polyurethane foam has a closed cell content of greater than 80 percent, greater than 85 percent, or greater than 88 percent as measured in accordance with ASTM D6226-15, and / or the rigid polyurethane foam has a closed cell content of 0.126 BTU-in / h-ft2 measured at 35°F (2°C) for foam from a core of a 2-inch thick panel as measured in accordance with ASTM C518-15. 2 Thermal conductivity below -°F and 0.140 BTU-in / h-ft measured at 75°F (24°C) 2 A rigid polyurethane foam formed from the polyurethane foam-forming composition according to any one of items 1 to 36, or produced by the method according to any one of items 36 to 72, having a thermal conductivity of less than -°F.

[0138] Item 74. A composite article comprising the rigid polyurethane foam of item 73 sandwiched between one or more facing substrates, for example, the facing substrates comprising plastic (e.g., polypropylene resin reinforced with continuous bidirectional glass fibers or fiberglass reinforced polyester copolymer), paper, wood, or metal.

[0139] Item 75. The composite article of item 74, wherein the composite article comprises a refrigeration device, such as a refrigerator, freezer, or cooler, having an outer metal skin and an inner plastic liner, or a trailer floor or wall.

[0140] Item 76. An isocyanate-reactive composition comprising: (a) a polyol; and (b) a catalyst composition comprising: (i) a tertiary amine; and (ii) a catalyst composition having the structure: [ka] wherein each R may be the same or different and is a saturated or unsaturated, optionally substituted, (cyclo)alkyl group having 2 to 25 carbon atoms; x is 2 or 3; and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium; (c) a blowing agent composition comprising: (i) a physical blowing agent, and (ii) water; and (d) a metal carboxylate having the structure: [ka] (In the formula, (i) each R 1 may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, or halogen atoms such as fluorine, and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R 2 is hydrogen or R 1 and a β-dicarbonyl compound having a formula:

[0141] Item 77. The isocyanate-reactive composition according to item 76, wherein the polyol comprises a polyether polyol, such as a polyol blend comprising two or more different polyether polyols, such as those prepared by adding an alkylene oxide to a starter compound having an isocyanate-reactive hydrogen atom, optionally in the presence of a base catalyst or a catalyst such as a double metal cyanide (DMC) compound.

[0142] Item 78. The isocyanate-reactive composition according to item 77, wherein the polyol blend comprises an aromatic amine-initiated polyether polyol which is the reaction product of an H-functional starter material containing an aromatic amine, such as TDA (e.g., o-TDA), with an alkylene oxide.

[0143] Item 79. The isocyanate-reactive composition of item 78, wherein the aromatic amine is present in an amount greater than 50 wt%, at least 80 wt%, at least 90 wt%, or 100 wt%, based on the total weight of H-functional starting materials used to prepare the aromatic amine-initiated polyether polyol.

[0144] Item 80. The alkylene oxide used to prepare the aromatic amine-initiated polyether polyol comprises ethylene oxide, propylene oxide, butylene oxide, amylene oxide, or a mixture of any two or more thereof, for example, propylene oxide is used in an amount of more than 50 wt%, at least 60 wt%, or 60 wt% to 70 wt%, based on the total weight of alkylene oxide used to prepare the aromatic amine-initiated polyether polyol, and ethylene oxide is used in an amount of 50 wt% or less, 40 wt% or less, or 30 wt% to 40 wt%, based on the total weight of alkylene oxide used to prepare the aromatic amine-initiated polyether polyol. The isocyanate-reactive composition according to item 78 or 79.

[0145] Item 81. The aromatic amine-initiated polyether polyol has an OH number of 200 mg KOH / g to 600 mg KOH / g, 300 mg KOH / g to 500 mg KOH / g, or 380 mg KOH / g to 420 mg KOH / g, and a functionality of at least 2.5, 3.5 to 4.5, 3.8 to 4.2, or 4.0. The isocyanate-reactive composition according to any one of items 78 to 80.

[0146] Item 82. The aromatic amine-initiated polyether polyol is present in an amount of at least 10% by weight, 10% to 40% by weight, 10% to 30% by weight, 10% to 25% by weight, or 15% to 25% by weight, based on the total weight of the polyol blend. The isocyanate-reactive composition according to any one of items 78 to 81.

[0147] Item 83. The isocyanate-reactive composition according to any one of items 78 to 82, wherein the polyol blend also contains a sugar-initiated polyether polyol that is the reaction product of an H-functional starting material, including a sugar such as sucrose, with an alkylene oxide.

[0148] Item 84. The isocyanate-reactive composition of item 83, wherein the sugar is present in an amount of greater than 50% by weight, at least 70% by weight, or at least 80% by weight, based on the total weight of H-functional starting materials used to make the sugar-initiated polyether polyol.

[0149] Item 85. The isocyanate-reactive composition of item 83 or 84, wherein the propylene oxide is used in an amount greater than 50 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt%, based on the total weight of alkylene oxide used to prepare the sugar-initiated polyether polyol, and ethylene oxide is present in an amount of 50 wt% or less, 20 wt% or less, or 10 wt% or less, based on the total weight of alkylene oxide used to prepare the sugar-initiated polyether polyol.

[0150] Item 86. The isocyanate-reactive composition according to any one of items 83 to 85, wherein the sugar-initiated polyether polyol has an OH number of 200 mg KOH / g to 600 mg KOH / g, 300 mg KOH / g to 550 mg KOH / g, 300 mg KOH / g to 400 mg KOH / g, or 350 mg KOH / g to 400 mg KOH / g, and a functionality of 4 to 6, 5 to 6, or 5.5 to 6.

[0151] Item 87. The isocyanate-reactive composition according to any one of items 83 to 86, wherein the sugar-initiated polyether polyol is present in an amount of at least 10% by weight, 10% to 50% by weight, 20% to 40% by weight, or 25% to 35% by weight, based on the total weight of the polyol blend.

[0152] Item 88. The polyol blend comprises a triol-initiated polyether polyol that is a reaction product of an alkylene oxide and a starting material in the presence of a suitable catalyst, and the starting material comprises a triol such as glycerin, trimethylolpropane, trimethylolethane, 2-methylpropane-1,2,3-triol, 1,2,6-hexanetriol, or a mixture of any two or more thereof. An isocyanate-reactive composition according to any one of items 77 to 87.

[0153] Item 89. The isocyanate-reactive composition according to item 88, wherein the triol, such as glycerin, is present in an amount of more than 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 98% by weight, or 100% by weight, based on the total weight of the starting materials used to produce the triol-initiated polyether polyol.

[0154] Item 90. The isocyanate-reactive composition according to item 88 or 89, wherein propylene oxide is present in an amount greater than 50 weight percent, at least 80 weight percent, at least 90 weight percent, at least 95 weight percent, at least 99 weight percent, or 100 weight percent, based on the total weight of alkylene oxide used to prepare the triol-initiated polyether polyol, and ethylene oxide is present in an amount of 50 weight percent or less, 20 weight percent or less, or 10 weight percent or less, based on the total weight of alkylene oxide used to prepare the triol-initiated polyether polyol.

[0155] Item 91. The isocyanate-reactive composition according to any one of items 88 to 90, wherein the triol-initiated polyether polyol has an OH number of 300 mg KOH / g to 600 mg KOH / g, 400 mg KOH / g to 500 mg KOH / g, or 450 mg KOH / g to 500 mg KOH / g, a functionality of at least 2.5, 2.5 to 3.5, 2.8 to 3.2, or 3.0, and is present in an amount of at least 30 wt%, 30 wt% to 70 wt%, 40 wt% to 60 wt%, or 45 wt% to 55 wt%, based on the total weight of the polyol blend.

[0156] Item 92. The isocyanate-reactive composition according to any one of items 83 to 91, wherein the sugar-initiated polyether polyol and the aromatic amine-initiated polyether polyol are present in a weight ratio of at least 1:1, 1:1 to 3:1, 1:1 to 2:1, or 1.2 to 1.8:1.

[0157] Item 93. The isocyanate-reactive composition according to any one of items 88 to 92, wherein the triol-initiated polyether polyol and the aromatic amine-initiated polyether polyol are present in a weight ratio of at least 1:1, 1:1 to 5:1, 2:1 to 4:1, or 2.0:1 to 3.0:1.

[0158] Item 94. The isocyanate-reactive composition according to any one of items 88 to 93, wherein the triol-initiated polyether polyol and the sugar-initiated polyether polyol are present in a weight ratio of 1:1, 1:1 to 3:1, 1:1 to 2:1, or 1.2 to 1.8:1.

[0159] Item 95. The isocyanate-reactive composition according to any one of items 77 to 94, wherein the polyol blend has a weighted average functionality of 3 to 5, 3.5 to 4.5, or 3.8 to 4.2.

[0160] Item 96. The isocyanate-reactive composition according to any one of items 77 to 95, wherein the polyol blend has a weighted average hydroxyl number of 300 mg KOH / g to 500 mg KOH / g or 350 mg KOH / g to 450 mg KOH / g.

[0161] Item 97. The isocyanate-reactive composition according to any one of items 77 to 96, wherein the polyol blend is present in an amount of at least 50% by weight, 50% to 90% by weight, or 80% to 90% by weight, based on the total weight of the isocyanate-reactive composition.

[0162] Item 98. The sum of the amounts of the aromatic amine-initiated polyether polyol, the sugar-initiated polyether polyol, and the triol-initiated polyether polyol is at least 90% by weight, at least 95% by weight, at least 98% by weight, or 100% by weight, based on the total weight of the polyol blend. The isocyanate-reactive composition according to any one of items 88 to 97.

[0163] Item 99. The isocyanate-reactive composition according to any one of items 76 to 98, wherein the physical blowing agent is a hydrocarbon such as cyclopentane, isopentane, n-pentane, butane, and propane, 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene, 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)-2-pentene or cis-1,1,1,4,4,4-hexafluoro-2-butene, or a perfluorinated alkene, such as trans-1-chloro-3,3,3-trifluoropropene, or a mixture of two or more thereof.

[0164] Item 100. The isocyanate-reactive composition according to any one of items 76 to 99, wherein the physical blowing agent is present in an amount of at least 5% by weight, 5% to 30% by weight, 5% to 20% by weight, or 5% to 15% by weight, based on the total weight of the isocyanate-reactive composition.

[0165] Item 101. The isocyanate-reactive composition according to any one of items 76 to 100, wherein the water is present in an amount of at least 1.0% by weight, 1.0% to 5.0% by weight, 1.0% to 4.0% by weight, 1.0% to 3.0% by weight, or 1.0% to 2.0% by weight, based on the total weight of the isocyanate-reactive composition.

[0166] Item 102. The isocyanate-reactive composition according to any one of items 76 to 101, wherein the physical blowing agent composition and water are present in a relative weight ratio of at least 5:1, 5:1 to 50:1, 5:1 to 20:1, 5:1 to 9:1, or 5:1 to 7:1.

[0167] Item 103. The tertiary amine is trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, dimethylbenzylamine, dibutylcyclohexylamine, dimethylethanolamine, triethanolamine, diethylethanolamine, ethyldiethanolamine, dimethylisopropanolamine, dimethyloctylamine, triisopropanolamine, triethylenediamine, tetramethyl-1,3-butanediamine, N,N,N',N '-Tetramethylethylenediamine, N,N,N',N'-Tetramethylhexane-1,6-diamine, N,N,N',N',N''-Pentamethyldiethylenetriamine, Bis(2-dimethylaminoethoxy)methane, N,N,N'-Trimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-Dimethyl-N',N'-(2-hydroxyethyl)ethylenediamine, Tetramethylguanidine, N-Methylpiperidine, N-Ethylpiperidine, N-Methylmorpholine, N-Ethylmorph morpholine, 1,4-dimethylpiperidine, 1,2,4-trimethylpiperidine, N-(2-dimethylaminoethyl)morpholine, 1-methyl-4-(2-dimethylamino)piperidine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]-5-nonane, or any combination of two or more thereof, for example, the tertiary amine includes an unblocked tertiary amine and a chemically blocked tertiary amine. Item 76 to Item 102. The isocyanate-reactive composition according to any one of Items 76 to 102, wherein, for example, the unblocked tertiary amine and the chemically blocked tertiary amine are present in a weight ratio of 1:5 to 5:1, 1:3 to 3:1, 1:2 to 2:1 or 1.1:1 to 1:1.1, and / or each of the unblocked tertiary amine and the chemically blocked tertiary amine is present in an amount of 0.1% to 1% by weight, 0.1% to 0.5% by weight, or 0.3% to 0.5% by weight, based on the total weight of the isocyanate-reactive composition.

[0168] Item 104. The isocyanate-reactive composition according to any one of items 76 to 103, wherein the tertiary amine is present in an amount of 0.01% by weight to 3.0% by weight, 0.3% by weight to 2.5% by weight, or 1.0% by weight to 2.0% by weight, based on the total weight of the isocyanate-reactive composition.

[0169] Item 105. The isocyanate-reactive composition according to any one of items 76 to 104, wherein each R may be the same or different and has 5 to 15, 5 to 10, or 7 to 9 carbon atoms.

[0170] Item 106. The metal carboxylate includes a metal salt of an aliphatic monocarboxylic acid having 2 to 25 carbon atoms, and for example, the aliphatic monocarboxylic acid includes a saturated aliphatic monocarboxylic acid, an unsaturated aliphatic monocarboxylic acid, or a mixture thereof, and for example, the aliphatic monocarboxylic acid includes ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, naphthenic acid, 9-hexadecenoic acid, Item 76 to Item 105. The isocyanate-reactive composition according to any one of claims 76 to 105, comprising cis-9-octadecenoic acid, 11-octadecenoic acid, cis,cis-9,12-octadecadienoic acid, 9,12,15-octadecatrienoic acid, 6,9,12-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, 5,8,11,14-eicosatetraenoic acid, tung oil acid, linseed oil acid, soybean oil acid, resin acid, tall oil fatty acid, rosin acid, abietic acid, neoabietic acid, palustric acid, pimaric acid, dehydroabietic acid, or a mixture of any two or more thereof.

[0171] Item 107. The isocyanate-reactive composition according to any one of items 76 to 106, wherein the metal carboxylate is present in an amount of 0.01% by weight to 1.0% by weight, 0.02% by weight to 0.5% by weight, or 0.05% by weight to 0.15% by weight, based on the total weight of the isocyanate-reactive composition.

[0172] Section 108.Each R 1 may be the same or different and are saturated or unsaturated linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, for example, each R 1 may be the same or different and are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, dodecanyl, octadecanyl, vinyl, allyl, prenyl, crotyl, cyclopentadienyl, phenyl, tolyl, xylyl, or a substituted aryl group; and / or R 2 is a saturated or unsaturated linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, R 2 may be the same or different and are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, dodecanyl, octadecanyl, vinyl, allyl, prenyl, crotyl, cyclopentadienyl, phenyl, tolyl, xylyl, or a substituted aryl group. The isocyanate-reactive composition according to any one of claims 76 to 107.

[0173] Item 109. The β-dicarbonyl compound is 2,4-pentanedione, 3-chloro-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 3-(1-hydroxyethylidene)-2,4-pentanedione, 3-nitro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 2,4-hexanedione, 5-methyl-2,4-hexanedione, 5 ,5-Dimethyl-2,4-hexanedione, 3-Ethyl-2,4-pentanedione, 2,4-Octanedione, 2,4-Decanedione, 2,2-Dimethyl-3,5-nonanedione, 2,4-Tridecanedione, 1-Cyclohexyl-1,3-butanedione, 5,5-Dimethyl-1,3-cyclohexanedione, 1,3-Cyclohexanedione, 1-Phenyl-1,3-butanedione, 1-Phenyl-1,3-pentanedione 1-(4-biphenyl)-1,3-butanedione, 3-benzyl-2,4-pentanedione, 1-phenyl-5,5-dimethyl-2,4-hexanedione, 1-phenyl-2-butyl-1,3-butanedione, and 1-phenyl-3,3-(2-methoxyphenyl)-1,3-propanedione, 3-oxobutanamide, methylenediformamide, methyl-3-oxobutanoate, N-(2-methyloxyethyl)-1,3-propanedione, Item 76 to Item 108, comprising 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 3-methyl-2,4-pentanedione, or any combination of two or more thereof.

[0174] Item 110. The isocyanate-reactive composition according to any one of items 76 to 109, wherein the β-dicarbonyl compound and the metal carboxylate are present in a relative weight ratio of at least 0.5:1, for example, 0.5:1 to 10:1, 1:1 to 10:1, 1:1 to 5:1, or 1:1 to 3:1.

[0175] The following non-limiting and non-exhaustive examples are intended to further illustrate various non-limiting and non-exhaustive embodiments without limiting the scope of the embodiments described herein. EXAMPLES

[0176] A foam-forming composition was prepared using the ingredients and amounts (parts by weight) shown in Table 1. The following materials were used: Polyol 1: a polyether polyol having a hydroxyl number of 470 mg KOH / g and a functionality of 3, prepared by propoxylating glycerin; Polyol 2: a polyether polyol having a hydroxyl number of 380 mg KOH / g and a functionality of 5.8, prepared by propoxylating a mixture of sucrose and water (83 wt. % sucrose and 17 wt. % water); Polyol 3: A polyether polyol having a hydroxyl number of 388 mg kOH / g and a functionality of 4, prepared by alkoxylating o-TDA, the alkylene oxide being 63% by weight propylene oxide and 37% by weight ethylene oxide; Surfactant: Tegostab™ B-8433 from Evonik; Catalyst 1: Bis(2-dimethylaminoethyl) ether, commercially available as Niax™ A-1 from Momentive; Catalyst 2: A formic acid blocked version of bis(2-dimethylaminoethyl) ether, commercially available as Niax™ A-107 from Momentive; Catalyst 3: Dimethylpiperazine, commercially available from Huntsman as Jeffcat™ DMP; Catalyst 4: Iron octoate, commercially available from Reaxis as Reaxis™ C3001; Catalyst 5: A blend of bismuth neodecanoate and zinc neodecanoate, commercially available from Reaxis as Reaxis™ C708; Additive 1: 2,4-pentanedione; Blowing agent: cyclopentane; and Isocyanate: polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%, viscosity 200 mPa·s at 25° C. (MONDUR® MR from Covestro).

[0177] In each case, a masterbatch was prepared by mixing polyol, catalyst, surfactant, additives, water, and blowing agent in the amounts shown in Table 1. Foams were prepared by mixing the masterbatch with isocyanate in an amount sufficient to provide the Isocyanate Index shown in Table 1 and pouring the mixture into an 83 ounce paper cup. Cream time, gel time, and free rise density ("FRD") were recorded.

[0178] Flow was evaluated as described in U.S. Pat. No. 10,106,641 (column 12, lines 22-61, the cited portion of which is incorporated herein by reference). Additionally, a pressure transducer was placed 10 cm above the edge of the protruding sheet metal base, which recorded the foam pressure during the process. Rise rate was derived from the foam height data as a function of time. Rise rate profiles for selected examples are shown in FIG. 1(a)-FIG. 1(d). These examples demonstrate the ability to tune both gel and flow behavior based on the incorporation of iron octoate catalyst and β-dicarbonyl compounds. This flexibility allows the user to optimize foam flow, specifically the balance between flow and gelation, and overall foam performance, which is currently believed to result in improved cell structure and foam performance, as well as improved k values, i.e., improved thermal insulation. Additionally, the incorporation of bismuth / zinc catalyst and β-dicarbonyl compounds improves the flow profile by increasing the amount of flow that occurs before gelation and viscosity buildup.

[0179] The results are shown in Table 1. Examples 3 to 5 and Examples 7 to 8 are inventive examples, and Examples 1 to 2 and Example 6 are comparative examples.

[0180] [Table 1]

[0181] Although the invention has been described in detail above for purposes of illustration, it is to be understood that such detail is for that purpose only and changes may be made by those skilled in the art without departing from the spirit and scope of the invention, except as it may be limited by the claims.

Claims

1. 1. A polyurethane foam-forming composition comprising: (a) a polyol; (b) a catalyst composition comprising: (i) a tertiary amine, and (ii) Structure: 【Chemistry 1】 wherein each R may be the same or different, is a saturated or unsaturated, optionally substituted (cyclo)alkyl group having from 2 to 25 carbon atoms, x is 2 or 3, and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), cobalt(III), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium; (c) a blowing agent composition comprising: (i) a physical blowing agent, and (ii) water; A blowing agent composition comprising: (d) Structure: 【Chemistry 2】 (In the formula, (i) each R １ may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with a heteroatom and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R ２ is hydrogen or R １ and a β-dicarbonyl compound having (e) a polyisocyanate; and 1. A polyurethane foam-forming composition comprising:

2. 2. The polyurethane foam-forming composition of claim 1, wherein the polyisocyanate comprises a methylene bridged polyphenyl polyisocyanate and / or a prepolymer of a methylene bridged polyphenyl polyisocyanate having an average functionality of 1.8 to 3.5 isocyanate moieties per molecule and an NCO content of 25% to 32% by weight.

3. 2. The polyurethane foam-forming composition of claim 1, wherein the polyol comprises a polyol blend comprising two or more different polyether polyols, the polyol blend comprising an aromatic amine-initiated polyether polyol that is the reaction product of an H-functional starting material and an alkylene oxide, the H-functional starting material comprising an aromatic amine present in an amount greater than 50 weight percent, based on the total weight of H-functional starting materials used to make the aromatic amine-initiated polyether polyol, propylene oxide is present in an amount greater than 50 weight percent, based on the total weight of alkylene oxide used to prepare the aromatic amine-initiated polyether polyol, and the aromatic amine-initiated polyether polyol has an OH number from 200 mg KOH / g to 600 mg KOH / g and a functionality of at least 2.

5.

4. The polyurethane foam-forming composition of claim 3, wherein the aromatic amine-initiated polyether polyol is present in an amount from 10% to 30% by weight, based on the total weight of the polyol blend.

5. 5. The polyurethane foam-forming composition of claim 4, wherein the polyol blend comprises a sugar-initiated polyether polyol that is the reaction product of an H-functional starting material and an alkylene oxide, the H-functional starting material comprising a sugar present in an amount greater than 50 weight percent, based on the total weight of H-functional starting materials used to make the sugar-initiated polyether polyol, propylene oxide is present in an amount greater than 50 weight percent, based on the total weight of alkylene oxide used to prepare the sugar-initiated polyether polyol, and the sugar-initiated polyether polyol has an OH number of from 200 mg KOH / g to 600 mg KOH / g and a functionality of 4 to 6.

6. 6. The polyurethane foam-forming composition of claim 5, wherein the sugar-initiated polyether polyol is present in an amount of from 20% to 40% by weight, based on the total weight of the polyol blend.

7. 7. The polyurethane foam-forming composition of claim 6, wherein the polyol blend comprises a triol-initiated polyether polyol that is the reaction product of an H-functional starting material and an alkylene oxide, the triol being present in an amount greater than 50 weight percent, based on the total weight of H-functional starting materials used to make the triol-initiated polyether polyol, propylene oxide being present in an amount greater than 50 weight percent, based on the total weight of alkylene oxide used to prepare the triol-initiated polyether polyol, the triol-initiated polyether polyol having an OH number of from 300 mg KOH / g to 600 mg KOH / g and a functionality of from 2.5 to 3.5, and the triol-initiated polyether polyol being present in an amount of from 30 weight percent to 70 weight percent, based on the total weight of the polyol blend.

8. 2. The polyurethane foam-forming composition of claim 1, wherein the physical blowing agent comprises a hydrocarbon present in an amount of from 5% to 20% by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

9. 2. The polyurethane foam-forming composition of claim 1, wherein said physical blowing agent composition and said water are present in a relative weight ratio of from 5:1 to 9:

1.

10. 2. The polyurethane foam-forming composition of claim 1, wherein the tertiary amine comprises an unblocked tertiary amine and a chemically blocked tertiary amine, and the unblocked tertiary amine and the chemically blocked tertiary amine are present in a relative weight ratio of from 1:5 to 5:

1.

11. 2. The polyurethane foam-forming composition according to claim 1, wherein each R, which may be the same or different, has from 5 to 15 carbon atoms.

12. The metal carboxylate is selected from the group consisting of ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, naphthenic acid, 9-hexadecenoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid, cis,cis-9,12-octadecadienoic acid, and 9,12,15-octadecatrienoic acid.

2. The polyurethane foam-forming composition of claim 1, comprising a metal salt of an aliphatic monocarboxylic acid comprising: 6,9,12-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, 5,8,11,14-eicosatetraenoic acid, tung oil acid, linseed oil acid, soybean oil acid, resin acids, tall oil fatty acids, rosin acid, abietic acid, neoabietic acid, palustric acid, pimaric acid, dehydroabietic acid, or a mixture of any two or more thereof.

13. Each R １ 2. The polyurethane foam-forming composition of claim 1, wherein x, y, y, and z are the same or different (cyclo)alkyl groups having 1 to 10 carbon atoms.

14. The β-dicarbonyl compound is 2,4-pentanedione, 3-chloro-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-butyl-2,4-pentanedione, 3-(1-hydroxyethylidene)-2,4-pentanedione, 3-nitro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 2,4-hexanedione, 5-methyl-2,4-hexanedione, 5,5- Dimethyl-2,4-hexanedione, 3-ethyl-2,4-pentanedione, 2,4-octanedione, 2,4-decanedione, 2,2-dimethyl-3,5-nonanedione, 2,4-tridecanedione, 1-cyclohexyl-1,3-butanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-cyclohexanedione, 1-phenyl-1,3-butanedione, 1-phenyl-1,3-pentanedione 1-(4-biphenyl)-1,3-butanedione, 3-benzyl-2,4-pentanedione, 1-phenyl-5,5-dimethyl-2,4-hexanedione, 1-phenyl-2-butyl-1,3-butanedione, and 1-phenyl-3,3-(2-methoxyphenyl)-1,3-propanedione, 3-oxobutanamide, methylenediformamide, methyl-3-oxobutanoate, N-(2-methyloxyethylene)-1,3-propanedione, 14. The polyurethane foam-forming composition of claim 13, comprising at least one of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 3-methyl-2,4-pentanedione, or a combination of any two or more thereof.

15. 2. The polyurethane foam-forming composition of claim 1, wherein said β-dicarbonyl compound and said metal carboxylate are present in a relative weight ratio of from 0.5:1 to 10:

1.

16. 16. The polyurethane foam-forming composition of claim 15, wherein said β-dicarbonyl compound and said metal carboxylate are present in a relative weight ratio of from 1:1 to 5:

1.

17. 1. A process for producing a polyurethane foam comprising reacting a polyurethane foam-forming composition at an isocyanate index of from 0.90 to 1.50, said polyurethane foam-forming composition comprising: (a) a polyol; (b) a polyisocyanate; and (c) a catalyst composition; and (d) a blowing agent composition; and (e) a β-dicarbonyl compound; and Including, (1) The catalyst composition comprises: (i) a tertiary amine, and (ii) Structure: 【Chemistry 3】 wherein each R may be the same or different, is a saturated or unsaturated, optionally substituted (cyclo)alkyl group having 2 to 25 carbon atoms, x is 2 or 3, and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), cobalt(III), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium; (2) The foaming agent composition is (i) a physical blowing agent, and (ii) contains water; (3) The β-dicarbonyl compound has the structure: 【Chemistry 4】 (In the formula, (i) each R １ may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with a heteroatom and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R ２ is hydrogen or R １ (wherein

18. 1. An isocyanate-reactive composition comprising: (a) a polyol; (b) a catalyst composition comprising: (i) a tertiary amine, and (ii) Structure: 【Chemistry 5】 wherein each R may be the same or different, is a saturated or unsaturated, optionally substituted (cyclo)alkyl group having from 2 to 25 carbon atoms, x is 2 or 3, and M is aluminum, barium, bismuth, cadmium, calcium, cerium(III), chromium(III), cobalt(II), cobalt(III), copper(II), indium, iron(III), lanthanum, lead(II), manganese(II), manganese(III), neodymium, nickel(II), palladium(II), potassium, samarium, sodium, terbium, tin(II), tin(IV), titanium, vanadium, yttrium, zinc, or zirconium; (c) a blowing agent composition comprising: (i) a physical blowing agent, and (ii) a blowing agent composition comprising water; and (d) Structure: 【Chemistry 6】 (In the formula, (i) each R １ may be the same or different and are an amide group, an ester group, a carboxylic acid group, a (cyclo)alkyl group, or a (cyclo)alkoxy group, the (cyclo)alkyl group and the (cyclo)alkoxy group being optionally substituted with a heteroatom and optionally containing an amide group, an ester group, or a carboxylic acid group; (ii) R ２ is hydrogen or R １ and a β-dicarbonyl compound having 1. An isocyanate-reactive composition comprising:

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