Halogenated olefin-containing polyurethane foam-forming compositions, related foams, and methods of making same

Abstract

A polyurethane foam forming composition includes a polyol blend, a blowing agent composition, and a polyisocyanate. The polyol blend has a weighted average functionality of from 3 to 6 and a weighted average OH number of from 300 to 500 mg KOH / g. The blowing agent composition comprises a physical blowing agent and a carbon dioxide-generating chemical blowing agent wherein the physical blowing agent comprises a halogenated olefin present in an amount (i) in the range of from 1 to 30% by weight, based on the total weight of the polyurethane foam-forming composition other than the weight of the polyisocyanate, and (ii) in the range of at least 80% by weight, based on the total weight of the polyurethane foam-forming composition, based on the total weight of the polyurethane foam-forming composition, based on the total weight of the polyurethane foam-forming composition. Based on the total weight of the physical blowing agent in the blowing agent composition. The physical blowing agent composition and the carbon dioxide-generating chemical blowing agent are present in a relative ratio by weight of at least 5: 1. The polyisocyanate includes a urethane-modified polyisocyanate, the urethane-modified polyisocyanate having an NCO group content of from 25 to 35 wt%, based on the total weight of the urethane-modified polyisocyanate, and including a reaction product of a polymethylene polyphenyl polyisocyanate and a mono-alcohol.

Description

Technical Field

[0001] This invention generally relates to polyurethane foam forming compositions containing halogenated olefins, and polyurethane foams prepared therefrom. Background Technology

[0002] Rigid polyurethane foams are used in many applications. They are prepared by reacting polyisocyanates with isocyanate reactive compounds (usually polyols) in the presence of a blowing agent. One use of this type of foam is as an insulation medium in the structure of refrigerated storage equipment, including refrigerated appliances and tractor trailers. The insulation performance of closed-cell rigid foams depends on many factors, including the average cell size and the thermal conductivity of the cell contents.

[0003] The thermal conductivity of the foam contents depends on the blowing agent used. Fluorocarbons have historically been used due to their low thermal conductivity. However, fluorocarbons (including chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), and hydrochlorofluorocarbons (HCFCs)) are greenhouse gases and are being phased out. Halogenated olefins (such as HCFO) are more environmentally friendly alternatives to these fluorocarbons, but are more expensive.

[0004] Thermal efficiency is typically assessed by low thermal conductivity, or the "K-value," a crucial characteristic of rigid polyurethane foam insulation. Even seemingly small reductions in the K-value, such as a few percentage points, can translate into significant reductions in energy consumption and costs over the lifespan of equipment using the foam. For example, some estimates suggest that a 2% reduction in the K-value can improve the energy performance of a refrigerator by approximately 1%, allowing for the use of a smaller compressor and thus providing potential energy and cost savings over the refrigerator's lifespan. Furthermore, the thickness of refrigerator walls or doors can be reduced while achieving similar insulation performance, allowing for increased internal storage space.

[0005] Therefore, rigid polyurethane foams with improved thermal conductivity, produced by halogenated olefins while maintaining good foam physical properties and processing characteristics, would be ideal. Summary of the Invention

[0006] In some aspects, the present invention relates to polyurethane foam forming compositions. These polyurethane foam forming compositions comprise a polyol blend, a blowing agent composition, and a polyisocyanate. The polyol blend has a weighted average functionality of 3 to 6 and a weighted average OH value of 300 to 500 mg KOH / g. The blowing agent composition comprises: (1) a physical blowing agent and (2) a carbon dioxide-generating chemical blowing agent, wherein the physical blowing agent comprises a halogenated olefin, the halogenated olefin being present in an amount (i) of 1 to 30% by weight based on the total weight of the polyurethane foam forming composition excluding the weight of the polyisocyanate, and (ii) of at least 80% by weight based on the total weight of the physical blowing agent in the blowing agent composition. The physical blowing agent composition and the carbon dioxide-generating chemical blowing agent are present in a relative ratio of at least 5:1 by weight. The polyisocyanate comprises a urethane-modified polyisocyanate having an NCO group content of 25 to 35% by weight, based on the total weight of the urethane-modified polyisocyanate, and comprising a reaction product containing the following components: (1) a polymethylene polyphenyl polyisocyanate; and (2) a monool. The presence of the polyisocyanate is sufficient to provide an isocyanate index of 0.90 to 1.50.

[0007] In other respects, the present invention relates to a method for preparing polyurethane foam. The method comprises reacting a polyurethane foam forming composition comprising a polyol blend, a blowing agent composition, and a polyisocyanate under conditions of an isocyanate index of 0.90 to 1.50. In these methods, the polyol blend has a weighted average functionality of 3 to 6 and a weighted average OH value of 300 to 500 mg KOH / g. The blowing agent composition comprises: (1) a physical blowing agent and (2) a carbon dioxide-generating chemical blowing agent, wherein the physical blowing agent comprises a halogenated olefin, said halogenated olefin being present in an amount (i) of 1 to 30% by weight, based on the total weight of the polyurethane foam forming composition excluding the weight of the polyisocyanate, and (ii) of at least 80% by weight, based on the total weight of the physical blowing agent in the blowing agent composition. The physical blowing agent composition and the carbon dioxide-generating chemical blowing agent are present in a relative ratio of at least 5:1 by weight. The polyisocyanate comprises a urethane-modified polyisocyanate having an NCO group content of 25 to 35% by weight based on the total weight of the urethane-modified polyisocyanate, and comprising a reaction product containing the following components: (1) a polymethylene polyphenyl polyisocyanate; and (2) a monool.

[0008] The present invention also relates to rigid polyurethane foam prepared from such foam forming compositions, rigid polyurethane foam prepared by such methods, composite articles comprising the rigid foam, and thermal insulation panels comprising the rigid foam. Detailed Implementation

[0009] Various embodiments are described and illustrated in this specification to provide a comprehensive understanding of the structure, function, performance, and use of the disclosed invention. The various embodiments described and illustrated in this specification are non-limiting and non-exhaustive. Therefore, the invention is not limited to the description of the various non-limiting and non-exhaustive embodiments disclosed in this specification. Features and characteristics described in conjunction 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 this specification. Therefore, the claims may be amended to include any feature or characteristic explicitly or inherently described in this specification or otherwise explicitly or inherently supported by this specification. Furthermore, the applicant reserves the right to amend the claims to explicitly exclude features or characteristics that may be present in the prior art. Therefore, any such modifications comply with the requirements of 35 USC § 112 and 35 USC § 132(a). The various embodiments disclosed and described in this specification may include, consist of, or consist substantially of features and characteristics as described herein.

[0010] Unless otherwise stated, the entire contents of any patent, publication, or other public material identified herein are incorporated herein by reference only to the extent that the incorporated material does not conflict with any existing definitions, statements, or other public materials expressly set forth herein. Consequently, and to the extent necessary, any conflicting material incorporated herein by reference will be replaced by the express disclosure set forth herein. Any material or portion thereof that is incorporated herein by reference but conflicts with any existing definitions, statements, or other public materials set forth herein will be incorporated only to the extent that there is no conflict between the incorporated material and the existing public materials. The applicant reserves the right to amend this specification to explicitly elaborate any subject matter or portion thereof incorporated herein by reference.

[0011] In this specification, unless otherwise stated, all numerical parameters should be understood to be predicated on and modified by the term "about" in all cases, where the numerical parameters have inherent fluctuation characteristics of the basic measurement techniques used to determine the values ​​of the parameters. To a minimum, and not at all, to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter described herein should be interpreted at least based on the recorded significant figures and by applying conventional rounding techniques.

[0012] Furthermore, any numerical range described herein includes all subranges with the same numerical precision contained within the range. For example, the range “1.0 to 10.0” is intended to include all subranges between (and including) the minimum value of 1.0 and the maximum value of 10.0, that is, all subranges where the minimum value is equal to or greater than 1.0 and the maximum value is equal to or less than 10.0, such as 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described herein is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to amend this specification (including the claims) to expressly describe any subranges contained within the range expressly stated herein. All such ranges are intended to be inherently described in this specification such that any modifications to any such subrange expressly described will comply with the requirements of 35 U.S.SC § 112 and 35 U.S.C § 132(a).

[0013] Unless otherwise stated, the grammatical articles “one,” “a,” and “an” used in this specification are intended to include “at least one” or “one or more.” Therefore, the articles used in this specification refer to one or more (i.e., “at least one”) grammatical objects of that article. For example, “a component” means one or more components, and therefore, more than one component may be considered, and more than one component may be employed or used in the implementation of the described embodiments. Furthermore, the use of singular nouns includes plural nouns, and the use of plural nouns includes singular nouns, unless the context requires otherwise.

[0014] As used herein, the term “functionality” refers to the average number of reactive hydroxyl groups (-OH) present in each molecule of the described -OH functional group raw material. In the preparation of polyurethane foam, hydroxyl groups react with isocyanate groups (-NCO) attached to the isocyanate compound. The terms “OH value” and “number of -OH” refer to the number of reactive hydroxyl groups available for the reaction and are expressed as milligrams of potassium hydroxide equivalent to the hydroxyl content of 1 gram of polyol (ASTM D4274-16). The term “equivalent weight” refers to the weight of a compound divided by its valence. For polyols, the equivalent weight is the weight of the polyol bonded to one isocyanate group 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 56,100 by the OH value of the polyol—equivalent weight (g / eq) = (56.1 x 1000) / OH value.

[0015] Some embodiments of this specification relate to polyurethane foam molding compositions used in the preparation of rigid polyurethane foams. Rigid foams are characterized by a compressive strength to tensile strength ratio of at least 0.5:1, elongation of less than 10%, and low deformation recovery and low elastic limit, as described in "Polyurethanes: Chemistry and Technology, Part II Technology," JH Saunders & KC Frisch, Interscience Publishers, 1964, page 239.

[0016] The polyurethane foam described in this specification is a reaction product of a polyurethane foam forming composition comprising a polyisocyanate. As used herein, the term "polyisocyanate" includes diisocyanates and isocyanates with a functionality greater than 2.0.

[0017] More specifically, in the polyurethane foam forming compositions of the present invention, the polyisocyanate includes urethane-modified polyisocyanates. The urethane-modified polyisocyanates used in the polyurethane foam forming compositions of this specification comprise the reaction products of the following components: (1) polymethylene polyphenyl polyisocyanate (“pMDI”); and (2) a monool. As used herein, the term “monool” refers to one or more isocyanate reactive compounds having an average isocyanate reactive group functionality of not more than 1.2, for example, from 0.8 to 1.2. Furthermore, the urethane-modified polyisocyanates described herein are not polyisocyanate prepolymers. As used herein, “polyisocyanate prepolymer” refers to the reaction product of a polyisocyanate with one or more isocyanate reactive compounds having an average isocyanate reactive group functionality greater than 1.2. However, in some embodiments, the polyurethane foam forming compositions of this specification may also include polyisocyanate prepolymers in addition to the urethane-modified polyisocyanates described herein.

[0018] It should be understood that pMDI is a mixture of diphenylmethane diisocyanate (“MDI”) and one or more homologues thereof, wherein the isocyanate functionality of the homologues is greater than 2. In some embodiments, the average isocyanate functionality of pMDI is 2.1 to 3.2, for example 2.5 to 3.2, or in some cases 2.6 to 3.2 or 2.8 to 3.2. The general formula of pMDI can be represented by the following general structure: Where n is an integer of 0 or greater.

[0019] More specifically, in some embodiments, pMDI comprises: i) up to 60% by weight of a first polymethylene polyphenyl polyisocyanate having the general formula (I), based on 100% by weight of the polymethylene polyphenyl polyisocyanate, (I), and At least 40% by weight of a second polymethylene polyphenyl polyisocyanate having general formula (II), based on 100% by weight of polymethylene polyphenyl polyisocyanate. (II), Where n is an integer of 1 or greater.

[0020] In some embodiments, pMDI has an NCO content of 25 to 35% by weight, 29 to 34% by weight, or 29.0 to 32.0% by weight, based on the total weight of the urethane-modified polyisocyanate. Furthermore, in some embodiments, the viscosity of pMDI at 25°C (measured according to EN ISO 3219, October 1994) is 100 to 750 mPa·s, for example 100 to 600 mPa·s, or 150 to 450 mPa·s.

[0021] As described, the urethane-modified polyisocyanate present in the polyurethane foam forming compositions of this specification comprises a reaction product containing pMDI and a monool. In some embodiments, the monool comprises a compound represented by the following structure: Where R 1 R 2 and R 3 Each independently represents H, C1-C 56 Alkyl groups, C6-C 56 aryl group, C3-C 56 Cycloalkyl groups or C7-C 56 Aryl groups, or groups R 1 R 2 and / or R 3 They can be connected via a ring system. In some implementations, R 1 R 2 and R 3 Any one or more of these groups may also represent any of the aforementioned groups, which further contain functional groups that do not react with isocyanate groups.

[0022] Examples of compounds represented by the above structures include primary alcohols, secondary alcohols, tertiary alcohols, or any combination of two or more thereof, as well as aromatic monools, aliphatic monools, cyclic aliphatic monools, or any combination of two or more thereof, each of which may be saturated or unsaturated, cyclic, straight-chain or branched. The alcohol may contain 1 to 56, 1 to 36, 1 to 26, 10 to 15, or 12 to 15 carbon atoms. Specific examples of suitable monools include, but are not limited to: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-hydroxypentane, 3-hydroxypentane, isomers of primary methylbutanol and secondary methylbutanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, 2-ethylhexanol, primary and secondary trimethylhexanol, cyclohexanol, alkyl-substituted cyclohexanol, cyclopentanol, cyclohexylmethanol, phenol, alkyl-substituted phenols (such as nonylphenol), benzyl alcohol, n-decyl alcohol, n-undecyl alcohol, n-dodecanol, n-tetanecanol, n-tridecyl alcohol, n-tetradecyl alcohol, Pentadecyl alcohol, hexadecyl alcohol, heptadecanol, octadecyl alcohol, nonadecanol, eicosanool, hexadecyl alcohol, heptadecanol, 2,2,4-trimethyl-1-pentanol, 2,6,8-trimethylnonanol, 4-cyclohexyl-1-butanol, 2,4,6-trimethylbenzyl alcohol, 2-methylprop-2-ol, 2-ethyl-1-butanol, 2-methyl-2-butanol, 2-methyl-3-buten-2-ol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 3-ethyl- 3-Pentanol, 3-Ethyl-3-nonanol, 3-Methyl-1-butyn-3-ol, 3-Methyl-1-pentyn-3-ol, 2,6-Dimethyl-4-heptanol, 3,5-Dimethyl-1-hexanol, 3,5-Dimethyl-1-hexyn-3-ol, 1-Methylcyclopentanol, 1-Methylcyclohexanol, 1-Ethylcyclohexanol, 1,1-Diphenylacetaldehyde, 1,1,2-Triphenylethanol, tert-Butanol, 3-Isopropenylcumenol, 2-Hydroxystyrene, 3-Hydroxystyrene, 4-Hydroxystyrene, 4 -Isopropenyl cumene alcohol, 3-isopropenylphenol, 4-isopropenylphenol, p-hydroxy-α-phenylstyrene, p-hydroxy-β-phenylstyrene, 4-hydroxy-α-ethylstyrene, α-chloromethyl-p-hydroxystyrene, allyl alcohol, 2-allylphenol, 2-allyl-6-methylphenol, cinnamyl alcohol, undecenol, allylamine, acrylic acid, undecenic acid, 9-hexadecen-1-ol, 9-octadecen-1-ol, and 10-eicoseno-1-ol, and mixtures of any two or more thereof. In some embodiments, the monool comprises C 12 Primary alcohol, C 13 Primary alcohol, C 14 Primary alcohols and C 15 A blend of primary alcohols, which is available from Shell as Neodol 25.

[0023] In addition to the above, in some embodiments, the monool may include fluorinated monools, specific examples of which include, but are not limited to: 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol, 2,2,3,3-tetrafluoro-1-propanol, 4,4,5,5,5-pentafluoro-1-pentanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 3,3,3-trifluoro-1-propanol, 6,6-nonafluoro-1-hexanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tetrafluoro-1-octanol, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexanol, 6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-teicosicofluoro-1-dodecyl alcohol, and mixtures of any two or more of the above.

[0024] In addition to the monomeric monools described above, in some embodiments, the monool may comprise oligomers or polymers derived from the monomeric monool in higher equivalent weights. For example, in some cases, the monool may comprise a polyether monool with an equivalent weight of at least 850 (e.g., at least 1000, at least 1100, or at least 1200) and up to 10000 (e.g., up to 7000 or up to 4500). As used herein, the term polyether monool refers to a compound having a theoretical functionality within the aforementioned specified equivalent weight range.

[0025] Such polyether monools can be prepared by polycondensation of alkyl epoxides with monool initiators. Suitable alkyl epoxides include, for example, ethylene oxide, propylene oxide, butane oxide, pentane oxide, hexane oxide, aromatic alkyl epoxides (such as styrene oxide), and haloalkyl epoxides (such as trichlorobutane oxide), and combinations of any two or more thereof. Suitable monool initiators include any of the monools mentioned above. In addition to monofunctional compounds, the initiator may also contain relatively small amounts of difunctional or higher functional compounds, such as ethylene glycol, propylene glycol, glycerol, etc. However, in some embodiments, the content of such difunctional or higher functional compounds is no more than 10% by weight, no more than 5% by weight, or no more than 1% by weight, based on the total weight of the initiator used to prepare the polyether monool. In some embodiments, the content of the monool initiator is at least 90% by weight, at least 95% by weight, or at least 99% by weight, based on the total weight of the initiator used to prepare the polyether monomer.

[0026] Alkoxylation can be carried out by suitable methods, such as base catalysis using strong bases like sodium hydroxide, potassium hydroxide, sodium methoxide, or potassium methoxide. Other suitable catalysts include diethylzinc, combinations of metal cycloalkanoates and tertiary amines, etc. In some embodiments, the catalyst comprises a bimetallic cyanide (DMC) complex catalyst, such as the hexacyanocobaltate-glycol catalyst described in U.S. Patent Nos. 4,843,054 and 5,158,922, and the substantially amorphous zinc hexacyanocobaltate tert-butanol complex catalyst described in U.S. Patent No. 5,470,813. In some cases, the amorphous zinc hexacyanocobaltate tert-butanol complex catalyst is used to prepare polyether monools.

[0027] In addition to the compounds described above, the isocyanate reactive compounds that react with pMDI to generate urethane-modified polyisocyanates for use in the polyurethane foam forming compositions of this specification may also include relatively small amounts of compounds with an isocyanate reactive functionality greater than 1 (e.g., glycols and highly functionalized polyols), provided that the amount of such highly functionalized compounds is insufficient to cause the average isocyanate reactive group functionality of the compounds reacting with pMDI to exceed 1.2. Therefore, in some embodiments, such difunctional and / or higher functionalized compounds may be present in amounts up to 10% by weight, for example up to 5% by weight or up to 1% by weight, based on the total weight of the isocyanate reactive compounds that react with pMDI to generate urethane-modified polyisocyanates.

[0028] Furthermore, in some embodiments, the monool is characterized by having a relatively high hydrocarbon content. For example, in some embodiments, the hydrocarbon content of the monool, based on the total weight of the monool, is at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, or in some cases at least 95% by weight. Additionally, the hydrocarbon content of the monool, based on the total weight of the monool, is less than 100% by weight, for example, not exceeding 99.99% by weight, not exceeding 99.9% by weight, not exceeding 99.5% by weight, or not exceeding 99% by weight. As used herein, "hydrocarbon content" refers to the total weight of all carbon and hydrogen atoms present in the molecule. Therefore, for example, in the case of the polyether monool discussed above, "hydrocarbon content" refers to the total weight of all carbon and hydrogen atoms present in the polyether monool, and not merely the weight of carbon and hydrogen atoms present in the monool used as an initiator to prepare the polyether monool.

[0029] To prepare the urethane-modified polyisocyanate used in the polyurethane foam forming composition of this specification, pMDI is reacted with a monool in relative amounts such that for every saturation of hydroxyl groups present, there are 5 to 5000, for example 7 to 4500 equivalents of NCO groups. Any suitable reaction temperature can be used, for example 20°C to 100°C or 40°C to 80°C.

[0030] As described above, in the foam forming compositions of this specification, the content of polyisocyanate is sufficient to provide an isocyanate index of 0.90 to 1.50 (e.g., 1.20 to 1.50). In some embodiments, the aforementioned urethane-modified polyisocyanate is essentially the only polyisocyanate present in the polyurethane foam forming composition. Therefore, in these embodiments, the content of urethane-modified polyisocyanate in the polyurethane foam forming composition is sufficient to provide an isocyanate index of 0.90 to 1.50, for example, 1.20 to 1.50.

[0031] The polyurethane foam forming composition described in this specification further comprises a polyol blend. The polyol blend has a weighted average functionality of 3 to 6, 3 to 5, 3.5 to 4.5, or 3.8 to 4.2, and / or a weighted average OH value of 300 to 500 mg KOH / g, for example, 350 to 450 mg KOH / g. In some embodiments, the polyol blend is present in the polyurethane foam forming composition at a content of at least 50% by weight, for example, 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.

[0032] More specifically, in some embodiments, the polyol blend comprises amine-initiated polyether polyols. As used herein, "amine-initiated polyether polyol" refers to a polyether polyol generated by reacting an H-functional initiator containing an amine (such as an aliphatic amine and / or an aromatic amine) with an epoxide. In some embodiments, the amine initiator comprises an aromatic amine. As used herein, "aromatic amine-initiated polyether polyol" refers to a polyether polyol generated by reacting an H-functional initiator containing an aromatic amine such as toluene diamine ("TDA") with an epoxide. However, in some embodiments, the amine H-functional initiator used to prepare the amine-initiated polyether polyol is not an alkanolamine, and therefore, in some cases, the amine-initiated polyether polyol is different from the alkanolamine-initiated polyether polyol described below.

[0033] In some embodiments, the amine used has an amine functionality of at least 2, for example, 2 to 3. Specific examples of suitable (cyclic)aliphatic amine initiators include, but are not limited to: 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine, pentanediamine, isophoronediamine, 1,10-decanediamine, diaminocyclohexylmethane, pentamethylenediamine, and any combination of two or more of the above. Specific examples of suitable aromatic amines include: crude TDA obtained by reduction after nitration with toluene; 2,3-TDA, 3,4-TDA, 2,4-TDA, 2,6-TDA or mixtures thereof; aniline; 4,4'-methylenediphenylamine; and methylene-bridged polyphenyl polyamines composed of isomers of methylenediphenylamine and triamines or higher molecular weight polyamines, prepared by methods known in the art through the reaction of aniline with formaldehyde. In some implementations, a mixture of 2,3-TDA and 3,4-TDA (often referred to as "ortho-TDA") is used.

[0034] Besides amines, other H-functional initiators can also be used to prepare amine-initiated polyether polyols. These other H-functional initiators include, for example, water, propylene glycol, glycerol, ethylene glycol, ethanolamine, diethylene glycol, or mixtures of any two or more of the above. As understood, multiple individual initiators can be used in combination. However, in some embodiments, the amine (in some cases, an aromatic amine) is the primary or substantially the only H-functional initiator used to prepare the amine-initiated polyether polyol. This means that in these embodiments, the content of the amine (in some cases, an aromatic amine) exceeds 50% by weight, for example, at least 80% by weight, at least 90% by weight, or even up to 100% by weight, based on the total weight of the H-functional initiator used to prepare the amine-initiated polyether polyol.

[0035] Various epoxides can be used to prepare amine-starting polyether polyols, such as ethylene oxide, propylene oxide, butane oxide, pentane oxide, and mixtures thereof. Epoxides can be added individually, sequentially, or in combination to form block structures, or mixed to form intercalation polyethers. Amine-starting polyether polyols may have primary or secondary hydroxyl end groups. In some embodiments, propylene oxide is the primary or substantially the only epoxide used in the preparation of the amine-starting polyether polyol. This means that in these embodiments, the amount of propylene oxide used is greater than 50% by weight, for example at least 80% by weight, at least 90% by weight, or even 100% by weight, based on the total weight of the epoxides used in the preparation of the amine-starting polyether polyol. In some embodiments, the amount of ethylene oxide used is relatively small. In these embodiments, the content of ethylene oxide is no more than 10% by weight, no more than 5% by weight, no more than 1% by weight, or in some cases 0% by weight, based on the total weight of the epoxides used in the preparation of the amine-starting polyether polyol.

[0036] In some embodiments, the amine-starting polyether polyol has an OH value of 200 to 600 mg KOH / g and a functionality of at least 2.5. In some embodiments, the amine-starting polyether polyol has an OH value of 300 to 500 mg KOH / g (e.g., 380 to 420 mg KOH / g) and an average functionality of 3.5 to 4.5, 3.8 to 4.2, or 4.0. Furthermore, in some embodiments, the -C2H4O- unit content of the amine-starting polyether polyol is less than 10% by weight, for example less than 5% by weight, less than 2% by weight, or in some cases 0% by weight, based on the total weight of the amine-starting polyether polyol.

[0037] In some embodiments, the content of amine-starting (e.g., aromatic amine-starting) polyether polyol is at least 30% by weight, based on the total weight of the polyol blend. More specifically, in some embodiments, the content of amine-starting (e.g., aromatic amine-starting) polyether polyol is 30 to 80% by weight, for example 30 to 60% by weight, or in some cases 40 to 60% by weight or 40 to 50% by weight, based on the total weight of the polyol blend.

[0038] In addition, in some cases, polyol blends also include sugar-initiated polyether polyols. As used herein, "sugar-initiated polyether polyol" refers to a polyether polyol generated by reacting an H-functional initiator containing a sugar (such as sucrose) with an alkylene oxide. Examples of suitable alkylene oxides include those previously mentioned in amine-initiated polyether polyols. Some examples of suitable sugar initiators are sucrose, sorbitol, maltitol, and other monosaccharides, disaccharides, trisaccharides, and polysaccharides. Other initiator compounds are often used in combination with sugar initiators to prepare sugar-initiated polyether polyols. Sugars can be used as co-initiators with compounds such as water, propylene glycol, glycerol, ethylene glycol, ethanolamine, diethylene glycol, or any mixture of two or more thereof; however, in some cases, only a small amount or no amine initiator is used to prepare sugar-initiated polyether polyols. It should be understood that multiple individual initiator compounds can be used in combination with sugar initiators.

[0039] In some embodiments, sugar is the primary H-functional initiator used to prepare the sugar-initiated polyether polyol. This means that in these embodiments, the sugar is present in an amount exceeding 50% by weight, for example at least 70% by weight or at least 80% by weight, based on the total weight of the H-functional initiator used to prepare the sugar-initiated polyether polyol.

[0040] In some embodiments, propylene oxide is the primary or substantially the only propylene oxide used in the preparation of sugar-starting polyether polyols. This means that in these embodiments, the amount of propylene oxide used exceeds 50% by weight, for example, at least 60% by weight or at least 70% by weight, based on the total weight of propylene oxide used in the preparation of sugar-starting polyether polyols. In some embodiments, the amount of ethylene oxide used is relatively small. Therefore, in these embodiments, the amount of ethylene oxide used does not exceed 50% by weight, for example, not more than 40% by weight, and in some cases even not more than 30% by weight, based on the total weight of propylene oxide used in the preparation of sugar-starting polyether polyols.

[0041] In some embodiments, the sugar-starting polyether polyol has an OH value of 200 to 600 mg KOH / g, 300 to 550 mg KOH / g, or 380 to 500 mg KOH / g, or in some cases 450 to 500 mg KOH / g, and a functionality of 4 to 6, such as 5 to 6, 5.2 to 5.8, or 5.2 to 5.6. Furthermore, in some embodiments, the content of -C2H4O- units in the sugar-starting polyether polyol is less than 50% by weight, for example less than 40% by weight, or not more than 30% by weight, based on the total weight of the sugar-starting polyether polyol.

[0042] In some embodiments, the sugar-starting polyether polyol is present in an amount of at least 30% by weight, based on the total weight of the polyol blend. More specifically, in some cases, the sugar-starting polyol is present in an amount of 30 to 60% by weight, for example, 30 to 50% by weight, or in some cases, 35 to 45% by weight, based on the total weight of the polyol blend.

[0043] In some embodiments, the polyol blend may include aliphatic triol-based polyether polyols. As used herein, "aliphatic triol-based polyether polyol" refers to a polyether polyol generated by reacting an H-functional initiator containing an aliphatic triol, such as glycerol, with an epoxide. Examples of suitable epoxides include those mentioned above in the section on amine-based polyether polyols. Other initiator compounds may be used in combination with aliphatic triol initiators to prepare aliphatic triol-based polyether polyols. Aliphatic triols may be used as co-initiators with compounds such as water, propylene glycol, sucrose, ethylene glycol, diethylene glycol, or any mixture of two or more thereof; however, in some cases, only a small amount or no amine initiator and no sugar initiator are used when preparing aliphatic triol-based polyether polyols. It should be understood that multiple individual initiator compounds may be used in combination with aliphatic triol initiators.

[0044] In some embodiments, the aliphatic triol is the primary H-functional initiator used to prepare the aliphatic triol-based polyether polyol. This means that in these embodiments, the aliphatic triol content is greater than 50% by weight, for example at least 70% by weight or at least 80% by weight, based on the total weight of the H-functional initiator used to prepare the aliphatic triol-based polyether polyol.

[0045] In some embodiments, propylene oxide is the primary or substantially sole propylene oxide used in the preparation of aliphatic triol-based polyether polyols. This means that in these embodiments, the amount of propylene oxide used exceeds 50% by weight, for example, at least 60% by weight or at least 70% by weight, based on the total weight of propylene oxide used in the preparation of aliphatic triol-based polyether polyols. In some embodiments, the amount of ethylene oxide used is relatively small. Therefore, in these embodiments, the amount of ethylene oxide used does not exceed 50% by weight, for example, not more than 40% by weight, and in some cases even not more than 30% by weight, based on the total weight of propylene oxide used in the preparation of aliphatic triol-based polyether polyols.

[0046] In some embodiments, the OH value of the aliphatic triol-based polyether polyol is 100 to 500 mg KOH / g, such as 200 to 400 mg KOH / g, 200 to 300 mg KOH / g, 200 to 250 mg KOH / g, 230 to 250 mg KOH / g, or 233 to 243 mg KOH / g, and its functionality is greater than 2 to 4, such as 2.5 to 3.5, or in some cases 3.0. Furthermore, in some embodiments, the -C2H4O- unit content of the aliphatic triol-based polyether polyol is less than 50% by weight, such as less than 40% by weight, or not more than 30% by weight, based on the total weight of the aliphatic triol-based polyether polyol.

[0047] In some embodiments, the aliphatic triol-based polyether polyol is present in an amount of at least 30% by weight, based on the total weight of the polyol blend. More specifically, in some cases, the aliphatic triol-based polyol is present in an amount of 30 to 60% by weight, for example, 30 to 50% by weight, or in some cases, 35 to 45% by weight, based on the total weight of the polyol blend.

[0048] Furthermore, in some cases, the polyol blends may comprise alkanolamine-based polyether polyols. As used herein, "alkanolamine-based polyether polyol" refers to a polyether polyol prepared by reacting at least one epoxide with one or more suitable initiator compounds in the presence of a suitable catalyst, wherein the initiator compound comprises one or more alkanolamines. Suitable catalysts include basic catalysts (e.g., sodium hydroxide or potassium hydroxide or tertiary amines such as methylimidazole) and DMC catalysts. In the polyol blends described herein, each of the polyether polyols, including "alkanolamine-based polyether polyols" and "aliphatic amine-based polyether polyols," is distinct from one another.

[0049] As used herein, the term "alkanolamine" refers to a compound represented by the following formula: NH2—Z—OH Where Z represents a divalent group, which is a straight-chain or branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 4 to 6 carbon atoms, or a diallyl ether group having 4 to 6 carbon atoms. A diallyl ether group can be represented by the following formula: —R—O—R— Each R represents a hydrocarbon group with 2 to 3 carbon atoms.

[0050] Suitable examples of alkanolamines for the preparation of alkanolamine-initiated polyether polyols include monoethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 1-(2-aminoethoxy)ethanol, 1-amino-2-butanol, 2-amino-3-butanol, 2-amino-2-methylpropanol, 5-aminopentanol, 3-amino-2,2-dimethylpropanol, 4-aminocyclohexanol, and mixtures of any two or more thereof. In some embodiments, the alkanolamine is the primary H-functional initiator for the preparation of alkanolamine-initiated polyether polyols. This means that in these embodiments, the alkanolamine is present in an amount greater than 50% by weight, for example at least 70% by weight or at least 80% by weight, based on the total weight of the H-functional initiator used for the preparation of the alkanolamine-initiated polyether polyol.

[0051] In some embodiments, propylene oxide is the primary or substantially sole propylene oxide used in the preparation of alkanolamine-based polyether polyols. This means that in these embodiments, the amount of propylene oxide used exceeds 50% by weight, for example, at least 60% by weight or at least 70% by weight, based on the total weight of propylene oxide used in the preparation of alkanolamine-based polyether polyols. In some embodiments, the amount of ethylene oxide used is relatively small. Therefore, in these embodiments, the amount of ethylene oxide used does not exceed 50% by weight, for example, not more than 40% by weight, and in some cases even not more than 30% by weight, based on the total weight of propylene oxide used in the preparation of alkanolamine-based polyether polyols.

[0052] In some embodiments, the OH value of the alkanolamine-based polyether polyol is at least 500 mg KOH / g, for example 500 to 900 mg KOH / g, 600 to 800 mg KOH / g, or in some cases 680 to 720 mg KOH / g, and its functionality is 2.5 to 4, for example 2.5 to 3.5.

[0053] If desired, polyol blends may include other compounds containing isocyanate reactive groups, such as chain extenders and / or crosslinking agents, as well as higher molecular weight polyether polyols and polyester polyols not described above. Chain extenders and / or crosslinking agents include, for example, ethylene glycol, propylene glycol, butanediol, glycerol, diethylene glycol, dipropylene glycol, dibutyl glycol, trimethylolpropane, pentaerythritol, ethylenediamine, and diethyltoluenediamine. Polyester polyols may be prepared from, for example, organic dicarboxylic acids having 2 to 12 carbon atoms (e.g., aliphatic dicarboxylic acids having 4 to 6 carbon atoms) and polyols (e.g., diols or triols having 2 to 12 carbon atoms). Examples of dicarboxylic acids are succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. As an alternative to free dicarboxylic acids, corresponding dicarboxylic acid derivatives can be used, such as dicarboxylic acid monoesters or diesters prepared by esterification with alcohols having 1 to 4 carbon atoms, or dicarboxylic acid anhydrides.

[0054] In some embodiments, the -C2H4O-unit content of the polyol blend is 3% to 6% by weight, for example, 4% to 6% by weight, based on the total weight of the polyurethane foam forming composition. As used herein, "-C2H4O-unit content" refers to the calculated weight of -C2H4O-units present in the polyol during the preparation of the polyol itself (as opposed to -C2H4O-units that may already be present in the reactants used to prepare the polyol). -C2H4O-units can be formed when the polyether polyol is the product of the alkoxylation reaction of an H-functional initiator with an alkylene oxide, for example, using ethylene oxide as the alkylene oxide and / or using an H-functional initiator containing a -C2H4Z group (where Z represents the Zerewitinoff active hydrogen atom, sometimes simply referred to as "active hydrogen," for example, when Z represents hydrogen bonded to N, O, or S). -C2H4Z-units can be formed when the polyester polyol is the product of the reaction of a carboxylic acid and / or its anhydride with a hydroxyl-containing substance, for example, using diethylene glycol as the hydroxyl-containing substance. Therefore, when the content of -C2H4O- units in the polyol blend described herein is 3 to 6% by weight based on the total weight of the polyurethane foam forming composition, this means that, based on the total weight of the polyurethane foam forming composition, 3 to 6% by weight of the composition is -C2H4O- units formed during the preparation of the polyol, and this content is calculated based on the weight of the raw materials used to prepare the polyol.

[0055] As described, the polyurethane foam forming compositions of this specification also include physical blowing agent compositions comprising halogenated olefins. More specifically, in some embodiments, the halogenated olefins include hydrofluoroolefins (“HFO”), hydrochlorofluoroolefins (“HCFO”), or combinations thereof. Suitable haloolefins include, but are not limited to: 1,1,1,4,4,4-hexafluoro-2-butene (cis and / or trans isomers), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, E and / or Z isomers), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), HCFO1223, 1,2-dichloro-1,2-difluoroethylene (E and / or Z isomers), 3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4-hexafluorobutene-2 ​​(E and / or Z isomers), and 2-chloro-1,1,1,3,4,4,4-heptafluorobutene-2 ​​(E and / or Z isomers), or any combination of two or more of these.

[0056] In some embodiments, the content of haloolefins is 1 to 30% by weight, for example 5 to 30% by weight, 10 to 30% by weight, 15 to 25% by weight, or 18 to 22% by weight, based on the total weight of the polyurethane foam forming composition excluding the weight of the polyisocyanate.

[0057] If desired, the isocyanate reactive composition may include one or more other physical blowing agents, such as other halogenated blowing agents, such as CFCs, HCFCs, and HFCs, and / or hydrocarbon blowing agents, such as butane, n-pentane, cyclopentane, hexane, and / or isopentane (i.e., 2-methylbutane). However, in other embodiments, the isocyanate reactive composition is substantially or, in some cases, completely free of such other physical blowing agents. Thus, in some embodiments, a halogenated olefin (e.g., HCFO) is present in an amount of at least 80% by weight, such as at least 90% by weight, at least 95% by weight, at least 99% by weight, or in some cases, 100% by weight, based on the total weight of the physical blowing agents in the blowing agent composition.

[0058] The polyurethane foam forming compositions described in this specification include a carbon dioxide-generating chemical blowing agent, such as water and / or formate-terminated amines. In some such embodiments, the carbon dioxide-generating chemical blowing agent (such as water) used is present in an amount of 0.5 to 5.0% by weight, for example 1 to 3% by weight, 1.0 to 2.0% by weight, or 1.2 to 1.8% by weight, based on the total weight of the polyurethane foam forming composition excluding the weight of the polyisocyanate.

[0059] In some embodiments, the weight ratio of the physical blowing agent composition to the chemical blowing agent that generates carbon dioxide is at least 5:1, for example 5:1 to 50:1, 5:1 to 20:1, or in some cases 10:1 to 15:1.

[0060] Polyurethane foam forming compositions typically also contain surfactants. Suitable surfactants include, for example, organosilicon compounds, such as polysiloxane-polyolefin block copolymers, such as polyether-modified polysiloxanes. Other possible surfactants include polyethylene glycol ethers of long-chain alcohols, tertiary amines or alkanolamine salts of long-chain alkyl sulfates, alkyl sulfonates, or alkyl aryl sulfonates. The amount of such surfactant is sufficient to stabilize the foaming reaction mixture, preventing it from collapsing and forming large, uneven cells. In some embodiments, the amount of surfactant is 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.

[0061] The polyurethane foam forming compositions described in this specification typically also include a catalyst, such as a tertiary amine, a tertiary phosphine, a metal chelate, an acidic metal salt, a strong base, a metal alkoxide and / or a phenolate, a metal salt of an organic acid, or a combination thereof. In some embodiments, the catalyst comprises an organotin catalyst and / or a tertiary amine catalyst. For example, in certain cases, a combination of at least one “foaming” catalyst that significantly promotes the reaction of isocyanate groups with water molecules to form carbon dioxide and at least one “gelling” catalyst that significantly promotes the reaction of alcohol groups with isocyanates to form polyurethane, or at least one trimerizing catalyst, may be used.

[0062] Specific examples of suitable tertiary amine catalysts include pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N′,N″-tris(3-dimethylaminopropyl)hexahydrotriazine, tetramethylethylenediamine, tetraethylenediamine, benzyldimethylamine, or combinations thereof. In some embodiments, the tertiary amine catalyst comprises pentamethyldiethylenetriamine, N,N′,N″-dimethylaminopropylhexahydrotriazine, N,N-dimethylcyclohexylamine, or combinations thereof. Specific examples of suitable organometallic catalysts include dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, potassium octoate, potassium acetate, potassium 2-ethylhexanoate, or combinations thereof. In some embodiments, the catalyst is present in an amount of 0.01 to 3.0 wt% or 0.3 to 2.5 wt% based on the total weight of the polyurethane foam forming composition excluding the weight of the polyisocyanate.

[0063] Other materials that may be optionally included in the foam-forming compositions of the present invention include: pigments, colorants, fillers, antioxidants, flame retardants, and stabilizers. Exemplary flame retardants that can be used in the foam-forming compositions of the present invention include, but are not limited to, active bromine compounds and chlorinated phosphates known for use in polyurethane chemistry, including but not limited to tris(2-chloroethyl) phosphate (TECP), tris(1,3-dichloro-2-propyl) phosphate, tris(1-chloro-2-propyl) phosphate (TCPP), and dimethylpropyl phosphate (DMPP).

[0064] The present invention also relates to a method for preparing rigid polyurethane foam. In this method, a polyisocyanate is reacted with an isocyanate reactive composition comprising a polyol blend. In some embodiments, the isocyanate functional group component and the polyol blend are mixed at an isocyanate index of 0.90 to 1.50, for example, 1.20 to 1.50.

[0065] The polyol blend is reacted with a polyisocyanate in the presence of a blowing agent composition, a catalyst composition, a surfactant, and any other optional components. Rigid foam can be formed by blending all polyurethane foaming composition components except the polyisocyanate to form a phase-stable mixture, and then mixing this mixture with the polyisocyanate in an appropriate proportion. Alternatively, one or more components, such as a surfactant, can be pre-mixed with the polyisocyanate and then mixed with the polyol blend. Other possible implementations include adding one or more components as separate streams along with the polyol blend and the polyisocyanate. As used herein, the term "phase-stable" refers to a composition that remains stable at about 70°C. (Or, when stored at 21°C for 7 days, there is no obvious separation.)

[0066] Many foaming devices are designed to only adjust and mix two components in appropriate proportions. When using such devices, premixes of all components except the polyisocyanate can be advantageously used. According to the two-component method (component A: polyisocyanate; component B: an isocyanate reactive composition typically containing a polyol blend, blowing agent, water, catalyst, and surfactant), the components can be mixed in appropriate proportions at temperatures from 5 to 50°C (e.g., 15 to 35°C) and then injected or poured into a mold with a temperature controlled in the range of 20 to 70°C (e.g., 35 to 60°C). The mixture then expands and fills the chamber to form a rigid polyurethane foam. This simplifies the metering and mixing process of the reactive components in the foam-forming mixture but requires the isocyanate reactive composition to have phase stability.

[0067] Alternatively, rigid polyurethane foam can also be prepared using a so-called "quasi-prepolymer" method. In this method, a portion of the polyol component is reacted with the polyisocyanate component in proportion in the absence of a polyurethane-forming catalyst, such that the free isocyanate group content in the reaction product is 10% to 35% based on the prepolymer. To prepare the foam, the remaining portion of the polyol is added, and the components are allowed to react together in the presence of a blowing agent and other suitable additives, such as catalysts and surfactants. Other additives can be added to the isocyanate prepolymer or the remaining polyol, or both, before mixing the components, thereby providing a rigid foam at the end of the reaction.

[0068] Furthermore, rigid foams can be prepared using any known foaming equipment via a one-step or quasi-prepolymer method in batch or continuous processes. Rigid foams can be prepared as slab stock, molded articles, cavity fillings, sprayed foam, frothed foam, or laminates with other materials (such as cardboard, drywall, plastics, paper, or metal) as finishing substrates.

[0069] For closed-cell insulating foams, the goal is to retain the foaming agent within the cells to maintain the low thermal conductivity of the insulating material, i.e., rigid foam. Therefore, a high closed-cell content is desirable in the foam. In some embodiments, the rigid foam prepared according to the embodiments of this specification has a closed-cell content greater than 80%, typically greater than 85%, or greater than 88%, as measured according to ASTM D6226-15. Furthermore, the thermal conductivity of the foams prepared according to various embodiments of this specification indicates that these foams possess acceptable insulation performance, i.e., the foam exhibits good thermal conductivity at 35°C. The thermal conductivity measured at 2°C is less than 0.126 BTU-in / h-ft. 2 - , in 75 The thermal conductivity measured at 24°C is less than 0.140 BTU-in / h-ft.2 - According to ASTM C518-15, the foam sampled from the core of a 2-inch thick board was measured.

[0070] This invention also relates to the use of the rigid foam described herein for thermal insulation. That is, the rigid foam of this specification can be used as an insulation material in refrigeration devices. For example, these rigid foams can be used as an intermediate layer in, for example, composite elements or for filling hollow spaces in refrigerators, freezers, or refrigerated trailers. These foams can also be used in the construction industry or for insulation of long-distance heating pipes and containers.

[0071] Thus, the present invention also provides a composite article comprising a rigid foam, as disclosed herein, sandwiched between one or more veneer substrates. In some embodiments, the veneer substrate may be plastic (e.g., polypropylene resin reinforced with continuous biaxial glass fibers or a polyester copolymer reinforced with glass fibers), paper, wood, or metal. For example, in some embodiments, the composite article may be a refrigeration device, such as a refrigerator, freezer, or cooler, having an outer metal shell and an inner plastic liner. In some embodiments, the refrigeration device may be a trailer, and the composite article may contain foam prepared according to the present invention within a sandwich composite material used for trailer sidewalls and roofs.

[0072] Surprisingly, it has been found that the specific polyurethane foam forming compositions described herein can produce rigid polyurethane foams with significantly improved thermal insulation properties (as determined by K-values) while still retaining other important foam properties and processing characteristics, such as dimensional stability, compressive strength, flowability, reactivity, and demolding properties.

[0073] The following non-limiting and non-exhaustive embodiments are intended to further describe various non-limiting and non-exhaustive implementations, without limiting the scope of the implementations described in this specification.

[0074] Example The present invention is further illustrated by the following embodiments, but is not limited thereto. The following materials were used in the embodiments: Polyol 1: A polyether polyol starting with o-toluene diamine (63% propylene oxide / 37% ethylene oxide epoxy block), with an OH value of 388 mg KOH / g and an average functionality of 4; Polyol 2: A polyether polyol (100% propylene oxide) starting from sucrose / glycerol / propylene glycol / water, with an OH value of 410 mg KOH / g and an average functionality of 4.28; Polyol 3: A sucrose / glycerol-based polyether polyol (100% propylene oxide), with an OH value of 470 mg KOH / g and an average functionality of 4.66; Polyol 4: A polyether polyol (100% propylene oxide) starting from o-toluene diamine, with an OH value of 400 mg KOH / g and an average functionality of 4; Polyol 5: An ethylenediamine-based polyether polyol (100% propylene oxide), with an OH value of 60 mg KOH / g and an average functionality of 3.71; Polyol 6: A polyether polyol (100% propylene oxide) starting from sucrose / propylene glycol / water, with an OH value of 470 mgKOH / g and an average functionality of 5.24; Polyol 7: A sucrose / water-based polyether polyol (100% propylene oxide), with an OH value of 380 mg KOH / g and an average functionality of 5.81; Polyol 8: A polyether polyol starting with monoethanolamine (100% propylene oxide), with an OH value of 700 mg KOH / g and an average functionality of 3.0; Polyol 9: A glycerol-based polyether polyol (100% propylene oxide), with an OH value of 470 mg KOH / g and an average functionality of 3.0; Polyol 10: A sucrose / water-based polyether polyol (70% propylene oxide / 30% ethylene oxide block), with an OH value of 470 mg KOH / g and an average functionality of 5.52; Polyol 11: A glycerol-based polyether polyol (100% propylene oxide) with an OH value of 112 mg KOH / g and an average functionality of 3; Polyol 12: A glycerol-based polyether polyol (100% propylene oxide) with an OH value of 240 mg KOH / g and an average functionality of 3.0; Polyol 13: Aromatic polyester polyol, OH value 230-250 mg KOH / g, functionality 2 (STEPANPOL®PS-2502A, purchased from Stepan). Alcohol 1: C12-C15 primary alcohol blend, OH value 267-276, Neodol™ 25, purchased from Shell Chemical Company; Alcohol 2: Tridecafluoro-1-octanol, Capstone 62™ AL, purchased from Chemours; Surfactant 1: Silicone surfactant with an OH value of 54 mg KOH / g, Vorasurf™ DC5357 from Dow; Surfactant 2: Polyorganosiloxane polyether copolymer, OH value 105 mg KOH / g, Tegostab® B-8465 from Evonik; Surfactant 3: Non-hydrolyzable silicone surfactant with an OH value of 66 mg KOH / g, from Momentive's Niax™ L-5440; Surfactant 4: Silicone surfactant with an OH value of 110 mg KOH / g, Tegostab® B-8499 from Evonik.

[0075] Catalyst 1: N,N,N',N'',N''-pentamethyldiethylenetriamine, from Evonik's Polycat™ 5; Catalyst 2: Diethylene glycol solution of potassium octanoate, Dabco® K-15 from Evonik; Catalyst 3: N,N-dimethylcyclohexylamine, Polycat™ 8 from Evonik; Catalyst 4: N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine, from Evonik's Polycat™ 41; Catalyst 5: (2-hydroxypropyl)trimethylammonium formate, Dabco® TMR-2 from Evonik; Catalyst 6: 2,2'-Dimorpholine diethyl ether, JEFFCAT® DMDEE from Huntsman; Catalyst 7: 1,2-Dimethylimidazole, Dabco® 2041 from Evonik; Catalyst 8: N-methylmorpholine, JEFFCAT® NMM from Huntsman; Catalyst 9: N,N-dimethylbenzylamine, from Lanxess's Addocat® DB; Additive 1: Tris(2-chloroisopropyl) phosphate, from Fyrol™ PCF of ICL Industrial Products; Foaming agent 1: Cyclopentane; Blowing agent 2: trans-1,1,1-trifluoro-3-chloropropene, Solstice® LBA from Honeywell International; Isocyanate 1: Polydiphenylmethane diisocyanate (pMDI); NCO content 31.5% by weight; viscosity 200 mPa.s @ 25℃ (Covestro's MONDUR® MR); Isocyanate 2: Polydiphenylmethane diisocyanate (pMDI); NCO content 31.3% by weight; viscosity 400 mPa.s @ 25℃ (Covestro's MONDUR® 44V40); Isocyanate 3: Isocyanate 1 (3000 g) was added to a 5 L three-necked flask and stirred under nitrogen protection. Isocyanate 1 was heated to 60°C, and alcohol 1 (180 g) was slowly added dropwise. The solution temperature was maintained at 60°C and the mixture was heated for 1 hour to obtain isocyanate 3, which has an isocyanate content of 27.1% and a viscosity of 413 mPa.s @ 25°C. Isocyanate 4: Isocyanate 1 (3000 g) was added to a 5 L three-necked flask and stirred under nitrogen protection. Isocyanate 1 was heated to 60°C, and alcohol 2 (240 g) was slowly added dropwise. The solution temperature was maintained at 60°C and the mixture was heated for 1 hour to obtain isocyanate 4, which has an isocyanate content of 26.8% and a viscosity of 358 mPa.s @ 25°C. Isocyanate 5: Isocyanate 1 (3000 g) was added to a 5 L three-necked flask and stirred under nitrogen protection. Isocyanate 1 was heated to 60°C, and alcohol 1 (75 g) was slowly added dropwise. The solution temperature was maintained at 60°C and the mixture was heated for 1 hour to obtain isocyanate 5, which has an isocyanate content of 29.5% and a viscosity of 261 mPa.s @ 25°C. Isocyanate 6: Isocyanate 1 (3000g) was added to a 5L three-necked flask and stirred under nitrogen protection. Isocyanate 1 was heated to 60°C, and alcohol 2 (90g) was slowly added dropwise. The solution temperature was maintained at 60°C and the mixture was heated for 1 hour to obtain isocyanate 6, which has an isocyanate content of 30.2% and a viscosity of 266 mPa·s @ 25°C.

[0076] In each case, a premix was prepared by mixing the polyol, catalyst, surfactant, water, and blowing agent in the amounts shown in Table 1. Foam was prepared by mixing the premix with an amount of isocyanate sufficient to achieve the isocyanate indices listed in Table 1 and pouring the mixture into 83-ounce paper cups. The milky time, gel time, surface drying time, and free foam density (“FRD”) were recorded.

[0077] The foam board is also made using a pneumatic mixer (~3000 rpm) and a temperature-controlled mold (120). Foam samples (25" x 13" x 2") were prepared by hand. The temperature of both the isocyanate reactive composition and the isocyanate was maintained at 25°C, and all samples were demolded after 3 minutes. The minimum filler content was determined by slightly overfilling the mold cavity and removing excess foam to ensure measurable foam weight within a 25" x 13" x 2" volume. After determining the minimum filler value, foam boards were prepared to obtain a target density approximately 8-12% higher than the minimum filler density. The results are shown in Table 1.

[0078] The results in Table 1 are the average results of three repeated experiments. Examples 2-3, 5-6, 8, 10-11, 13, 15, and 17 are examples of the invention, and Examples 1, 4, 7, 9, 12, 14, and 16 are comparative examples.

[0079] Table 1 Continuing from Table 1 Although the invention has been described in detail above for illustrative purposes, it should be understood that such detail is for this purpose only, and that various changes may be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims

1. A polyurethane foam-forming composition comprising: (a) a polyol blend having a weighted average functionality of 3 to 6 and a weighted average OH value of 300 to 500 mg KOH / g; (b) a blowing agent composition comprising: (1) a physical blowing agent; and (2) a carbon dioxide-generating chemical blowing agent; wherein the physical blowing agent comprising a halogenated olefin, the halogenated olefin being present in an amount (i) of 1 to 30 percent by weight, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate, and (ii) of at least 80 percent by weight, based on the total weight of the physical blowing agent in the blowing agent composition, wherein the physical blowing agent composition and the carbon dioxide-generating chemical blowing agent are present in a relative ratio of at least 5: 1 by weight; and (c) a polyisocyanate comprising a urethane-modified polyisocyanate having an NCO group content of 25 to 35 percent by weight, based on the total weight of the urethane-modified polyisocyanate, and comprising the reaction product of: (1) a polymethylene polyphenyl polyisocyanate; and (2) a mono-alcohol, wherein the polyisocyanate is present in an amount sufficient to provide an isocyanate index of 0.90 to 1.

50.

2. The polyurethane foam-forming composition of claim 1, wherein the mono-alcohol comprises one or more isocyanate-reactive compounds having an average isocyanate-reactive group functionality of no more than 1.2 or 0.8 to 1.

2.

3. The polyurethane foam-forming composition of claim 1 or 2, wherein the urethane-modified polyisocyanate is not a polyisocyanate prepolymer.

4. The polyurethane foam-forming composition of any one of claims 1 to 3, wherein the pMDI has an average isocyanate functionality of 2.1 to 3.2, 2.5 to 3.2, 2.6 to 3.2, or 2.8 to 3.

2.

5. The polyurethane foam-forming composition of any one of claims 1 to 4, wherein the pMDI comprises: i) up to 60 percent by weight of a first polymethylene polyphenyl polyisocyanate having the general formula (I), based on 100 percent by weight of the polymethylene polyphenyl polyisocyanate, (I), and at least 40 percent by weight of a second polymethylene polyphenyl polyisocyanate having the general formula (II), based on 100 percent by weight of the polymethylene polyphenyl polyisocyanate, (I), (II), wherein n is an integer having a value of 1 or higher.

6. The polyurethane foam-forming composition of any one of claims 1 to 5, wherein the pMDI has an NCO content of 29 to 34 percent by weight or 29.0 to 32.0 percent by weight, based on the total weight of the urethane-modified polyisocyanate.

7. The polyurethane foam-forming composition of any one of claims 1 to 6, wherein the pMDI has a viscosity at 25 °C (measured according to EN ISO 3219, October 1994) of 100 to 750 mPa-s, 100 to 600 mPa-s, or 150 to 450 mPa-s.

8. The polyurethane foam-forming composition of any of claims 1 to 7, wherein the monoalcohol is represented by the formula: wherein R 1 , R 2 , and R 3 independently of one another represent H, a C1-C 56 alkyl group, a C6-C 56 aryl group, a C3-C 56 cycloalkyl group or a C7-C 56 aralkyl group, or a group R 1 , R 2 and / or R 3 may be linked via a ring system, for example wherein any one or more of R 1 , R 2 and R 3 may also represent any of the above groups which further contain a functional group which does not react with isocyanate groups.

9. The polyurethane foam-forming composition of any of claims 1 to 8, wherein the monoalcohol comprises a primary alcohol, a secondary alcohol, a tertiary alcohol, or a combination of any two or more thereof.

10. The polyurethane foam-forming composition of any of claims 1 to 9, wherein the monoalcohol comprises an aromatic monoalcohol, an aliphatic monoalcohol, a cycloaliphatic monoalcohol, or a combination of any two or more thereof, each of which can be saturated or unsaturated, cyclic, straight-chain, or branched.

11. The polyurethane foam-forming composition of any of claims 1 to 10, wherein the monoalcohol contains 1 to 56, 1 to 36, 1 to 26, 10 to 15, or 12 to 15 carbon atoms.

12. The polyurethane foam-forming composition of any of claims 1 to 11, wherein the monoalcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-hydroxypentane, 3-hydroxypentane, isomers of primary methyl butanol, secondary methyl butanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, 2-ethylhexanol, primary trimethyl hexanol, secondary trimethyl hexanol, cyclohexanol, alkyl-substituted cyclohexanol, cyclopentanol, cyclohexylmethanol, phenol, alkyl-substituted phenol (such as nonyl phenol), benzyl alcohol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol, n-nonadecanol, eicosanol, n-hexacosanol, n-heptatriacontanol, 2,2,4-trimethyl-1-pentanol, 2,6,8-trimethylnonanol, 4-cyclohexyl-1-butanol, 2,4,6-trimethylbenzyl alcohol, 2-methylpropan-2-ol, 2-ethyl-1-butanol, 2-methyl-2-butanol, 2-methyl-3-buten-2-ol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 3-ethyl-3-nonyl alcohol, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 2,6-dimethyl-4-heptanol, 3,5-dimethyl-1-hexanol, 3,5-dimethyl-1-hexyne-3-ol, 1-methylcyclopentanol, 1-methylcyclohexanol, 1-ethylcyclohexanol, 1,1-diphenylacetaldehyde, 1,1,2-triphenylethanol, t-butyl alcohol, 3-isopropenylcumyl alcohol, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 4-isopropenylcumyl alcohol, 3-isopropenylphenol, 4-isopropenylphenol, p-hydroxy-a-phenylstyrene, p-hydroxy-β-phenylstyrene, 4-hydroxy-a-ethylstyrene, a-chloromethyl-p-hydroxystyrene, allyl alcohol, 2-allylphenol, 2-allyl-6-methylphenol, cinnamyl alcohol, undecylenic alcohol, allyl amine, acrylic acid, undecylenic acid, 9-hexadecen-1-ol, 9-octadecen-1-ol, and 10-eicosen-1-ol, or a mixture of any two or more thereof.

13. The polyurethane foam-forming composition of any one of claims 1 to 12, wherein the mono-alcohol comprises C 12 primary alcohol, C 13 primary alcohol, C 14 primary alcohol, and C 15 primary alcohol.

14. The polyurethane foam-forming composition of any of claims 1 to 13, wherein the mono-alcohol comprises a fluorinated mono-alcohol, such as 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-l-propanol, 2,2,3,3-tetrafluoro-l-propanol, 4,4,5,5,5-pentafluoro-l-pentanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 3,3,3-trifluoro-l-propanol, 6,6-nonfluoro-l-hexanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-l-octanol, 3,3,4,4,5,5,6,6,6-nonafluoro-l-hexanol, 6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-undecafluoro-l-dodecanol, or a mixture of any two or more of the foregoing.

15. The polyurethane foam-forming composition of any of claims 1 to 14, wherein the mono-alcohol comprises an oligomer or polymer, such as a polyether mono-alcohol having an equivalent weight of at least 850, at least 1000, at least 1100, or at least 1200 and up to 10,000, up to 7,000, or up to 4,500.

16. The polyurethane foam-forming composition of claim 15, wherein the polyether mono-alcohol is a condensation reaction product of an alkylene oxide and a mono-alcohol starter, such as wherein the alkylene oxide comprises ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, an aromatic alkylene oxide (such as epoxystyrene), and a halogenated alkylene oxide (such as trichlorobutylene oxide), or a combination of any two or more thereof, such as wherein the mono-alcohol starter is present in an amount of at least 90 wt%, at least 95 wt%, or at least 99 wt%, based on the total weight of the starter used to make the polyether mono-alcohol.

17. The polyurethane foam-forming composition of any of claims 1 to 16, wherein the hydrocarbon content of the mono-alcohol is at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, or at least 95 wt%, based on the total weight of the mono-alcohol, and the hydrocarbon content is less than 100 wt%, no more than 99.99 wt%, no more than 99.9 wt%, no more than 99.5 wt%, or no more than 99 wt%, based on the total weight of the mono-alcohol.

18. The polyurethane foam-forming composition of any of claims 1 to 17, wherein the pMDI and the mono-alcohol are reacted in relative amounts such that for each equivalent of hydroxyl present, 5 to 5,000, such as 7 to 4,500, equivalents of NCO groups are present.

19. The polyurethane foam-forming composition of any of claims 1 to 18, wherein the urethane-modified polyisocyanate is present in the polyurethane foam-forming composition in an amount sufficient to provide an isocyanate index of 0.90 to 1.50, such as 1.20 to 1.

50.

20. The polyurethane foam-forming composition of any of claims 1 to 19, wherein the polyol blend has a weighted average functionality of 3 to 5, 3.5 to 4.5, or 3.8 to 4.2, and / or a weighted average OH number of 350 to 450 mg KOH / g.

21. The polyurethane foam-forming composition of any of claims 1 to 20, wherein the polyol blend is present in the polyurethane foam-forming composition in an amount of at least 50 wt%, 50 to 90 wt%, or 60 to 80 wt%, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

22. The polyurethane foam-forming composition of any of claims 1 to 21, wherein the polyol blend comprises an amine-initiated polyether polyol that is a reaction product of an H-functional initiator comprising an amine, such as an aliphatic amine and / or an aromatic amine, and an alkylene oxide.

23. The polyurethane foam-forming composition of claim 22, wherein the amine has an amine functionality of at least 2 or 2 to 3.

24. The polyurethane foam-forming composition of any of claims 22 to 23, wherein the amine comprises a (cyclo)aliphatic amine such as 1,2-ethanediamine, 1,3- propanediamine, 1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine, pentanediamine, isophorone diamine, 1,10-decanediamine, diaminocyclohexylmethane, pentamethylenediamine, or a combination of any two or more of the foregoing.

25. The polyurethane foam-forming composition of any of claims 22 to 24, wherein the amine comprises an aromatic amine such as a mixture of 2,3-TDA and 3,4-TDA.

26. The polyurethane foam-forming composition of any of claims 22 to 25, wherein the 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 initiator used to make the amine-initiated polyether polyol.

27. The polyurethane foam-forming composition of any of claims 22 to 26, wherein the alkylene oxide comprises more than 50 wt%, at least 80 wt%, at least 90 wt%, or 100 wt% propylene oxide, based on the total weight of the alkylene oxide used to make the amine-initiated polyether polyol.

28. The polyurethane foam-forming composition of claim 27, wherein the alkylene oxide comprises no more than 10 wt%, no more than 5 wt%, or no more than 1 wt% ethylene oxide, based on the total weight of the alkylene oxide used to make the amine-initiated polyether polyol.

29. The polyurethane foam-forming composition of any of claims 22 to 28, wherein the amine-initiated polyether polyol has an OH number of 200 to 600 mg KOH / g, a functionality of at least 2.5, and / or an average functionality of 3.5 to 4.5, 3.8 to 4.2, or 4.

0.

30. The polyurethane foam-forming composition of any of claims 22 to 29, wherein the amine-initiated polyether polyol has a content of -C2H4O- units of less than 10 wt%, less than 5 wt%, less than 2 wt%, or 0 wt%, based on the total weight of the amine-initiated polyether polyol.

31. The polyurethane foam-forming composition of any of claims 22 to 30, wherein the amine-initiated polyether polyol has a content of at least 30 wt%, 30 to 80 wt%, 30 to 60 wt%, 40 to 60 wt%, or 40 to 50 wt%, based on the total weight of the polyol blend.

32. The polyurethane foam-forming composition of any of claims 1 to 31, wherein the polyol blend comprises a sugar-initiated polyether polyol that is a reaction product of an H-functional initiator containing a sugar and an alkylene oxide, for example wherein the sugar comprises sucrose, sorbitol, maltitol, or a combination of any two or more of the foregoing.

33. The polyurethane foam-forming composition of claim 32, wherein the sugar is present in an amount of more than 50 wt%, at least 70 wt%, or at least 80 wt%, based on the total weight of the H-functional initiator used to make the sugar-initiated polyether polyol.

34. The polyurethane foam-forming composition of any of claims 32 or 33, wherein the content of propylene oxide is more than 50 wt%, at least 60 wt%, or at least 70 wt%, based on the total weight of the alkylene oxide used to make the sugar-initiated polyether polyol.

35. The polyurethane foam-forming composition of claim 34, wherein the content of ethylene oxide is not more than 50 wt%, not more than 40 wt%, or not more than 30 wt%, based on the total weight of the alkylene oxide used to make the sugar-initiated polyether polyol.

36. The polyurethane foam-forming composition of any of claims 32 to 35, wherein the sugar-initiated polyether polyol has an OH value of 200 to 600 mg KOH / g, 300 to 550 mg KOH / g, 380 to 500 mg KOH / g, or 450 to 500 mg KOH / g, and a functionality of 4 to 6, 5 to 6, 5.2 to 5.8, or 5.2 to 5.

6.

37. The polyurethane foam-forming composition of any of claims 32 to 36, wherein the sugar-initiated polyether polyol has a content of -C2H4O- units of less than 50 wt%, less than 40 wt%, or not more than 30 wt%, based on the total weight of the sugar-initiated polyether polyol.

38. The polyurethane foam-forming composition of any of claims 32 to 37, wherein the sugar-initiated polyether polyol is present in an amount of at least 30 wt%, 30 to 60 wt%, 30 to 50 wt%, or 35 to 45 wt%, based on the total weight of the polyol blend.

39. The polyurethane foam-forming composition of any of claims 1 to 38, wherein the polyol blend comprises an aliphatic triol-initiated polyether polyol that is a reaction product of an H-functional initiator containing an aliphatic triol, such as glycerol, and an alkylene oxide.

40. The polyurethane foam-forming composition of claim 39, wherein the aliphatic triol is present in an amount of more than 50 wt%, at least 70 wt%, or at least 80 wt%, based on the total weight of the H-functional initiator used to make the aliphatic triol-initiated polyether polyol.

41. The polyurethane foam-forming composition of any of claims 39 or 40, wherein the propylene oxide is present in an amount of more than 50 wt%, at least 60 wt%, or at least 70 wt%, based on the total weight of the alkylene oxide used to make the aliphatic triol-initiated polyether polyol.

42. The polyurethane foam-forming composition of claim 41, wherein the ethylene oxide is present in an amount of no more than 50 wt%, no more than 40 wt%, or no more than 30 wt%, based on the total weight of the alkylene oxide used to make the aliphatic triol-initiated polyether polyol.

43. The polyurethane foam-forming composition of any of claims 39 to 42, wherein the aliphatic triol-initiated polyether polyol has an OH number of 100 to 500 mg KOH / g, 200 to 400 mg KOH / g, 200 to 300 mg KOH / g, 200 to 250 mg KOH / g, 230 to 250 mg KOH / g, or 233 to 243 mg KOH / g, a functionality of greater than 2 to 4, 2.5 to 3.5, or 3.

0.

44. The polyurethane foam-forming composition of any of claims 39 to 43, wherein the aliphatic triol-initiated polyether polyol contains a content of -C2H4O- units of less than 50 wt%, less than 40 wt%, or no more than 30 wt%, based on the total weight of the aliphatic triol-initiated polyether polyol.

45. The polyurethane foam-forming composition of any of claims 39 to 44, wherein the aliphatic triol-initiated polyether polyol is present in an amount of at least 30 wt%, 30 to 60 wt%, such as 30 to 50 wt%, or 35 to 45 wt%, based on the total weight of the polyol blend.

46. The polyurethane foam-forming composition of any of claims 1 to 45, wherein the polyol blend comprises a alkanolamine-initiated polyether polyol that is a reaction product of an alkylene oxide and a starter containing an alkanolamine.

47. The polyurethane foam-forming composition of claim 46, wherein the alkanolamine is represented by the formula: NH2— Z— OH wherein Z represents a divalent radical that is a straight chain or branched alkylene radical having 2 to 6 carbon atoms, a cycloalkylene radical having 4 to 6 carbon atoms, or a dialkylene ether radical having 4 to 6 carbon atoms, wherein the dialkylene ether radical can be represented by the formula: — R— O— R— wherein each R represents a hydrocarbon group having 2 to 3 carbon atoms. ​ ​ ​ ​ 48. The polyurethane foam-forming composition of any of claims 46-47, wherein the alkanolamine comprises monoethanolamine, l-amino-2-propanol, 2-amino-l-propanol, 3-amino-l-propanol, l-(2-aminoethoxy)ethanol, l-amino-2-butanol, 2-amino-3-butanol, 2-amino-2-methylpropanol, 5-aminopentanol, 3-amino-2,2-dimethylpropanol, 4-aminocyclohexanol, or a combination of any two or more thereof.

49. The polyurethane foam-forming composition of any of claims 46-48, wherein the alkanolamine 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 starter used to make the alkanolamine-initiated polyether polyol.

50. The polyurethane foam-forming composition of any of claims 46-49, wherein the propylene oxide is present in an amount of more than 50 wt%, at least 60 wt%, or at least 70 wt%, based on the total weight of alkylene oxide used to make the alkanolamine-initiated polyether polyol.

51. The polyurethane foam-forming composition of claim 50, wherein the ethylene oxide is present in an amount of no more than 50 wt%, no more than 40 wt%, or in some cases no more than 30 wt%, based on the total weight of alkylene oxide used to make the alkanolamine-initiated polyether polyol.

52. The polyurethane foam-forming composition of any of claims 46-51, wherein the alkanolamine-initiated polyether polyol has an OH number of at least 500 mg KOH / g, 500 to 900 mg KOH / g, 600 to 800 mg KOH / g, or 680 to 720 mg KOH / g, and a functionality of 2.5 to 4 or 2.5 to 3.

5.

53. The polyurethane foam-forming composition of any of claims 1-52, wherein the polyol blend has a -C2H4O- unit content of 3 to 6 wt% or 4 to 6 wt%, based on the total weight of the polyurethane foam-forming composition.

54. The polyurethane foam-forming composition of any of claims 1-53, wherein the haloolefin comprises HFO, HCFO, or a combination thereof, such as wherein the haloolefin comprises 1,1,1,4,4,4-hexafluoro-2-butene (cis and / or trans isomers), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, E and / or Z isomers), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), HCFO 1223, 1,2-dichloro-1,2-difluoroethylene (E and / or Z isomers), 3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4-hexafluorobutene-2 (E and / or Z isomers), and 2-chloro-1,1,1,3,4,4,4-heptafluorobutene-2 (E and / or Z isomers), or a combination of any two or more thereof.

55. The polyurethane foam-forming composition of any one of claims 1 to 54, wherein the halogenated alkene is present in an amount of 5 to 30 wt%, 10 to 30 wt%, 15 to 25 wt%, or 18 to 22 wt%, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

56. The polyurethane foam-forming composition of any one of claims 1 to 55, wherein the halogenated alkene is present in an amount of at least 90 wt%, at least 95 wt%, at least 99 wt%, or 100 wt%, based on the total weight of the physical blowing agent in the blowing agent composition.

57. The polyurethane foam-forming composition of any one of claims 1 to 56, wherein the carbon dioxide-generating chemical blowing agent comprises 0.5 to 5.0 wt%, 1 to 3 wt%, 1.0 to 2.0 wt%, or 1.2 to 1.8 wt% water and / or formate-terminated amine, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

58. The polyurethane foam-forming composition of any one of claims 1 to 57, wherein the physical blowing agent composition and the carbon dioxide-generating chemical blowing agent are present in a relative ratio of 5: 1 to 50: 1, 5: 1 to 20: 1, or 10: 1 to 15: 1 by weight.

59. The polyurethane foam-forming composition of any one of claims 1 to 58, wherein the polyurethane foam-forming composition further comprises a surfactant, such as a silicone compound, such as a polysiloxane-polyolefin block copolymer, such as a polyether-modified polysiloxane.

60. The polyurethane foam-forming composition of any one of claims 1 to 59, wherein the polyurethane foam-forming composition further comprises a catalyst, such as an organotin catalyst and / or a tertiary amine catalyst.

61. A polyurethane foam prepared from the polyurethane foam-forming composition of any one of claims 1 to 60, wherein the polyurethane foam has a closed cell content of greater than 80%, greater than 85%, or greater than 88%, as measured according to ASTM D6226-15.

62. The polyurethane foam of claim 61, wherein the polyurethane foam has a thermal conductivity of less than 0.126 BTU-in / h-ft2-°F (0.022 W / m-K) measured at 35 (2°C). 2 a thermal conductivity of less than 0.140 BTU-in / h-ft2-°F (0.025 W / m-K) measured at 75 (24°C). 2 measured according to ASTM C518-15 on foam sampled from the 2 inch thick slab core.​​ 63. A composite element comprising the polyurethane foam of claim 61 or claim 62 sandwiched between one or more layers of a facing substrate, such as wherein the facing substrate is composed of plastic (such as continuous bi-directional glass fiber reinforced polypropylene resin or glass fiber reinforced polyester copolymer), paper, wood, or metal.

64. A refrigeration device, such as a refrigerator, freezer, refrigerated trailer, or chiller, comprising the composite element of claim 63.

65. A method of preparing a polyurethane foam, comprising reacting a polyurethane foam-forming composition comprising: (a) a polyol blend having a weighted average functionality of 3 to 6 and a weighted average OH value of 300 to 500 mg KOH / g; (b) a blowing agent composition comprising: (1) a physical blowing agent; and (2) a carbon dioxide-generating chemical blowing agent; under conditions in which the isocyanate index is 0.90 to 1.

50. wherein the physical blowing agent comprises a halogenated olefin, the halogenated olefin is present in an amount (i) of 1 to 30 percent by weight based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate and (ii) of at least 80 percent by weight based on the total weight of the physical blowing agent in the blowing agent composition, wherein the physical blowing agent composition is present in a relative ratio of at least 5: 1 by weight with a chemical blowing agent that generates carbon dioxide; and (c) a polyisocyanate comprising a urethane-modified polyisocyanate having an NCO group content of 25 to 35 percent by weight based on the total weight of the urethane-modified polyisocyanate and comprising the reaction product of: (1) a polymethylene polyphenyl polyisocyanate; and (2) a mono-alcohol.

66. The method of claim 65, wherein the mono-alcohol comprises one or more isocyanate-reactive compounds having an average isocyanate-reactive group functionality of no more than 1.2 or 0.8 to 1.

2.

67. The method of claim 65 or 66, wherein the urethane-modified polyisocyanate is not a polyisocyanate prepolymer.

68. The method of any one of claims 65 to 67, wherein the pMDI has an average isocyanate functionality of 2.1 to 3.2, 2.5 to 3.2, 2.6 to 3.2, or 2.8 to 3.

2.

69. The method of any one of claims 65 to 68, wherein the pMDI comprises: i) up to 60 percent by weight of a first polymethylene polyphenyl polyisocyanate having the general formula (I) based on 100 percent by weight of the polymethylene polyphenyl polyisocyanate, (I), and at least 40 percent by weight of a second polymethylene polyphenyl polyisocyanate having the general formula (II) based on 100 percent by weight of the polymethylene polyphenyl polyisocyanate, (I), (II), wherein n is an integer having a value of 1 or higher.

70. The method of any one of claims 65 to 69, wherein the pMDI has an NCO content of 29 to 34 percent by weight or 29.0 to 32.0 percent by weight based on the total weight of the urethane-modified polyisocyanate.

71. The method of any one of claims 65 to 70, wherein the pMDI has a viscosity at 25 °C (measured according to EN ISO 3219, October 1994) of 100 to 750 mPa-s, 100 to 600 mPa-s, or 150 to 450 mPa-s.

72. The method of any one of claims 65 to 71, wherein the mono-alcohol is represented by the formula: wherein R 1 , R 2 , and R 3 independently of one another represent H, a C1-C 56 alkyl group, a C6-C 56 aryl group, a C3-C 56 cycloalkyl group, or a C7-C 56 aralkyl group, or a group R 1 , R 2 , and / or R 3 may be attached by a ring system. In some embodiments, any one or more of R 1 , R 2 , and R 3 may also represent any of the above groups further containing a functional group that does not react with isocyanate groups.

73. The method of any one of claims 65 to 72, wherein the mono-alcohol comprises a primary alcohol, a secondary alcohol, a tertiary alcohol, or a combination of any two or more thereof.

74. The method of any one of claims 65 to 73, wherein the mono-alcohol comprises an aromatic mono-alcohol, an aliphatic mono-alcohol, a cycloaliphatic mono-alcohol, or a combination of any two or more thereof, each of which can be saturated or unsaturated, cyclic, straight-chain, or branched.

75. The method of any one of claims 65-74, wherein the monoalcohol contains 1 to 56, 1 to 36, 1 to 26, 10 to 15, or 12 to 15 carbon atoms.

76. The method of any one of claims 65-75, wherein the monoalcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-hydroxypentane, 3-hydroxypentane, isomers of primary methyl butanol, secondary methyl butanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, 2-ethylhexanol, primary trimethyl hexanol, secondary trimethyl hexanol, cyclohexanol, alkyl substituted cyclohexanols, cyclopentanol, cyclohexylmethanol, phenol, alkyl substituted phenols (such as nonyl phenol), benzyl alcohol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol, n-nonadecanol, eicosanol, n-hexacosanol, n-heptatriacontanol, 2,2,4-trimethyl-1-pentanol, 2,6,8-trimethylnonan-1-ol, 4-cyclohexyl-1-butanol, 2,4,6-trimethylbenzyl alcohol, 2-methylpropan-2-ol, 2-ethylbutan-1-ol, 2-methylbutan-2-ol, 2-methyl-3-buten-2-ol, 2-methylpentan-1-ol, 2-methylpentan-2-ol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 3-ethyl-3-nonanol, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 2,6-dimethyl-4-heptanol, 3,5-dimethyl-1-hexanol, 3,5-dimethyl-1-hexyne-3-ol, 1-methylcyclopentanol, 1-methylcyclohexanol, 1-ethylcyclohexanol, 1,1-diphenylacetaldehyde, 1,1,2-triphenylethanol, t-butanol, 3-isopropenylcumyl alcohol, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 4-isopropenylcumyl alcohol, 3-isopropenylphenol, 4-isopropenylphenol, p-hydroxy-a-phenylstyrene, p-hydroxy-β-phenylstyrene, 4-hydroxy-a-ethylstyrene, a-chloromethyl-p-hydroxystyrene, allyl alcohol, 2-allylphenol, 2-allyl-6-methylphenol, cinnamyl alcohol, undecenyl alcohol, allylamine, acrylic acid, undecylenic acid, 9-hexadecen-1-ol, 9-octadecen-1-ol, and 10-eicosen-1-ol, or a mixture of any two or more thereof.

77. The method of any one of claims 65-76, wherein the mono-alcohols comprise C 12 primary alcohols, C 13 primary alcohols, C 14 primary alcohols and C 15 primary alcohols.

78. The process of any of claims 65 to 77, wherein the monoalcohol comprises a fluorinated monoalcohol, such as 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-l- propanol, 2,2,3,3-tetrafluoro-l-propanol, 4,4,5,5,5-pentafluoro-l-pentanol, 1,1,1,3,3,3- hexafluoro-2-propanol, 3,3,3-trifluoro-l-propanol, 6,6-nonafluoro-l-hexanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-l-octanol, 3,3,4,4,5,5,6,6,6-nonafluoro-l-hexanol, 6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-undecafluoro-l-dodecanol, or a mixture of any two or more of the foregoing.

79. The process of any of claims 65 to 78, wherein the monoalcohol comprises an oligomer or polymer, such as a polyether monoalcohol having an equivalent weight of at least 850, at least 1000, at least 1100, or at least 1200 and up to 10,000, up to 7,000, or up to 4,500.

80. The process of claim 79, wherein the polyether monoalcohol is a polycondensation reaction product of an alkylene oxide and a monoalcohol starter, such as wherein the alkylene oxide comprises ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, an aromatic alkylene oxide (such as epoxystyrene), and a halogenated alkylene oxide (such as trichlorobutylene oxide), or a combination of any two or more thereof, such as wherein the monoalcohol starter comprises at least 90 wt%, at least 95 wt%, or at least 99 wt%, based on the total weight of the starter used to make the polyether monomer.

81. The process of any of claims 65 to 80, wherein the hydrocarbon content of the monoalcohol is at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, or at least 95 wt%, based on the total weight of the monoalcohol, and the hydrocarbon content is less than 100 wt%, no more than 99.99 wt%, no more than 99.9 wt%, no more than 99.5 wt%, or no more than 99 wt%, based on the total weight of the monoalcohol.

82. The process of any of claims 65 to 81, wherein the pMDI and the monoalcohol are reacted in relative amounts such that for each equivalent of hydroxyl present, 5 to 5,000, such as 7 to 4,500, equivalents of NCO groups are present.

83. The process of any of claims 65 to 82, wherein the urethane-modified polyisocyanate is present in the polyurethane foam-forming composition in an amount sufficient to provide an isocyanate index of 0.90 to 1.50, such as 1.20 to 1.

50.

84. The process of any of claims 65 to 83, wherein the polyol blend has a weighted average functionality of 3 to 5, 3.5 to 4.5, or 3.8 to 4.2, and / or a weighted average OH value of 350 to 450 mg KOH / g.

85. The method of any of claims 65-84, wherein the polyol blend is present in the polyurethane foam-forming composition in an amount of at least 50 wt%, 50 to 90 wt%, or 60 to 80 wt%, based on the total weight of the polyurethane foam-forming composition excluding the weight of the polyisocyanate.

86. The method of any of claims 65-85, wherein the polyol blend comprises an amine- initiated polyether polyol that is a reaction product of an H-functional initiator comprising an amine, such as an aliphatic amine and / or an aromatic amine, and an alkylene oxide.

87. The method of claim 87, wherein the amine has an amine functionality of at least 2 or 2 to 3.

88. The method of claim 86 or 87, wherein the amine comprises a (cyclo)aliphatic amine such as 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine, pentanediamine, isophorone diamine, 1,10-decanediamine, diaminocyclohexylmethane, pentamethylenediamine, or a combination of any two or more of the foregoing.

89. The method of any of claims 86-88, wherein the amine comprises an aromatic amine such as a mixture of 2,3-TDA and 3,4-TDA.

90. The method of any of claims 86-89, wherein the 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 initiator used to make the amine-initiated polyether polyol.

91. The method of any of claims 86-90, wherein the alkylene oxide comprises more than 50 wt%, at least 80 wt%, at least 90 wt%, or 100 wt% propylene oxide, based on the total weight of the alkylene oxide used to make the amine-initiated polyether polyol.

92. The method of claim 91, wherein the alkylene oxide comprises no more than 10 wt%, no more than 5 wt%, or no more than 1 wt% ethylene oxide, based on the total weight of the alkylene oxide used to make the amine-initiated polyether polyol.

93. The method of any of claims 86-92, wherein the amine-initiated polyether polyol has an OH number of 200 to 600 mg KOH / g, a functionality of at least 2.5 and / or an average functionality of 3.5 to 4.5, 3.8 to 4.2, or 4.

0.

94. The method of any of claims 86-93, wherein the amine-initiated polyether polyol has a content of -C2H4O- units of less than 10 wt%, less than 5 wt%, less than 2 wt%, or 0 wt%, based on the total weight of the amine-initiated polyether polyol.

95. The method of any of claims 86-94, wherein the amine-initiated polyether polyol is present in an amount of at least 30 wt%, 30 to 80 wt%, 30 to 60 wt%, 40 to 60 wt%, or 40 to 50 wt%, based on the total weight of the polyol blend.

96. The method of any one of claims 65-95, wherein the polyol blend comprises a sugar- initiated polyether polyol that is a reaction product of an H-functional initiator containing a sugar and an alkylene oxide, e.g., wherein the sugar comprises sucrose, sorbitol, maltitol, or a combination of any two or more of the foregoing.

97. The method of claim 96, wherein the sugar is present in an amount of more than 50 wt%, at least 70 wt%, or at least 80 wt%, based on the total weight of the H-functional initiator used to make the sugar-initiated polyether polyol.

98. The method of claim 96 or 97, wherein the propylene oxide content is more than 50 wt%, at least 60 wt%, or at least 70 wt%, based on the total weight of the alkylene oxide used to make the sugar-initiated polyether polyol.

99. The method of claim 98, wherein the ethylene oxide content is no more than 50 wt%, no more than 40 wt%, or no more than 30 wt%, based on the total weight of the alkylene oxide used to make the sugar-initiated polyether polyol.

100. The method of any one of claims 96-99, wherein the sugar-initiated polyether polyol has an OH value of 200 to 600 mg KOH / g, 300 to 550 mg KOH / g, 380 to 500 mg KOH / g, or 450 to 500 mg KOH / g, and a functionality of 4 to 6, 5 to 6, 5.2 to 5.8, or 5.2 to 5.

6.

101. The method of any one of claims 96-100, wherein the sugar-initiated polyether polyol has a -C2H4O- unit content of less than 50 wt%, less than 40 wt%, or no more than 30 wt%, based on the total weight of the sugar-initiated polyether polyol.

102. The method of any one of claims 96-101, wherein the sugar-initiated polyether polyol is present in an amount of at least 30 wt%, 30 to 60 wt%, 30 to 50 wt%, or 35 to 45 wt%, based on the total weight of the polyol blend.

103. The method of any one of claims 65-102, wherein the polyol blend comprises an aliphatic triol-initiated polyether polyol that is a reaction product of an H-functional initiator containing an aliphatic triol, e.g., glycerol, and an alkylene oxide.

104. The method of claim 103, wherein the aliphatic triol is present in an amount of more than 50 wt%, at least 70 wt%, or at least 80 wt%, based on the total weight of the H-functional initiator used to make the aliphatic triol-initiated polyether polyol.

105. The method of claim 103 or 104, wherein the propylene oxide content is more than 50 wt%, at least 60 wt%, or at least 70 wt%, based on the total weight of the alkylene oxide used to make the aliphatic triol-initiated polyether polyol.

106. The method of claim 105, wherein the ethylene oxide content is no more than 50 wt%, no more than 40 wt%, or no more than 30 wt%, based on the total weight of alkylene oxides used to make the aliphatic triol-initiated polyether polyol.

107. The method of any one of claims 103 to 106, wherein the aliphatic triol-initiated polyether polyol has an OH number of 100 to 500 mg KOH / g, 200 to 400 mg KOH / g, 200 to 300 mg KOH / g, 200 to 250 mg KOH / g, 230 to 250 mg KOH / g, or 233 to 243 mg KOH / g, and a functionality of greater than 2 to 4, 2.5 to 3.5, or 3.

0.

108. The method of any one of claims 103 to 107, wherein the aliphatic triol-initiated polyether polyol contains a -C2H4O- unit content of less than 50 wt%, less than 40 wt%, or no more than 30 wt%, based on the total weight of the aliphatic triol-initiated polyether polyol.

109. The method of any one of claims 103 to 108, wherein the aliphatic triol-initiated polyether polyol is present in an amount of at least 30 wt%, 30 to 60 wt%, such as 30 to 50 wt%, or 35 to 45 wt%, based on the total weight of the polyol blend.

110. The method of any one of claims 65 to 109, wherein the polyol blend comprises a polyether polyol initiated with a alkanolamine, the polyether polyol initiated with a alkanolamine being a reaction product of an alkylene oxide and a starter containing an alkanolamine.

111. The method of claim 110, wherein the alkanolamine is represented by the formula: NH2— Z— OH wherein Z represents a divalent radical that is a straight chain or branched alkylene radical having 2 to 6 carbon atoms, a cycloalkylene radical having 4 to 6 carbon atoms, or a dialkylene ether radical having 4 to 6 carbon atoms, wherein the dialkylene ether radical can be represented by the formula: — R— O— R— wherein each R represents a hydrocarbon group having 2 to 3 carbon atoms.

112. The method of claim 110 or 111, wherein the alkanolamine comprises monoethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 1-(2- aminoethoxy)ethanol, 1-amino-2-butanol, 2-amino-3-butanol, 2-amino-2-methylpropanol, 5- aminopentanol, 3-amino-2,2-dimethylpropanol, 4-aminocyclohexanol, or a combination of any two or more thereof.

113. The method of any one of claims 110 to 112, wherein the alkanolamine content is greater than 50 wt%, at least 70 wt%, or at least 80 wt%, based on the total weight of the starter used to make the polyether polyol initiated with an alkanolamine. ​ ​ ​ ​ 114. The method of any of claims 110 to 113, wherein the content of propylene oxide is more than 50 wt%, at least 60 wt% or at least 70 wt%, based on the total weight of alkylene oxides used to make the alkanolamine-initiated polyether polyol.

115. The method of claim 114, wherein the content of ethylene oxide is no more than 50 wt%, no more than 40 wt% or in some cases no more than 30 wt%, based on the total weight of alkylene oxides used to make the alkanolamine-initiated polyether polyol.

116. The method of any of claims 110 to 115, wherein the alkanolamine-initiated polyether polyol has an OH number of at least 500 mg KOH / g, 500 to 900 mg KOH / g, 600 to 800 mg KOH / g or 680 to 720 mg KOH / g and a functionality of 2.5 to 4 or 2.5 to 3.

5.

117. The method of any of claims 65 to 116, wherein the polyol blend has a content of -C2H4O- units of 3 to 6 wt% or 4 to 6 wt%, based on the total weight of the polyurethane foam-forming composition.

118. The method of any of claims 65 to 117, wherein the haloolefin comprises HFO, HCFO or a combination thereof, for example wherein the haloolefin comprises 1,1,1,4,4,4-hexafluoro-2-butene (cis and / or trans isomers), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, E and / or Z isomers), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), HCFO 1223, 1,2-dichloro-1,2-difluoroethylene (E and / or Z isomers), 3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4-hexafluorobutene-2 (E and / or Z isomers) and 2-chloro-1,1,1,3,4,4,4-heptafluorobutene-2 (E and / or Z isomers), or a combination of any two or more thereof.

119. The method of any of claims 65 to 118, wherein the content of haloolefin is 5 to 30 wt%, 10 to 30 wt%, 15 to 25 wt% or 18 to 22 wt%, based on the total weight of the polyurethane foam-forming composition excluding the weight of polyisocyanate.

120. The method of any of claims 65 to 119, wherein the haloolefin is present in an amount of at least 90 wt%, at least 95 wt%, at least 99 wt% or 100 wt%, based on the total weight of physical blowing agent in the blowing agent composition.

121. The method of any of claims 65 to 120, wherein the carbon dioxide-generating chemical blowing agent comprises 0.5 to 5.0 wt%, 1 to 3 wt%, 1.0 to 2.0 wt% or 1.2 to 1.8 wt% water and / or formate-terminated amine, based on the total weight of the polyurethane foam-forming composition excluding the weight of polyisocyanate.

122. The method of any one of claims 65-121, wherein the physical blowing agent composition is present in a relative ratio by weight of 5: 1 to 50: 1, 5: 1 to 20: 1, or 10: 1 to 15: 1 to the chemical blowing agent that generates carbon dioxide.

123. The method of any one of claims 65-120, wherein the polyurethane foam-forming composition further comprises a surfactant, such as a silicone compound, such as a polysiloxane- polyolefin block copolymer, such as a polyether-modified polysiloxane.

124. The method of any one of claims 65-123, wherein the polyurethane foam-forming composition further comprises a catalyst, such as an organotin catalyst and / or a tertiary amine catalyst.

125. A polyurethane foam prepared from the method of any one of claims 65-124.

126. The polyurethane foam of claim 125, wherein the polyurethane foam has a closed cell content of greater than 80%, greater than 85%, or greater than 88%, as measured according to ASTM D6226-15.

127. The polyurethane foam of claim 126, wherein the polyurethane foam has a thermal conductivity of less than 0.126 BTU-in / h-ft2-°F (0.022 W / m-K) measured at 35 (2°C). 2 a thermal conductivity of less than 0.140 BTU-in / h-ft2-°F (0.025 W / m-K) measured at 75 (24°C). 2 measured according to ASTM C518-15 on foam sampled from the 2 inch thick slab core.​​ 128. A composite element comprising the polyurethane foam of claim 126 or claim 127 sandwiched between one or more layers of a facing substrate, such as wherein the facing substrate is constructed of plastic (such as continuous bi-directional glass fiber reinforced polypropylene resin or glass fiber reinforced polyester copolymer), paper, wood, or metal.

129. A refrigeration device, such as a refrigerator, freezer, refrigerated trailer, or chiller, comprising the composite element of claim 128.

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