Method for preparing foam from ternary blowing agent

Abstract

The present application relates to a method of making a foam from a composition comprising a ternary blowing agent component. Foamable compositions and foams prepared according to the methods provided herein are also disclosed.

Description

Technical Field

[0001] The present invention relates to a method for preparing a foam from a composition comprising a ternary blowing agent component. Background Art

[0002] Closed-cell polyisocyanate-based foams are widely used for thermal insulation purposes, for example, in building construction and in the manufacture of energy-efficient appliances. In the construction industry, polyurethane (polyisocyanurate) panels are used for roofs and wall panels due to their thermal insulation and load-bearing capabilities. Pour-in-place and spray polyurethane foams are widely used in a variety of applications, including insulated roofs, large structures such as storage tanks, equipment such as refrigerators and freezers, refrigerated trucks, and rail cars.

[0003] All of these various types of polyurethane foams require a blowing agent (expanding agent) for their manufacture. Thermal insulation foams rely on the use of halogenated hydrocarbon blowing agents, which are used not only to foam the polymer but also to obtain a low vapor thermal conductivity, which is a very important property for the thermal insulation value. Historically, polyurethane foams have used CFCs (chlorofluorocarbons, such as CFC-11, trichlorofluoromethane), HCFCs (hydrochlorofluorocarbons, such as HCFC-141b, 1,1-dichloro-1-fluoroethane), and HFCs (hydrofluorocarbons, such as HFC-245fa, HFC-365mfc) as the main blowing agents.

[0004] Generally, CFCs produce foams that exhibit good thermal insulation, low flammability, and excellent dimensional stability. However, despite these advantages, CFCs have fallen out of favor due to the chlorine-containing molecules' destruction of stratospheric ozone. In addition, the production and use of CFCs are restricted by the Montreal Protocol. HCFCs have been proposed as CFC alternatives and are currently used as blowing agents. However, HCFCs have also been shown to contribute to the depletion of stratospheric ozone, and thus their use has also come under scrutiny. According to the Montreal Protocol, the widespread use of HCFCs has been scheduled for eventual phase-out. Summary of the Invention

[0005] The present application particularly provides a method for forming a foam, the method comprising reacting or extruding a foamable composition under conditions effective to form a foam, wherein the foamable composition comprises a blowing agent component, the blowing agent component comprising:

[0006] from about 5 wt% to about 40 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E);

[0007] from about 8 wt% to about 30 wt% of a C5 hydrocarbon; and

[0008] From about 40 wt% to about 85 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)). This application provides a foamable composition comprising a blowing agent component, the blowing agent component comprising:

[0009] From about 5 wt% to about 40 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E);

[0010] From about 8 wt% to about 30 wt% of C5 hydrocarbons; and

[0011] From about 40 wt% to about 85 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0012] This application also provides a foam (such as polyisocyanurate or polyurethane) prepared from the foamable composition according to the method described herein.

[0013] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Methods and materials for use in the present invention are described herein; in addition, suitable methods and materials known in the art may also be used. The materials, methods, and examples are illustrative only and not intended to be limiting. All publications, patent applications, patents, sequences, database entries, and other references mentioned herein are incorporated herein by reference in their entirety. In case of conflict, the present specification and the definitions included therein shall prevail. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 Shows the measured thermal properties (K-factor) of the foams prepared from B-side compositions 2A-2D compared to the control composition as described in Example 2, where "1150" refers to HFO-1336mzz-E.

[0015] Figure 2 Shows the calculated ternary azeotrope prediction of a blend of HFO-1336mzz-E, isopentane, and HCFO-1233ze(E). The darker color indicates a stronger azeotrope region.

[0016] Figure 3 Shows the measured thermal properties (K-factor) of the foams prepared from B-side compositions 3A-3D compared to the control composition as described in Example 3.

[0017] Figure 4 Shows the calculated ternary azeotrope prediction of a blend of HFO-1336mzz-E, cyclopentane, and HCFO-1233ze(E). The darker color indicates a stronger azeotrope region. DETAILED DESCRIPTION

[0018] Polyisocyanurate (PIR) foam is an increasingly important market segment in the rigid insulation industry due to its excellent thermal properties and fire classification capabilities. The main blowing agents for PIR panel foams are C5 hydrocarbons such as cyclopentane, n-pentane, isopentane, or mixtures thereof. While these C5 blowing agents may provide sufficient insulation performance for current requirements, increasingly stringent energy efficiency regulations are driving further improvements. Hydrofluoroolefins (HFOs) represent a class of compounds used as blowing agents in polyurethanes and related foams. Additionally, many HFOs react and decompose relatively rapidly in the atmosphere. As a result, many HFOs have no or very low global warming potential (GWP) and do not contribute to stratospheric ozone depletion and global warming. It has been shown that HFOs have improved insulation performance compared to C5 hydrocarbons, but are significantly more expensive. Therefore, there is a need to add a minimal amount of HFO to C5 hydrocarbons to deliver the greatest improvement in insulation performance.

[0019] Spray polyurethane foam (SPF) is an increasingly important market segment in the rigid insulation industry due to its excellent thermal properties and building envelope sealing capabilities. When applied, the speed and quality of the applied layer are crucial for the effective application and efficacy of performance parameters including density and surface appearance. Additionally, such foams are applied in situ in buildings of interest under a variety of environmental conditions including cold winter temperatures. Typical physical blowing agents require heat to evaporate and expand. This becomes difficult at cold temperatures when the catalysis of polyurethane polymerization slows down, thus reducing the only heat source on the surface of the spray area. Therefore, providing a method for applying SPF with effective spreading under cold conditions represents a benefit to the industry.

[0020] Common techniques for preparing the insulating properties of closed-cell PIR and polyurethane (PUR) foams involve using binary blowing agent blends that contain, for example, hydrochlorofluorolefins (such as HCFO-1233zd) combined with hydrocarbons (such as isopentane, n-pentane, or cyclopentane). This application discloses a ternary blowing agent blend containing HCFO-1233zd combined with a C5 hydrocarbon and a hydrofluoroolefin component HFO-1336mzz-E, and unexpectedly finds that the blends described herein exhibit synergistic results and provide foams with improved insulating properties and long-life effects.

[0021] Definitions and Abbreviations

[0022] As used herein, the terms "comprising", "including", "having" or any other variation thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to inclusive or and not exclusive or. For example, condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0023] As used herein, the term "consisting essentially of" is used to define a composition, method that includes materials, steps, feature structures, components, or elements in addition to those disclosed in the document, provided that these additionally included materials, steps, feature structures, components, or elements do not significantly affect one or more of the basic and novel features of the invention claimed, particularly the mode of operation for achieving any of the desired results of the methods of the present invention. The term "consisting essentially of" occupies an intermediate position between "comprising" and "consisting of".

[0024] In addition, the use of "a" or "an" is employed to describe elements and components herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that there is another meaning.

[0025] As used herein, the term "about" is intended to account for variations that arise due to experimental error (e.g., plus or minus approximately 10% of the indicated value). Unless otherwise expressly stated, all measurements reported herein should be understood to be modified by the term "about", whether or not the term is explicitly used.

[0026] As used herein, the term "C n hydrocarbon" refers to a saturated hydrocarbon group having n carbons that can be straight-chain or branched-chain.

[0027] When an equivalent, concentration, or other value or parameter is given as a range, a preferred range, or a list of preferred upper and / or lower values, it is to be understood as specifically disclosing all ranges formed by any pair of any range upper limit or preferred value and any range lower limit or preferred value, whether or not the ranges are separately disclosed. Wherever a numerical range is given herein, that range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0028] The following abbreviations may be used throughout this patent application:

[0029] CFC: chlorofluorocarbon

[0030] Cp: Cyclopentane

[0031] GWP: Global warming potential

[0032] HCFO: Hydrochlorofluorolefin

[0033] HFC: Hydrofluorocarbon

[0034] HFO: Hydrofluoroolefin

[0035] HFO-1336mzz-E or 1336mzz(E): E-CF3CH=CHCF3

[0036] HCFO-1233zd(E) or 1233zd(E): E-CHCl=CHCF3

[0037] pcf: Pound-force per cubic foot

[0038] PIR: Polyisocyanurate

[0039] pphp: Parts per hundred parts of polyol

[0040] PUR: Polyurethane

[0041] SPF: Sprayed polyurethane foam

[0042] TCPP: Tris(1-chloro-2-propyl) phosphate

[0043] wt%: Weight percent

[0044] Foamable Compositions and Methods for Preparing Foams

[0045] In some embodiments, the present application provides a foamable composition comprising a blowing agent component, wherein the blowing agent component comprises E-CF3CH=CHCF3 (HFO-1336mzz-E), a C5 hydrocarbon, and E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the foamable composition provided herein can be used in a method for forming a foam.

[0046] In some embodiments, the blowing agent component comprises from about 5 wt% to about 40 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), for example, from about 5 wt% to about 35 wt%, from about 5 wt% to about 30 wt%, from about 5 wt% to about 25 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 15 wt%, from about 5 wt% to about 10 wt%, from about 10 wt% to about 40 wt%, from about 10 wt% to about 35 wt%, from about 10 wt% to about 30 wt%, from about 10 wt% to about 25 wt%, from about 10 wt% to about 20 wt%, from about 10 wt% to about 15 wt%, from about 15 wt% to about 40 wt%, from about 15 wt% to about 35 wt%, from about 15 wt% to about 30 wt%, from about 15 wt% to about 25 wt%, from about 15 wt% to about 20 wt%, from about 20 wt% to about 40 wt%, from about 20 wt% to about 35 wt%, from about 20 wt% to about 30 wt%, from about 20 wt% to about 25 wt%, from about 25 wt% to about 40 wt%, from about 25 wt% to about 35 wt%, from about 25 wt% to about 30 wt%, from about 30 wt% to about 40 wt%, from about 30 wt% to about 35 wt%, or from about 30 wt% to about 40 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0047] In some embodiments, the blowing agent component comprises from about 10 wt% to about 35 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises from about 10 wt% to about 30 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises from about 10 wt% to about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0048] In some embodiments, the blowing agent component comprises about 30 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 20 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 15 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 10 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0049] In some embodiments, the blowing agent component comprises from about 8 wt% to about 30 wt% of a C5 hydrocarbon, such as from about 8 wt% to about 25 wt%, from about 8 wt% to about 20 wt%, from about 8 wt% to about 15 wt%, from about 8 wt% to about 10 wt%, from about 10 wt% to about 30 wt%, from about 10 wt% to about 25 wt%, from about 10 wt% to about 20 wt%, from about 10 wt% to about 15 wt%, from about 15 wt% to about 30 wt%, from about 15 wt% to about 25 wt%, from about 15 wt% to about 20 wt%, from about 20 wt% to about 30 wt%, from about 20 wt% to about 25 wt%, or from about 25 wt% to about 30 wt% of a C5 hydrocarbon.

[0050] In some embodiments, the blowing agent component comprises from about 10 wt% to about 25 wt% of a C5 hydrocarbon. In some embodiments, the blowing agent component comprises from about 8 wt% to about 12 wt% of a C5 hydrocarbon.

[0051] In some embodiments, the C5 hydrocarbon is selected from n-pentane, isopentane, and cyclopentane.

[0052] In some embodiments, the C5 hydrocarbon is cyclopentane. In some embodiments, the blowing agent component comprises from about 8 wt% to about 12 wt% of cyclopentane. In some embodiments, the blowing agent component comprises about 10 wt% of cyclopentane.

[0053] In some embodiments, the C5 hydrocarbon is isopentane. In some embodiments, the blowing agent component comprises from about 10 wt% to about 25 wt% of isopentane. In some embodiments, the blowing agent component comprises about 25 wt% of isopentane. In some embodiments, the blowing agent component comprises about 20 wt% of isopentane. In some embodiments, the blowing agent component comprises about 10 wt% of isopentane.

[0054] In some embodiments, the blowing agent composition comprises from about 40 wt% to about 85 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)), for example, from about 40 wt% to about 80 wt%, from about 40 wt% to about 75 wt%, from about 40 wt% to about 70 wt%, from about 40 wt% to about 65 wt%, from about 40 wt% to about 60 wt%, from about 40 wt% to about 55 wt%, from about 40 wt% to about 50 wt%, from about 40 wt% to about 45 wt%, from about 45 wt% to about 85 wt%, from about 45 wt% to about 80 wt%, from about 45 wt% to about 75 wt%, from about 45 wt% to about 70 wt%, from about 45 wt% to about 65 wt%, from about 45 wt% to about 60 wt%, from about 45 wt% to about 55 wt%, from about 45 wt% to about 50 wt%, from about 50 wt% to about 85 wt%, from about 50 wt% to about 80 wt%, from about 50 wt% to about 75 wt%, from about 50 wt% to about 70 wt%, from about 50 wt% to about 65 wt%, from about 50 wt% to about 60 wt%, from about 50 wt% to about 55 wt%, from about 55 wt% to about 85 wt%, from about 55 wt% to about 80 wt%, from about 55 wt% to about 75 wt%, from about 55 wt% to about 70 wt%, from about 55 wt% to about 65 wt%, from about 55 wt% to about 60 wt%, from about 60 wt% to about 85 wt%, from about 60 wt% to about 80 wt%, from about 60 wt% to about 75 wt%, from about 60 wt% to about 70 wt%, from about 60 wt% to about 65 wt%, from about 65 wt% to about 85 wt%, from about 65 wt% to about 80 wt%, from about 65 wt% to about 75 wt%, from about 65 wt% to about 70 wt%, from about 70 wt% to about 85 wt%, from about 70 wt% to about 80 wt%, from about 70 wt% to about 75 wt%, from about 75 wt% to about 85 wt%, from about 75 wt% to about 80 wt%, or from about 80 wt% to about 85 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0055] In some embodiments, the blowing agent composition comprises from about 65 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent composition comprises from about 45 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0056] In some embodiments, the blowing agent composition comprises about 45 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent composition comprises about 60 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent composition comprises about 65 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent composition comprises about 70 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent composition comprises about 75 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent composition comprises about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0057] In some embodiments, the blowing agent composition comprises:

[0058] from about 5 wt% to about 40 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E);

[0059] from about 8 wt% to about 30 wt% of C5 hydrocarbons; and

[0060] from about 40 wt% to about 85 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0061] In some embodiments, the blowing agent composition comprises:

[0062] from about 10 wt% to about 30 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-

[0063] E);

[0064] from about 10 wt% to about 25 wt% of C5 hydrocarbons; and

[0065] from about 45 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0066] In some embodiments, the blowing agent composition comprises:

[0067] from about 10 wt% to about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-

[0068] E);

[0069] about 10 wt% of C5 hydrocarbons; and

[0070] About 65 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0071] In some embodiments, the blowing agent composition comprises:

[0072] About 10 wt% to about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-

[0073] E);

[0074] About 10 wt% of cyclopentane; and

[0075] About 65 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0076] In some embodiments, the blowing agent composition comprises:

[0077] About 10 wt% to about 30 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-

[0078] E);

[0079] About 10 wt% to about 25 wt% of isopentane; and

[0080] About 45 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0081] In some embodiments, the blowing agent composition comprises:

[0082] About 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 65 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0083] About 20 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 70 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0084] About 15 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 75 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0085] Approximately 10% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), approximately 10% by weight of cyclopentane, and approximately 80% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0086] Approximately 30% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), approximately 25% by weight of isopentane, and approximately 45% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0087] Approximately 20% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), approximately 20% by weight of isopentane, and approximately 60% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0088] Approximately 15% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), approximately 10% by weight of isopentane, and approximately 75% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0089] Approximately 10% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), approximately 10% by weight of isopentane, and approximately 80% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0090] In some embodiments, the foamable composition further comprises one or more polyols. In some embodiments, one or more additives may be included in the foamable composition described herein. For example, the foamable composition may further comprise one or more additives, including but not limited to catalysts, surfactants, flame retardants, stabilizers, preservatives, chain extenders, crosslinking agents, water, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, nucleating agents, smoke suppressants, and pigments.

[0091] In some embodiments, the foamable composition further comprises one or more additional components selected from at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent.

[0092] In some embodiments, the foamable composition comprises at least one polyol. In some embodiments, the polyol comprises polyester polyol and polyether polyol in any ratio. One or more of each polyester polyol and polyether polyol can be used. In some embodiments, the polyol comprises polyester polyol and polyether polyol in a weight ratio of about 1:1 to about 2:1. In some embodiments, the polyol comprises polyester polyol and polyether polyol in a weight ratio of about 1:1. In some embodiments, the polyol comprises polyester polyol and polyether polyol in a weight ratio of about 1:1. In some embodiments, the polyol comprises polyester polyol and polyether polyol in a weight ratio of about 1:1.

[0093] In some embodiments, polyol is polyester polyol. Suitable polyester polyol includes those prepared by reacting carboxylic acid and / or its derivative or polycarboxylic acid anhydride with polyol. Polycarboxylic acid can be any one of known aliphatic polycarboxylic acid, alicyclic polycarboxylic acid, aromatic polycarboxylic acid and / or heterocyclic polycarboxylic acid, and can be substituted (for example, substituted by halogen atom) and / or be unsaturated. The example of suitable polycarboxylic acid and acid anhydride comprises oxalic acid, malonic acid, glutaric acid, pimelic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride acid, maleic acid, maleic anhydride, fumaric acid and dimerization and trimerization fatty acid, such as those oleic acids that can be mixed with monomeric fatty acids. Also can use the simple ester of polycarboxylic acid, such as dimethyl terephthalate, glycol terephthalate and their extract.The polyol that is applicable to the preparation of polyester polyol can be aliphatic, alicyclic, aromatic and / or heterocyclic. The polyols may optionally include substituents that are inert in the reaction, such as chlorine and bromine substituents, and / or may be unsaturated. Suitable amino alcohols such as monoethanolamine, diethanolamine, etc. may also be used. Examples of suitable polyols include ethylene glycol, propylene glycol, polyoxyalkylene glycols (e.g., diethylene glycol, polyethylene glycol, dipropylene glycol, and polypropylene glycol), glycerol, and trimethylolpropane.

[0094] Other suitable polyester polyols include, but are not limited to, aromatic polyester polyols, such as those made by transesterifying polyethylene terephthalate (PET) waste with ethylene glycol, such as diethylene glycol, or by reacting phthalic anhydride with ethylene glycol. The resulting polyester polyols can be further reacted with ethylene oxide and / or propylene oxide to form extended polyester polyols containing additional internal alkyleneoxy groups.

[0095] In some embodiments, the polyester polyol has an average molecular weight of from about 400 g / mol to about 500 g / mol, such as from about 450 g / mol to about 475 g / mol. In some embodiments, the polyester polyol is an aromatic polyester polyol having an average hydroxyl number of from about 200 to about 325, such as from about 235 to about 265, or from about 230 to about 250, or from about 295 to about 315.

[0096] Exemplary polyester polyols that are commercially available include polyester polyols PS-2352 (Stepan Company, Chicago, IL), PS-2502A (Stepan Company, Chicago, IL), PS-2412 (Stepan Company, Chicago, IL), PS-2520 (Stepan Company, Chicago, IL), PS-3021 (Stepan Company, Chicago, IL), PS-3024 (Stepan Company, Chicago, IL), 256 (Huntsman, The Woodlands, TX), and 925 (Huntsman, The Woodlands, TX), 250 (Huntsman, The Woodlands, TX), 305 (Huntsman, The Woodlands, TX), 563 (Huntsman, The Woodlands, TX), 649 (Huntsman, The Woodlands, TX), 1465 (Huntsman, The Woodlands, TX), TB-305 (COIM, West Deptford, NJ), TB-306 (COIM, West Deptford, NJ), HT5510 (Invista), 5232 (Invista), 5100 (Invista), 5150 (Invista), 5170 (Invista), PES-240 (Carpenter Co., Richmond, VA), PES-265 (Carpenter Co., Richmond, VA), PES-305 (Carpenter Co., Richmond, VA), PES-295 (Carpenter Co., Richmond, VA),

[0097] In some embodiments, the foamable composition comprises one or more polyether polyols. Examples of suitable polyether polyols include, but are not limited to, polyethylene oxide, polypropylene oxide, mixed polyethylene oxide - propylene oxide with terminal hydroxyl groups, etc. Other suitable polyols can be prepared by reacting ethylene oxide and / or propylene oxide with initiators having 2 to 16, or 3 to 8 hydroxyl groups (such as polyhydroxy compounds in the form of glycerol, pentaerythritol, and carbohydrates such as sorbitol, glucose, sucrose, etc.). Suitable polyether polyols can also include polyols based on aliphatic amines or aromatic amines. Exemplary commercially available polyether polyols include polyether polyol PPG-400 (Huntsman, The Woodlands, TX), PPG-1000 (Huntsman, The Woodlands, TX), FX31-240 (Huntsman, The Woodlands, TX), G31-28 (Huntsman, The Woodlands, TX), R-425X (Huntsman, The Woodlands, TX), R-470X (Huntsman, The Woodlands, TX), S-490 (Huntsman, The Woodlands, TX), SG-360 (Huntsman, The Woodlands, TX), SG-522 (Huntsman, The Woodlands, TX), PGP-400 (Carpenter Co., Richmond, VA), PGP-1000 (Carpenter Co., Richmond, VA), GP-700 (Carpenter Co., Richmond, VA)、 GP-6015 (Carpenter Co., Richmond, VA)、 MX-425 (Carpenter Co., Richmond, VA)、 MX-470 (Carpenter Co., Richmond, VA)、 GSP-355 (Carpenter Co., Richmond, VA)、 GSP-520 (Carpenter Co., Richmond, VA)、 SP-477 (Carpenter Co., Richmond, VA)、 220-260 (Dow Chemical, Midland, MI)、 220-110 (Dow Chemical, Midland, MI)、 230-238 (Dow Chemical, Midland, MI)、 232-027 (Dow Chemical, Midland, MI)、 470 (Dow Chemical, Midland, MI)、 360 (Dow Chemical, Midland, MI)、 520 (Dow Chemical, Midland, MI)、 391 (Dow Chemical, Midland, MI)、 P410R (BASF, Germany)、 P1010 (BASF, Germany)、 GP730 (BASF, Germany)、 220 (BASF, Germany)、 3422 (BASF, Germany)、 SG-360 (BASF, Germany)、 824 (BASF, Germany)、 735 (BASF, Germany), PPG - 425 (Covestro, Leverkusen, Germany), 1000 (Covestro, Leverkusen, Germany), LHT - 240 (Covestro, Leverkusen, Germany), 9139 (Covestro, Leverkusen, Germany), 3901 (Covestro, Leverkusen, Germany), 4034 (Covestro, Leverkusen, Germany), 20 - 265 (Monument Chemical, Indianapolis, IN), 20 - 112 (Monument Chemical, Indianapolis, IN), 30 - 240 (Monument Chemical, Indianapolis, IN), 85 - 29 (Monument Chemical, Indianapolis, IN), 73 - 490 (Monument Chemical, Indianapolis, IN), 74 - 376 (Monument Chemical, Indianapolis, IN) and 74 - 532.

[0098] In some embodiments, the polyether polyol is a moderately functionalized polyether polyol. For example, the polyether polyol has a functionality of about four. In some embodiments, the polyether polyol is sucrose / glycerol-initiated. In some embodiments, the polyether polyol is a Mannich-based polyether polyol. As used herein, the term "Mannich-based polyol" refers to an aromatic polyol obtained by alkoxylating a Mannich base with propylene oxide and / or ethylene oxide, said Mannich base being obtained by the classical Mannich reaction between a phenol (e.g., phenol, p-nonylphenol), formaldehyde, and an alkanolamine (diethanolamine, diisopropanolamine, monoethanolamine, monoisopropanolamine, etc.). Exemplary commercially available polyether polyols include 490 (Dow Chemical, Midland, MI), MX-425 (Carpenter Co., Richmond, VA), and MX-470 (Carpenter Co., Richmond, VA).

[0099] In some embodiments, the polyol is a polyester polyol having a hydroxyl number of from about 200 mg KOH / g to about 300 mg KOH / g.

[0100] In some embodiments, the polyol is a polyester polyol having a hydroxyl number of from about 230 mg KOH / g to about 250 mg KOH / g.

[0101] In some embodiments, the blowing agent composition described herein that includes E-CF3CH=CHCF3 (HFO-1336mzz-E), C5 hydrocarbons, and E-CHCl=CHCF3 (HCFO-1233zd(E)) is soluble in the polyol blend. In some embodiments, the solubility is measured by visual assessment.

[0102] In some embodiments, the foamable composition includes at least one catalyst for the reaction of the polyol with the polyisocyanate (i.e., the A-side). Any suitable urethane catalyst can be used, including amine-based compounds such as tertiary amine compounds, for example, dimethylethanolamine and bis(2-dimethylaminoethyl) ether, and organometallic compounds. Such catalysts are used in an amount that increases the reaction rate of the polyisocyanate. By way of example, a typical amount of catalyst used per 100 parts by weight of the polyol is from about 0.1 to about 5 parts of catalyst. In some embodiments, the foamable composition includes a gelling catalyst such as a non-nucleophilic gelling catalyst. In some embodiments, the foamable composition includes a blowing catalyst. In some embodiments, the foamable composition includes a metal catalyst. In some embodiments, the foamable composition includes a metal catalyst and an amine catalyst.

[0103] Exemplary catalysts are disclosed, for example, in U.S. Patent No. 5,164,419, the disclosure of which is incorporated herein by reference. For example, catalysts for the trimerization reaction of polyisocyanates, such as alkali metal alkoxides, alkali metal carboxylates, or quaternary amine salts, can also optionally be employed herein. Such catalysts are used in an amount that measurably increases the reaction rate of the polyisocyanate. A typical amount of catalyst is from about 0.1 wt% to about 5 wt% based on the total weight of all the foaming components. Non-limiting examples of catalysts include 8, N,N-dimethylcyclohexylamine from Evonik Industries; 5; pentamethyldiethylenetriamine from Evonik Industries; and 52; 2-Methyl(n-methylaminob-acetate nonylphenol) from Evonik Industries; 30 (Evonik Industries); 36 (Evonik Industries); 46 (Evonik Industries); 77 (Evonik Industries); 2039 (Evonik Industries); 204 (Evonik Industries); 2040 (Evonik Industries); BL-19 (Evonik Industries); BL-17 (Evonik Industries); T (Evonik Industries); T-125 (Evonik Industries); K-15 (Evonik Industries); TMR (Evonik Industries); TMR-2 (Evonik Industries); TMR-3 (Evonik Industries); TMR-30 (Evonik Industries); 8210 (The Shepard Chemical Company, Cincinnati, OH); 8840 (The Shepard Chemical Company, Cincinnati, OH); 8842 (The Shepard Chemical Company, Cincinnati, OH); XK 651 (King Industries, Norwalk, CT); 614 (King Industries, Norwalk, CT); 672 (King Industries, Norwalk, CT); 604 (King Industries, Norwalk, CT); UL1 (Momentive Performance Materials Inc., Waterford, NY); UL22; UL1 (Momentive Performance Materials Inc., Waterford, NY); D - 230 (Huntsman, The Woodlands, TX); T403 (Huntsman, The Woodlands, TX); D2000 (Huntsman, The Woodlands, TX), T5000 (Huntsman, The Woodlands, TX); PMDETA (Huntsman, The Woodlands, TX); DMCHA (Huntsman, The Woodlands, TX); ZF20 (Huntsman, The Woodlands, TX); ZF54 (Huntsman, The Woodlands, TX); tin; dibutyltin mercaptide; potassium octoate; potassium acetate; bismuth; bismuth carboxylate mixture, etc.

[0104] In some embodiments, the foamable composition comprises a surfactant. Suitable surfactants can include liquid or solid silicone compounds. Other surfactants include polyethylene glycol ethers of long - chain alcohols, tertiary amines or alkanolamine salts of long - chain alkyl acid sulfates, alkyl sulfonates, and alkyl aryl sulfonic acids. In some embodiments, the surfactant is a silicone surfactant. In some embodiments, the surfactant is a silicone polyether surfactant. In some embodiments, the surfactant is DC5585. In some embodiments, the surfactant is B8871.

[0105] In some embodiments, the foamable composition comprises a flame retardant. Available flame retardants include, but are not limited to, tris(2 - chloroethyl) phosphate, tris(2 - chloropropyl) phosphate, tris(1 - chloro - 2 - propyl) phosphate (TCPP), tris(2,3 - dibromopropyl) phosphate, tris(1,3 - dichloropropyl) phosphate, diammonium phosphate, halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, brominated diester / ether diols of tetrabromophthalic anhydride, such as mixed esters of tetrabromophthalic anhydride with diethylene glycol and propylene glycol. Exemplary commercially available flame retardants include RB-79, a reactive brominated diester / ether diol of tetrabromophthalic anhydride (Albemarle Corporation, Baton Rouge, LA). In some embodiments, the flame retardant is tris(1-chloro-2-propyl) phosphate (TCPP).

[0106] In some embodiments, the foamable composition comprises a nucleating agent. Nucleating agents are mainly used to increase the number of cells and reduce the cell size in the foam, and can be used in an amount of about 0.1 to about 10 parts by weight per 100 parts by weight of the resin. Typical nucleating agents include at least one member selected from the group consisting of talc, sodium bicarbonate-citric acid mixture, calcium silicate, and carbon dioxide. In some embodiments, the foamable composition does not contain a nucleating agent. In some embodiments, the methods provided herein are carried out in the absence of a nucleating agent. Exemplary nucleating agents include, but are not limited to, talc, sodium bicarbonate-citric acid mixture, calcium silicate, carbon dioxide, and the like.

[0107] In some embodiments, the foamable composition further comprises water.

[0108] In some embodiments, the present application also provides a method of forming a foam, the method comprising reacting or extruding the foamable composition provided herein under conditions effective to form a foam, wherein the foamable composition comprises the blowing agent component described herein.

[0109] In some embodiments, the method of forming a foam comprises: (a) adding the foamable composition disclosed herein (e.g., the B-side composition) to a composition comprising an isocyanate (e.g., the A-side composition); and (b) reacting the compositions under conditions effective to form a foam. The isocyanate or isocyanate-containing mixture may include an isocyanate and chemical additives such as catalysts, surfactants, stabilizers, chain extenders, crosslinking agents, water, flame retardants, smoke suppressants, pigments, coloring materials, fillers, and the like. In some embodiments, the isocyanate is PAPI-27. According to the compositions disclosed herein, any method known in the art can be used or is suitable for use, such as those described in "Polyurethanes Chemistry and Technology", Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons (New York, N.Y.), which is incorporated herein by reference.

[0110] In a process for preparing a polyisocyanate-based foam, a polyol, a polyisocyanate, and other components are contacted, thoroughly mixed, and allowed to expand and cure into a cellular polymer. The specific mixing apparatus is not critical, and various types of mixing heads and spraying devices are used. It is often convenient, but not necessary, to pre-blend certain ingredients prior to reacting the polyisocyanate and the polyol. For example, it is often useful to prepare a foamable composition (e.g., a B-side composition) as disclosed herein and then contact the composition with a polyisocyanate.

[0111] It is to be understood that the present application also provides a foamable composition as described herein for use in a process for preparing a foam as described herein. In some embodiments, the foamable composition described herein can be used in one or more of the methods described herein.

[0112] Foam

[0113] The present application also provides a foam prepared according to one or more of the methods provided herein (e.g., a foam prepared from one or more of the foamable compositions provided herein according to one or more of the methods provided herein). The types of foams prepared can include, for example, closed-cell foams, open-cell foams, rigid foams, flexible foams, and self-skins. In some embodiments, a foam prepared from the foamable composition described herein (e.g., a B-side composition) is disclosed. In some embodiments, the foam is a spray foam. In some embodiments, the foam is a thermoset foam.

[0114] In some embodiments, the foam is a polyurethane foam or a polyisocyanurate foam. In some embodiments, the foam is a closed-cell foam. In some embodiments, the foam is a closed-cell polyisocyanurate foam. In some embodiments, the foam is a rigid closed-cell polyisocyanurate foam. In some embodiments, the foam is a rigid closed-cell polyurethane foam. In some embodiments, the rigid closed-cell polyisocyanate-based foam can be used for spray insulation, appliance foam as in-situ foam, rigid insulation panels, or in laminates.

[0115] In some embodiments, the foams disclosed herein can be used in a variety of applications, including but not limited to appliance foams, including refrigerator foams, freezer foams, refrigerator / freezer foams, panel foams, and other cold or cryogenic manufacturing applications. In some embodiments, the foams formed from the compositions disclosed herein have excellent thermal properties, such as can be measured by the K-factor. As used herein, "K-factor" represents the thermal conductivity or the ability of the foam to conduct heat. The K-factor is a measure of the amount of heat that passes through one square foot of a material one inch thick in one hour. Generally, the lower the K-factor, the better the insulation.

[0116] In some embodiments, the foam has a K-factor of about 0.135 Btu in / ft 2 h °C or less at about 24 °C. In some embodiments, the foam has a K-factor of about 0.130 Btu in / ft 2 h °C to about 0.135 Btu in / ft 2 h °C at 24 °C.

[0117] In some embodiments, the foam has a K-factor of about 0.124 Btu in / ft 2 h °C or less at about 10 °C. In some embodiments, the foam has a K-factor of about 0.118 Btu in / ft 2 h °C to about 0.124 Btu in / ft 2 h °C at 10 °C.

[0118] In some embodiments, the foam has a K-factor of about 0.118 Btu in / ft 2 h °C or less at about -6.7 °C. In some embodiments, the foam has a K-factor of about 0.110 Btu in / ft 2 h °C to about 0.118 Btu in / ft 2 h °C at -6.7 °C.

[0119] In some embodiments, the foam has a K-factor of about 0.135 Btu in / ft 2 h °C or less at about 24 °C, a K-factor of about 0.124 Btu in / ft 2 h °C or less at about 10 °C, and a K-factor of about 0.118 Btu in / ft 2 h °C or less at about -6.7 °C.

[0120] In some embodiments, the foam has a K-factor of about 0.130 Btu in / ft 2 h °C to about 0.135 Btu in / ft 2 h °C at 24 °C, a K-factor of about 0.118 Btu in / ft 2 h °C to about 0.124 Btu in / ft 2 h °C at 10 °C, and a K-factor of about 0.110 Btu in / ft 2 h °C to about 0.118 Btu in / ft 2 h °C at -6.7 °C.

[0121] In some embodiments, the foam has a K-factor of about 0.142 Btu in / ft 2A K-factor of h °C or less. In some embodiments, the foam has a K-factor of about 0.140 Btu in / ft at 24 °C 2 h °C to about 0.139 Btu in / ft 2 h °C.

[0122] In some embodiments, the foam has a K-factor of about 0.129 Btu in / ft at about 10 °C 2 h °C or less. In some embodiments, the foam has a K-factor of about 0.127 Btu in / ft at 10 °C 2 h °C to about 0.129 Btu in / ft 2 h °C.

[0123] In some embodiments, the foam has a K-factor of about 0.120 Btu in / ft at about -6.7 °C 2 h °C or less. In some embodiments, the foam has a K-factor of about 0.116 Btu in / ft at -6.7 °C 2 h °C to about 0.120 Btu in / ft 2 h °C.

[0124] In some embodiments, the foam has a K-factor of about 0.142 Btu in / ft at about 24 °C 2 h °C or less, about 0.129 Btu in / ft at about 10 °C 2 h °C or less, and about 0.120 Btu in / ft at about -6.7 °C 2 h °C or less.

[0125] In some embodiments, the foam has a K-factor of about 0.140 Btu in / ft at 24 °C 2 h °C to about 0.139 Btu in / ft 2 h °C, about 0.127 Btu in / ft at 10 °C 2 h °C to about 0.129 Btu in / ft 2 h °C, and about 0.116 Btu in / ft at -6.7 °C 2 h °C to about 0.120 Btu in / ft 2 h °C.

[0126] In some embodiments, the foam has a cream time of from about 1 second to about 30 seconds, such as from about 1 second to about 25 seconds, from about 1 second to about 20 seconds, from about 1 second to about 15 seconds, from about 1 second to about 10 seconds, from about 1 second to about 5 seconds, from about 5 seconds to about 30 seconds, from about 5 seconds to about 25 seconds, from about 5 seconds to about 20 seconds, from about 5 seconds to about 15 seconds, from about 5 seconds to about 10 seconds, from about 10 seconds to about 30 seconds, from about 10 seconds to about 25 seconds, from about 10 seconds to about 20 seconds, from about 10 seconds to about 15 seconds, from about 15 seconds to about 30 seconds, from about 15 seconds to about 25 seconds, from about 15 seconds to about 20 seconds, from about 20 seconds to about 30 seconds, from about 20 seconds to about 25 seconds, or from about 25 seconds to about 30 seconds. In some embodiments, the present application provides a foam having a cream time of from about 20 seconds to about 30 seconds. In some embodiments, the present application provides a foam having a cream time of from about 5 seconds to about 12 seconds.

[0127] In some embodiments, the foam has a gelling time of from about 30 seconds to about 70 seconds, such as from about 30 seconds to about 65 seconds, from about 30 seconds to about 60 seconds, from about 30 seconds to about 55 seconds, from about 30 seconds to about 50 seconds, from about 30 seconds to about 45 seconds, from about 30 seconds to about 40 seconds, from about 30 seconds to about 35 seconds, from about 35 seconds to about 70 seconds, from about 35 seconds to about 65 seconds, from about 35 seconds to about 60 seconds, from about 35 seconds to about 55 seconds, from about 35 seconds to about 50 seconds, from about 35 seconds to about 45 seconds, from about 35 seconds to about 40 seconds, from about 40 seconds to about 70 seconds, from about 40 seconds to about 65 seconds, from about 40 seconds to about 60 seconds, from about 40 seconds to about 55 seconds, from about 40 seconds to about 50 seconds, from about 40 seconds to about 45 seconds, from about 45 seconds to about 70 seconds, from about 45 seconds to about 65 seconds, from about 45 seconds to about 60 seconds, from about 45 seconds to about 55 seconds, from about 45 seconds to about 50 seconds, from about 50 seconds to about 70 seconds, from about 50 seconds to about 65 seconds, from about 50 seconds to about 60 seconds, from about 50 seconds to about 55 seconds, from about 55 seconds to about 70 seconds, from about 55 seconds to about 65 seconds, from about 55 seconds to about 60 seconds, from about 60 seconds to about 70 seconds, from about 60 seconds to about 65 seconds, or from about 65 seconds to about 70 seconds. In some embodiments, the foam has a gelling time of from about 50 seconds to about 65 seconds. In some embodiments, the foam has a gelling time of from about 35 seconds to about 45 seconds.

[0128] In some embodiments, the foam has a non-stick time of from about 85 seconds to about 140 seconds, such as from about 85 seconds to about 135 seconds, from about 85 seconds to about 130 seconds, from about 85 seconds to about 125 seconds, from about 85 seconds to about 120 seconds, from about 85 seconds to about 115 seconds, from about 85 seconds to about 110 seconds, from about 85 seconds to about 105 seconds, from about 85 seconds to about 100 seconds, from about 85 seconds to about 95 seconds, from about 85 seconds to about 90 seconds, from about 90 seconds to about 140 seconds, from about 90 seconds to about 135 seconds, from about 90 seconds to about 130 seconds, from about 90 seconds to about 125 seconds, from about 90 seconds to about 120 seconds, from about 90 seconds to about 115 seconds, from about 90 seconds to about 110 seconds, from about 90 seconds to about 105 seconds, from about 90 seconds to about 100 seconds, from about 90 seconds to about 95 seconds, from about 95 seconds to about 140 seconds, from about 95 seconds to about 135 seconds, from about 95 seconds to about 130 seconds, from about 95 seconds to about 125 seconds, from about 95 seconds to about 120 seconds, from about 95 seconds to about 115 seconds, from about 95 seconds to about 110 seconds, from about 95 seconds to about 105 seconds, from about 95 seconds to about 100 seconds, from about 100 seconds to about 140 seconds, from about 100 seconds to about 135 seconds, from about 100 seconds to about 130 seconds, from about 100 seconds to about 125 seconds, from about 100 seconds to about 120 seconds, from about 100 seconds to about 115 seconds, from about 100 seconds to about 110 seconds, from about 100 seconds to about 105 seconds, from about 105 seconds to about 140 seconds, from about 105 seconds to about 135 seconds, from about 105 seconds to about 130 seconds, from about 105 seconds to about 125 seconds, from about 105 seconds to about 120 seconds, from about 105 seconds to about 115 seconds, from about 105 seconds to about 110 seconds, from about 110 seconds to about 140 seconds, from about 110 seconds to about 135 seconds, from about 110 seconds to about 130 seconds, from about 110 seconds to about 125 seconds, from about 110 seconds to about 120 seconds, from about 110 seconds to about 115 seconds, from about 115 seconds to about 140 seconds, from about 115 seconds to about 135 seconds, from about 115 seconds to about 130 seconds, from about 115 seconds to about 125 seconds, from about 115 seconds to about 120 seconds, from about 120 seconds to about 140 seconds, from about 120 seconds to about 135 seconds, from about 120 seconds to about 130 seconds, from about 120 seconds to about 125 seconds, from about 125 seconds to about 140 seconds, from about 125 seconds to about 135 seconds, from about 125 seconds to about 130 seconds, from about 130 seconds to about 140 seconds, from about 130 seconds to about 135 seconds, or from about 135 seconds to about 140 seconds. In some embodiments, the foam has a non-stick time of from about 120 seconds to about 135 seconds. In some embodiments, the foam has a non-stick time of from about 90 seconds to about 100 seconds.

[0129] In some embodiments, the foam has a density of from about 2.5 pcf to about 3.5 pcf. For example, the foam can have a density of about 2.5 pcf, 2.6 pcf, 2.7 pcf, 2.8 pcf, 2.9 pcf, 3.0 pcf, 3.1 pcf, 3.2 pcf, 3.3 pcf, 3.4 pcf, or 3.5 pcf. In some embodiments, the present application provides a foam having a density of from about 2.90 pcf to about 3.10 pcf. In some embodiments, the foam has a density of from about 2.53 pcf to about 2.56 pcf.

[0130] In some embodiments, the foam has a closed cell content of from about 90% to about 99%. For example, the foam can have a closed cell content of about 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%. In some embodiments, the foam has a closed cell content of from about 96% to about 99%. In some embodiments, the foam has a closed cell content of from about 90% to about 95%. In some embodiments, the foam has a closed cell content of from about 96% to about 99%.

[0131] Representative foamed products that can be manufactured in accordance with the present disclosure include, for example: (1) polystyrene foam sheets for producing disposable thermoformed packaging materials, such as those disclosed in U.S. Patent No. 5,204,169; (2) extruded polystyrene foam boards used as residential and industrial siding and roofing materials, which can be from about 0.5 inches to 6 inches (1.25 cm to 15 cm) thick, up to 4 feet (122 cm) wide, and have a cross-sectional area of from 0.17 square feet to 3 square feet (0.016 square meters to 0.28 square meters), and up to 27 feet (813 meters) long, with a density of from about 1.5 pounds per cubic foot (pcf) to 10 pounds per cubic foot (pcf) (25 kilograms per cubic meter (kg / m 3 ) to 160 kilograms per cubic meter (kg / m 3 )); (3) expandable foam in the form of billets, which can be up to about 2 feet (61 cm) thick, typically at least 1.5 feet (46 cm) thick, up to 4 feet (1.22 meters) wide, up to 16 feet (4.8 meters) long, having a cross-sectional area of from about 2 square feet to 8 square feet (0.19 square meters to 0.74 square meters) and a density of from 6 pcf to 15 pcf (96 kg / m 3 to 240 kg / m 3) The density of such foam products is more fully described by Stockdopole and Welsh in "Encyclopedia of Polymer Science and Engineering", Volume 16, pages 193 - 205, John Wiley & Sons, 1989, which reference is hereby incorporated by reference.

[0132] Examples

[0133] The present disclosure is further defined in the following examples. It should be understood that these examples, while indicating preferred embodiments, are given by way of illustration only. From the above discussion and these examples, those skilled in the art can determine the preferred features and make various changes and modifications without departing from the spirit and scope of the invention to adapt it to various uses and conditions.

[0134] The formulations of the examples were prepared using the following components:

[0135] The polyol was PS - 2352, which is an aromatic polyester polyol available from Stepan Company.

[0136] The stabilizer was B 8871, which is a modified silicone stabilizer available from Evonik Industries, AG.

[0137] The amine catalyst was 5, which is a tertiary amine catalyst available from Evonik Industries, AG.

[0138] The metal catalyst was K - 15, which is a potassium - based catalyst available from Evonik Industries, AG.

[0139] The flame retardant was TCPP.

[0140] The isocyanate was PAPI - 27, which is an MDI - containing polymethylene polyphenyl polyisocyanate available from DowDuPont Chemical Company.

[0141] Example 1. General Preparation of A-Side and B-Side Compositions

[0142] Weigh the components on the B side on a mass balance as the masterbatch and mix them together in a 1 L plastic beaker, excluding the blowing agent. Then divide the masterbatch equally among three separate 1 L beakers, and then add the blowing agent and mix until completely incorporated. Add the blowing agents in the order of decreasing solubility in the B-side system (e.g., first add HCFO-1233zd-E, then add isopentane, and finally add HFO-1336mzz-E). Weigh the isocyanate (A-side), mainly PAPI 27, in a 500 mL plastic beaker, which has an additional 15 wt% for sufficient headspace pouring, and pour it into the B-side mixture. Place the A + B mixture in a mixing head and mix at 4000 rpm for 3 s. After mixing, quickly pour the mixed A + B solution into a wax-coated cardboard box and start the timer. Leave the resulting foam under the fume hood for 24 h to complete the polyurethane reaction. Then cut the foam into 8” x 8” x 1.5” blocks. Test the thermal conductivity of the foam blocks using a hot flow meter according to ASTM C-518.

[0143] Example 2. Ternary Blends of Blowing Agents of HFO-1336mzz-E, Isopentane, and HCFO-1233zd-E

[0144] Table 1 shows a summary of the formulations (A-side and B-side formulations) of a ternary blowing agent blend containing HFO-1336mzz-E, isopentane, and HCFO-1233zd-E, which were prepared according to the general procedure described in Example 1.

[0145] Table 1 .

[0146] Ingredients (pphp Polyol) Control 2A 2B 2C 2D Polyol 100 100 100 100 100 Surfactant 3 3 3 3 3 Amine Catalyst 0.40 0.40 0.40 0.40 0.40 Metal Catalyst 3 3 3 3 3 Flame Retardant 10 10 10 10 10 Water 0.40 0.40 0.40 0.40 0.40 B-Side without Blowing Agent 116.8 116.8 116.8 116.8 116.8 HFO-1336mzz-E 0 2.09 3.14 4.18 6.27 Isopentane 2.09 2.09 2.09 4.18 5.23 HCFO-1233zd-E 18.82 16.73 15.68 12.55 9.41 Total B-Side with Blowing Agent 137.71 137.71 137.71 137.71 137.71 Isocyanate (A-Side) 197.82 197.82 197.82 197.82 197.82

[0147] By weight percentage (% by weight) of the total amount of blowing agent, the blowing agent components in Table 1 are as follows:

[0148] Control Preparation : 90 wt% HCFO-1233zd-E, 10 wt% isopentane, and 0 wt% HFO-1336mzz-E relative to the total mass of the blowing agent present in the B side.

[0149] Preparation 2A : 80 wt% HCFO-1233zd-E, 10 wt% isopentane, and 10 wt% HFO-1336mzz-E relative to the total mass of the blowing agent present in the B side.

[0150] Preparation 2B : 75 wt% HCFO-1233zd-E, 10 wt% isopentane, and 15 wt% HFO-1336mzz-E relative to the total mass of the blowing agent present in the B side.

[0151] Preparation 2C: 60 wt% HCFO-1233zd-E, 20 wt% isopentane, and 20 wt% HFO-1336mzz-E, relative to the total mass of the blowing agent present in Side B.

[0152] Preparation 2D : 45 wt% HCFO-1233zd-E, 25 wt% isopentane, and 35 wt% HFO-1336mzz-E, relative to the total mass of the blowing agent present in Side B.

[0153] After testing, the data values were compiled for analysis and are shown in Table 2 below and Figure 1 herein.

[0154] Table 2 .

[0155]

[0156] The maximum k-factor performance was achieved in Foam 2B prepared with a blowing agent composition containing 75 wt% HCFO-1233zd-E, 10 wt% isopentane, and 15 wt% HFO-1336mzz-E, relative to the total mass of the blowing agent present in Side B.

[0157] Theoretical calculations provided information on where these improvement regions might be located. Figure 2 Shown are the ternary azeotrope predictions from the calculations, where the darker colors indicate stronger azeotrope regions. Figure 2 Illustrates the regions explored in the above foam synthesis. Notably, the best performance does not directly coincide with the predicted azeotrope. Without being bound by theory, it is believed that other factors are involved, leading to unexpected behavior.

[0158] When we replaced 1233zd with 1336E, a decrease in thermal conductivity was observed and continued to improve up to about 15 wt%. At about 20% of 1336E, the trend reversed and the thermal conductivity increased. This behavior was unexpected because the vapor thermal conductivity of 1336E is greater than that of 1233zd, and based on the gas thermal conductivity, an increase in thermal conductivity was expected when 1336E replaced 1233zd.

[0159] Example 3. Ternary Blends of Blowing Agents of HFO-1336mzz-E, Cyclopentane, and HCFO-1233zd-E

[0160] Table 3 shows a summary of the formulations (Side A and Side B formulations) of ternary blowing agent blends containing HFO-1336mzz-E, cyclopentane, and HCFO-1233zd-E, which were prepared according to the general procedure described in Example 1.

[0161] Table 3 .

[0162] Ingredients (pphp Polyol) Control 3A 3B 3C 3D Polyol 100 100 100 100 100 Surfactant 3 3 3 3 3 Amine Catalyst 0.40 0.40 0.40 0.40 0.40 Metal Catalyst 3 3 3 3 3 Flame Retardant 10 10 10 10 10 Water 0.40 0.40 0.40 0.40 0.40 B-Side without Blowing Agent 116.8 116.8 116.8 116.8 116.8 HFO-1336mzz-E 0 2.09 3.14 4.18 6.27 Cyclopentane 2.09 2.09 2.09 4.18 5.23 HCFO-1233zd-E 18.82 16.73 15.68 12.55 9.41 Total B-Side with Blowing Agent 137.71 137.71 137.71 137.71 137.71 Isocyanate (A-Side) 197.82 197.82 197.82 197.82 197.82

[0163] Based on the weight percentage (% by weight) of the total amount of blowing agent, the blowing agent components in Table 3 are as follows:

[0164] Control Preparation : 90% by weight of HCFO-1233zd-E, 10% by weight of cyclopentane, and 0% by weight of HFO-1336mzz-E, relative to the total mass of the blowing agent present in Side B.

[0165] Preparation 3A : 80% by weight of HCFO-1233zd-E, 10% by weight of cyclopentane, and 10% by weight of HFO-1336mzz-E, relative to the total mass of the blowing agent present in Side B.

[0166] Preparation 3B : 75% by weight of HCFO-1233zd-E, 10% by weight of cyclopentane, and 15% by weight of HFO-1336mzz-E, relative to the total mass of the blowing agent present in Side B.

[0167] Preparation 3C : 70% by weight of HCFO-1233zd-E, 10% by weight of cyclopentane, and 20% by weight of HFO-1336mzz-E, relative to the total mass of the blowing agent present in Side B.

[0168] Preparation 3D : 65% by weight of HCFO-1233zd-E, 10% by weight of cyclopentane, and 25% by weight of HFO-1336mzz-E, relative to the total mass of the blowing agent present in Side B.

[0169] After testing, the data values were compiled for analysis and are shown in Table 4 below and Figure 3 in.

[0170] Table 4 .

[0171]

[0172] It was found that the maximum k-factor performance was achieved in Foam 3B prepared using a blowing agent component containing 75% by weight of HCFO-1233zd-E, 10% by weight of cyclopentane, and 15% by weight of HFO-1336mzz-E, relative to the total mass of the blowing agent present in Side B.

[0173] Theoretical calculations provided information on where these improvement regions might be located. Figure 4 The ternary azeotrope predictions from the calculations are shown, where the darker colors indicate stronger azeotrope regions. Figure 4Illustrates the region explored for the above foam synthesis. It is noted that the optimal performance does not directly coincide with the predicted azeotrope. Without being bound by theory, it is believed that other factors are involved, leading to unexpected behavior.

[0174] Other Embodiments

[0175] 1. In some embodiments, the present application provides a method of forming a foam, the method comprising reacting or extruding a foamable composition under conditions effective to form a foam, wherein the foamable composition comprises a blowing agent component, and the blowing agent component comprises:

[0176] (i) from about 5 wt% to about 40 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-

[0177] E);

[0178] (ii) from about 8 wt% to about 30 wt% of a C5 hydrocarbon; and

[0179] (iii) from about 40 wt% to about 85 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0180] 2. The method according to embodiment 1, wherein the blowing agent component comprises from about 10 wt%

[0181] to about 35 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0182] 3. The method according to embodiment 1, wherein the blowing agent component comprises from about 10 wt%

[0183] to about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0184] 4. The method according to any one of embodiments 1 to 3, wherein the blowing agent component comprises from about 10 wt% to about 25 wt% of a C5 hydrocarbon.

[0185] 5. The method according to any one of embodiments 1 to 3, wherein the blowing agent component comprises from about 8 wt% to about 12 wt% of a C5 hydrocarbon.

[0186] 6. The method according to any one of embodiments 1 to 5, wherein the C5 hydrocarbon is selected from n-pentane, isopentane, and cyclopentane.

[0187] 7. The method according to any one of embodiments 1 to 5, wherein the C5 hydrocarbon is cyclopentane.

[0188] 8. The method according to any one of embodiments 1 to 5, wherein the C5 hydrocarbon is isopentane.

[0189] 9. The method according to any one of embodiments 1 to 8, wherein the blowing agent component

[0190] comprises from about 65% to about 80% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0191] 10. The method according to any one of embodiments 1 to 8, wherein the blowing agent component

[0192] comprises from about 45% to about 80% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0193] 11. The method according to embodiment 1, wherein the blowing agent component comprises:

[0194] (i) from about 10% to about 25% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-

[0195] E);

[0196] (ii) about 10% by weight of cyclopentane; and

[0197] (iii) from about 65% to about 80% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0198] 12. The method according to embodiment 1 or 11, wherein the method forms a foam having a K-factor of about

[0199] 0.135 Btu in / ft 2 h °C or less at 24 °C.

[0200] 13. The method according to embodiment 1 or 11, wherein the method forms a foam having a K-factor of from about 0.130 Btu in / ft 2 h °C to about 0.135 Btu in / ft 2 h °C at 24 °C.

[0201] 14. The method according to embodiment 1 or 11, wherein the method forms a foam having a K-factor of about

[0202] 0.124 Btu in / ft 2 h °C or less at 10 °C.

[0203] 15. The method according to embodiment 1 or 11, wherein the method forms a foam having a K-factor of about 0.118 Btu in / ft 2 h °C to about 0.124 Btu in / ft 2 h °C at 10 °C.

[0204] 16. The method according to embodiment 1 or 11, wherein the method forms a foam having a K-factor of about 0.118 Btu in / ft 2 h °C or less at about -6.7 °C.

[0205] 17. The method according to embodiment 1 or 11, wherein the method forms a foam having a K-factor of about 0.110 Btu in / ft 2 h °C to about 0.118 Btu in / ft 2 h °C at -6.7 °C.

[0206] 18. The method according to embodiment 1 or 11, wherein the method forms a foam having a K-factor of about 0.135 Btu in / ft 2 h °C or less at about 24 °C, about 0.124 Btu in / ft 2 h °C or less at about 10 °C, and about 0.118 Btu in / ft 2 h °C or less at about -6.7 °C.

[0207] 19. The method according to embodiment 1 or 11, wherein the method forms a foam having a K-factor of about 0.130 Btu in / ft 2 h °C to about 0.135 Btu in / ft 2 h °C at 10 °C, about 0.118 Btu in / ft 2 h °C to about 0.124 Btu in / ft 2 h °C, and at -6.7 °C about

[0208] 0.110 Btu in / ft 2 h °C to about 0.118 Btu in / ft 2 h °C.

[0209] 20. The method according to any one of embodiments 1 and 11 to 19, wherein the method forms a foam having a cream time of about 20 seconds to about 30 seconds.

[0210] 21. The method according to any one of embodiments 1 and 11 to 20, wherein the method forms a foam having a gelling time of about 50 seconds to about 65 seconds.

[0211] 22. The method according to any one of embodiments 1 and 11 to 21, wherein the method forms a foam having a non-stick time of from about 120 seconds to about 135 seconds.

[0212] 23. The method according to any one of embodiments 1 and 11 to 22, wherein the method forms a foam having a density of from about 2.90 pcf to about 3.10 pcf.

[0213] 24. The method according to any one of embodiments 1 and 11 to 23, wherein the method forms a foam having a closed cell content of from about 90% to about 95%.

[0214] 25. The method according to any one of embodiments 1 and 11 to 24, wherein the blowing agent composition comprises:

[0215] about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 65 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0216] about 20 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 70 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0217] about 15 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 75 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0218] about 10 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10

[0219] wt% of cyclopentane, and about 80 wt% of E-CHCl=CHCF3 (HCFO-

[0220] 1233zd(E)).

[0221] 26. The method according to embodiment 1, wherein the blowing agent composition comprises:

[0222] (i) from about 10 wt% to about 30 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-

[0223] E);

[0224] (ii) from about 10 wt% to about 25 wt% of isopentane; and

[0225] (iii) from about 45 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-

[0226] 1233zd(E)).

[0227] 27. The method according to embodiment 1 or 26, wherein the method forms a foam having a K-factor of about

[0228] 0.142 Btu in / ft 2 h °C or less at about 24 °C.

[0229] 28. The method according to embodiment 1 or 26, wherein the method forms a foam having a K-factor of from about

[0230] 0.140 Btu in / ft 2 h °C to about 0.139 Btu in / ft 2 h °C at 24 °C.

[0231] 29. The method according to embodiment 1 or 26, wherein the method forms a foam having a K-factor of about

[0232] 0.129 Btu in / ft 2 h °C or less at about 10 °C.

[0233] 30. The method according to embodiment 1 or 26, wherein the method forms a foam having a K-factor of from about

[0234] 0.127 Btu in / ft 2 h °C to about 0.129 Btu in / ft 2 h °C at 10 °C.

[0235] 31. The method according to embodiment 1 or 26, wherein the method forms a foam having a K-factor of about

[0236] 0.120 Btu in / ft 2 h °C or less at about -6.7 °C.

[0237] 32. The method according to embodiment 1 or 26, wherein the method forms a foam having a K-factor of from about

[0238] 0.116 Btu in / ft 2 h °C to about 0.120 Btu in / ft 2 h °C at -6.7 °C.

[0239] 33. The method according to embodiment 1 or 26, wherein the method forms a foam having at about

[0240] 0.142 Btu in / ft at about 24 °C 2 h °C or less, about 0.129 Btu at about 10 °C

[0241] in / ft 2 h °C or less, and about 0.120 Btu in / ft at about -6.7 °C 2 h °C or less of K-

[0242] factor foam.

[0243] 34. Method V, wherein the method forms a foam having from about 0.140 Btu in / ft at 24 °C 2 h °C to about

[0244] 0.139 Btu in / ft 2 h °C, about 0.127 Btu in / ft at 10 °C 2 h °C to about 0.129 Btu

[0245] in / ft 2 h °C, and about 0.116 Btu in / ft at -6.7 °C 2 h °C to about 0.120 Btu in / ft 2 h °C of K-factor foam.

[0246] 35. The method according to any one of embodiments 1 and 26 to 34, wherein the method forms a foam having a cream time of about 5 seconds to about 12 seconds.

[0247] 36. The method according to any one of embodiments 1 and 26 to 35, wherein the method forms a foam having a gelling time of about 35 seconds to about 45 seconds.

[0248] 37. The method according to any one of embodiments 1 and 26 to 36, wherein the method forms a foam having a non-stick time of about 90 seconds to about 100 seconds.

[0249] 38. The method according to any one of embodiments 1 and 26 to 37, wherein the method forms a foam having a density of about 2.53 pcf to about 2.56 pcf.

[0250] 39. The method according to any one of embodiments 1 and 26 to 38, wherein the method forms a foam having a closed cell content of about 96% to about 99%.

[0251] 40. The method according to any one of embodiments 1 and 26 to 39, wherein the blowing agent component comprises:

[0252] About 30 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 wt% of isopentane, and about 45 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0253] About 20 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 20 wt% of isopentane, and about 60 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0254] About 15 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of isopentane, and about 75 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0255] About 10 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of isopentane, and about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0256] 41. The method according to any one of embodiments 1 to 40, wherein the foamable composition further comprises one or more additional components selected from at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent.

[0257] 42. The method according to any one of embodiments 1 to 40, wherein the foamable composition comprises at least one polyol.

[0258] 43. The method according to embodiment 41 or 42, wherein the polyol is a polyester polyol.

[0259] 44. The method according to any one of embodiments 1 to 40, wherein the foamable composition comprises at least one catalyst.

[0260] 45. The method according to any one of embodiments 1 to 40, wherein the foamable composition comprises a metal catalyst and an amine catalyst.

[0261] 46. The method according to any one of embodiments 1 to 40, wherein the foamable composition comprises a surfactant.

[0262] 47. The method according to embodiment 41 or 46, wherein the surfactant is a silicone surfactant.

[0263] 48. The method according to any one of embodiments 1 to 40, wherein the foamable composition comprises water.

[0264] 49. The method according to any one of embodiments 1 to 40, wherein the foamable composition comprises a flame retardant.

[0265] 50. The method according to any one of embodiments 1 to 40, wherein the foamable composition comprises a nucleating agent.

[0266] 51. The method according to any one of embodiments 1 to 40 and 42 to 49, wherein the method is carried out in the absence of a nucleating agent.

[0267] 52. The method according to any one of embodiments 1 to 51, wherein the foam is a spray foam.

[0268] 53. The method according to any one of embodiments 1 to 52, wherein the foam is a thermoset foam.

[0269] 54. The method according to any one of embodiments 1 to 53, wherein the foam is a polyurethane foam or a polyisocyanurate foam.

[0270] 55. The method according to any one of embodiments 1 to 54, wherein the foam is a closed-cell foam.

[0271] 56. The method according to embodiment 1, wherein the foamable composition comprises a blowing agent component, the blowing agent component comprising:

[0272] about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 65 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0273] about 20 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 70 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0274] about 15 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 75 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0275] About 10 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); and

[0276] At least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant.

[0277] 57. The method according to embodiment 1, wherein the foamable composition comprises a blowing agent component, and the blowing agent component comprises:

[0278] About 30 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 wt% of isopentane, and about 45 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0279] About 20 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 20 wt% of isopentane, and about 60 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0280] About 15 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of isopentane, and about 75 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or

[0281] About 10 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of isopentane, and about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); and

[0282] At least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant.

[0283] 58. A foamable composition, the foamable composition comprising a blowing agent component, wherein the

[0284] blowing agent component comprises:

[0285] (i) About 5 wt% to about 40 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-

[0286] E);

[0287] (ii) About 8 wt% to about 30 wt% of C5 hydrocarbon; and

[0288] (iii) from about 40 wt% to about 85 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0289] 59. A foam prepared by the method according to any one of embodiments 1 to 57.

[0290] 60. The foam according to embodiment 59, wherein the foam is a closed-cell polyisocyanurate foam.

[0291] 61. The foam according to embodiment 59, wherein the foam is a closed-cell polyurethane foam.

[0292] It should be understood that although the present invention has been described in connection with the detailed description of the present invention, the foregoing description is intended to illustrate rather than limit the scope of the present invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. Those of ordinary skill in the art to which the present invention pertains should understand that any feature described herein with respect to any particular aspect and / or embodiment of the present invention can be combined with one or more features of any other aspect and / or embodiment of the present invention described herein, with appropriate modifications to ensure compatibility of the combination. Such combinations are considered to be part of the present invention contemplated by the present disclosure.

Claims

1. A method of forming a foam, the method comprising reacting or extruding a foamable composition under conditions effective to form a foam, wherein the foamable composition comprises a blowing agent component, and the blowing agent component comprises: from about 5 wt% to about 40 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E); from about 8 wt% to about 30 wt% of C5 hydrocarbons; and from about 40 wt% to about 85 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

2. The method according to claim 1, wherein the blowing agent component comprises from about 10 wt% to about 35 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E).

3. The method according to claim 1, wherein the blowing agent component comprises from about 10 wt% to about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E).

4. The method according to claim 1, wherein the blowing agent component comprises from about 10 wt% to about 25 wt% of C5 hydrocarbons.

5. The method according to claim 1, wherein the blowing agent component comprises from about 8 wt% to about 12 wt% of C5 hydrocarbons.

6. The method according to claim 1, wherein the C5 hydrocarbons are selected from n-pentane, isopentane, and cyclopentane.

7. The method according to claim 1, wherein the C5 hydrocarbon is cyclopentane.

8. The method according to claim 1, wherein the C5 hydrocarbon is isopentane.

9. The method according to claim 1, wherein the blowing agent component comprises from about 65 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E).

10. The method according to claim 1, wherein the blowing agent component comprises from about 45 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E).

11. The method according to claim 1, wherein the blowing agent component comprises: from about 10 wt% to about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E); about 10 wt% of cyclopentane; and from about 65 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO- 1233zd(E)).

12. The method according to claim 11, wherein the method forms a foam having a K-factor of about 0.135 Btu in / ft 2 h °C or less at about 24 °C.

13. The method according to claim 11, wherein the method forms a foam having a K-factor of from about 0.130 Btu in / ft 2 h °C to about 0.135 Btu in / ft 2 h °C.

14. The method according to claim 11, wherein the method forms a foam having a K-factor of about 0.124 Btu in / ft 2 h °C or less at about 10 °C.

15. The method according to claim 11, wherein the method forms a foam having a K-factor of from about 0.118 Btu in / ft 2 h °C to about 0.124 Btu in / ft 2 h °C.

16. The method according to claim 11, wherein the method forms a foam having a K-factor of about 0.118 Btuin / ft 2 h℃ or less at about -6.7 °C.

17. The method according to claim 11, wherein the method forms a foam having a K-factor of from about 0.110 Btu in / ft 2 h °C to about 0.118 Btu in / ft 2 h °C.

18. The method according to claim 11, wherein the method forms a foam having a K-factor of about 0.135 Btu in / ft 2 h °C or less at about 24 °C, about 0.124 Btu in / ft 2 h °C or less at about 10 °C, and about 0.118 Btu in / ft 2 h °C or less at about -6.7 °C.

19. The method according to claim 11, wherein the method forms a foam having a K-factor of from about 0.130 Btu in / ft 2 h °C to about 0.135 Btu in / ft 2 h °C, from about 0.118 Btu in / ft 2 h °C to about 0.124 Btu in / ft 2 h °C at 10 °C, and from about 0.110 Btu in / ft 2 h °C to about 0.118 Btu in / ft 2 h °C.

20. The method according to claim 11, wherein the method forms a foam having a cream time of from about 20 seconds to about 30 seconds.

21. The method according to claim 11, wherein the method forms a foam having a gelling time of from about 50 seconds to about 65 seconds.

22. The method according to claim 11, wherein the method forms a foam having a non-stick time of from about 120 seconds to about 135 seconds.

23. The method according to claim 11, wherein the method forms a foam having a density of from about 2.90 pcf to about 3.10 pcf.

24. The method according to claim 11, wherein the method forms a foam having a closed cell content of from about 90% to about 95%.

25. The method according to claim 1, wherein the blowing agent component comprises: about 25 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 65 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or about 20 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 70 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or about 15 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 75 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or about 10 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 wt% of cyclopentane, and about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

26. The method according to claim 1, wherein the blowing agent component comprises: about 10 wt% to about 30 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E); about 10 wt% to about 25 wt% of isopentane; and about 45 wt% to about 80 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)).

27. The method according to claim 26, wherein the method forms a foam having a K-factor of about 0.142 Btu in / ft 2 h °C or less at about 24 °C.

28. The method according to claim 26, wherein the method forms a foam having a K-factor of from about 0.140 Btu in / ft 2 h °C to about 0.139 Btu in / ft 2 h °C.

29. The method according to claim 26, wherein the method forms a foam having a K-factor of about 0.129 Btu in / ft 2 h °C or less at about 10 °C.

30. The method according to claim 26, wherein the method forms a foam having a K-factor of from about 0.127 Btu in / ft 2 h °C to about 0.129 Btu in / ft 2 h °C.

31. The method according to claim 26, wherein the method forms a foam having a K-factor of about 0.120 Btu in / ft 2 h °C or less at about -6.7 °C.

32. The method according to claim 26, wherein the method forms a foam having a K-factor of from about 0.116 Btu in / ft 2 h °C to about 0.120 Btu in / ft 2 h °C.

33. The method according to claim 26, wherein the method forms a foam having a K-factor of about 0.142 Btu in / ft 2 h °C or less at about 24 °C, about 0.129 Btu in / ft 2 h °C or less at about 10 °C, and about 0.120 Btu in / ft 2 h °C or less at about -6.7 °C.

34. The method according to claim 26, wherein the method forms a foam having a K-factor of from about 0.140 Btu in / ft 2 h °C to about 0.139 Btu in / ft 2 h °C, from about 0.127 Btu in / ft 2 h °C to about 0.129 Btu in / ft 2 h °C at 10 °C, and from about 0.116 Btu in / ft 2 h °C to about 0.120 Btu in / ft 2 h °C.

35. The method according to claim 26, wherein the method forms a foam having a cream time of about 5 seconds to about 12 seconds.

36. The method according to claim 26, wherein the method forms a foam having a gelling time of about 35 seconds to about 45 seconds.

37. The method according to claim 26, wherein the method forms a foam having a non-stick time of about 90 seconds to about 100 seconds.

38. The method according to claim 26, wherein the method forms a foam having a density of about 2.53 pcf to about 2.56 pcf.

39. The method according to claim 26, wherein the method forms a foam having a closed cell content of about 96% to about 99%.

40. The method according to claim 1, wherein the blowing agent component comprises: about 30 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 wt% of isopentane, and about 45 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or about 20 wt% of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 20 wt% of isopentane, and about 60 wt% of E-CHCl=CHCF3 (HCFO-1233zd(E)); or About 15% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10% by weight of isopentane, and about 75% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or About 10% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10% by weight of isopentane, and about 80% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)).

41. The method according to claim 1, wherein the foamable composition further comprises one or more additional components selected from at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent.

42. The method according to claim 18, wherein the foamable composition comprises at least one polyol.

43. The method according to claim 19, wherein the polyol is a polyester polyol.

44. The method according to claim 18, wherein the foamable composition comprises at least one catalyst.

45. The method according to claim 23, wherein the foamable composition comprises a metal catalyst and an amine catalyst.

46. The method according to claim 18, wherein the foamable composition comprises a surfactant.

47. The method according to claim 25, wherein the surfactant is a silicone surfactant.

48. The method according to claim 18, wherein the foamable composition comprises water.

49. The method according to claim 18, wherein the foamable composition comprises a flame retardant.

50. The method according to claim 18, wherein the foamable composition comprises a nucleating agent.

51. The method according to claim 3, wherein the method is carried out in the absence of a nucleating agent.

52. The method according to claim 1, wherein the foam is a spray foam.

53. The method according to claim 3, wherein the foam is a thermoset foam.

54. The method according to claim 3, wherein the foam is a polyurethane foam or a polyisocyanurate foam.

55. The method according to claim 3, wherein the foam is a closed-cell foam.

56. The method according to claim 1, wherein the foamable composition comprises a blowing agent component, the blowing agent component comprising: About 25% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10% by weight of cyclopentane, and about 65% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or About 20% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10% by weight of cyclopentane, and about 70% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or About 15% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10% by weight of cyclopentane, and about 75% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or About 10% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10% by weight of cyclopentane, and about 80% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); and At least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant.

57. The method according to claim 1, wherein the blowing agent component comprises:[[]] About 30% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25% by weight of isopentane, and about 45% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or About 20% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 20% by weight of isopentane, and about 60% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or About 15% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10% by weight of isopentane, and about 75% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); or About 10% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10% by weight of isopentane, and about 80% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)); and At least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant.

58. A foamable composition, the foamable composition comprising a blowing agent component, wherein the blowing agent component comprises:[[]] About 5% to about 40% by weight of E-CF3CH=CHCF3 (HFO-1336mzz-E); About 8% to about 30% by weight of C5 hydrocarbon; and About 40% to about 85% by weight of E-CHCl=CHCF3 (HCFO-1233zd(E)).

59. A foam prepared by the method according to claim 1.

60. The foam according to claim 59, wherein the foam is a closed-cell polyisocyanurate foam.

61. The foam according to claim 59, wherein the foam is a closed-cell polyurethane foam.

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