Process for preparing foams from ternary blowing agents

Abstract

The present application relates to processes for preparing foams from compositions including a ternary blowing agent component. Foamable compositions and foams prepared according to the processes provided herein are also disclosed.

Description

[Technical Field]

[0001] The present invention relates to a process for preparing foams from compositions containing a ternary blowing agent component. [Background technology]

[0002] Closed-cell polyisocyanate-based foams are widely used for thermal insulation purposes, for example, in the construction of buildings and the manufacture of energy-efficient appliances. In the construction industry, polyurethane (polyisocyanurate) boards are used in roofing and siding for their thermal insulation and load-bearing properties. Injection and spray polyurethane foams are widely used in a variety of applications, including insulating roofing, insulating large structures such as storage tanks, insulating appliances such as refrigerators and freezers, insulating refrigerated trucks and rail cars, and the like.

[0003] All of these various types of polyurethane foams require a blowing (expanding) agent for their production. Thermal insulating foams rely on the use of halocarbon blowing agents not only to expand the polymer but also to provide low vapor thermal conductivity, a very important characteristic of thermal insulating value. Historically, polyurethane foams have used chlorofluorocarbons (CFCs, e.g., CFC-11, trichlorofluoromethane), hydrochlorofluorocarbons (HCFCs, e.g., HCFC-141b, 1,1-dichloro-1-fluoroethane), and hydrofluorocarbons (HFCs, e.g., HFC-245fa, HFC-365mfc) as their primary blowing agents.

[0004] CFCs generally produce foams with good thermal insulation, low flammability, and excellent dimensional stability. However, despite these advantages, CFCs have gained a bad reputation due to the speculation that chlorine-containing molecules play a role in the depletion of stratospheric ozone. Furthermore, the production and use of CFCs is regulated by the Montreal Protocol. HCFCs have been proposed as replacements for CFCs and are currently used as blowing agents in foams. However, HCFCs have also been shown to contribute to the depletion of stratospheric ozone, and as a result, their use is also under scrutiny. Widespread use of HCFCs is scheduled for eventual phaseout under the Montreal Protocol. Summary of the Invention [Means for solving the problem]

[0005] This application relates, inter alia, to a process for forming a foam, comprising reacting or extruding a foamable composition under conditions effective to form a foam, wherein the blowing agent component comprises: about 5 to about 40 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 8 to about 30 weight percent C5 hydrocarbons; and about 40 to about 85 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0006] The present application relates to a foam foaming composition comprising a blowing agent component, about 5 to about 40 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 8 to about 30 weight percent C5 hydrocarbons; and about 40 to about 85 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0007] The present application further provides foams (e.g., polyisocyanurates, or polyurethanes) prepared from the foamable compositions according to the processes described herein.

[0008] 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; other suitable methods and materials known in the art can also be used. The materials, methods, and examples are illustrative only and are 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, including definitions, will control. [Brief explanation of the drawings]

[0009] [Figure 1]

[0033] Figure 1 shows the measured thermal performance (K-factor) of 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. [Figure 2] 1 shows the calculated ternary azeotrope prediction for a blend of HFO-1336mzz-E, isopentane, and HCFO-1233ze(E). Darker colors indicate stronger azeotrope regions. [Figure 3] 1 shows the measured thermal performance (K-factor) of foams prepared from B-side compositions 3A-3D compared to a control composition, as described in Example 3. [Figure 4] 1 shows the calculated ternary azeotrope prediction for a blend of HFO-1336mzz-E, cyclopentane, and HCFO-1233ze(E). Darker colors indicate stronger azeotrope regions. DETAILED DESCRIPTION OF THE INVENTION

[0010] Polyisocyanurate (PIR) foams are a growing and important market segment in the rigid insulation industry due to their excellent thermal performance and fire classification capabilities. The primary blowing agents used in PIR panel foams are C5 hydrocarbons, such as cyclopentane, n-pentane, isopentane, or mixtures thereof. While these C5 blowing agents can provide adequate 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 for polyurethane and related foams. Furthermore, many HFOs react and decompose relatively rapidly in the atmosphere. Therefore, many HFOs have no or very low global warming potential (GWP) and do not contribute to stratospheric ozone depletion and global warming. HFOs have been shown to have improved insulation performance compared to C5 hydrocarbons, but are significantly more expensive. Therefore, there is a need to add a minimum amount of HFO to C5 hydrocarbons to maximize insulation performance improvement.

[0011] Spray polyurethane foam (SPF) is a growing and important market segment in the rigid insulation industry due to its excellent thermal performance and building envelope sealing capabilities. During application, speed and quality of the applied layer are critical to effective application and efficiency of performance parameters, including density and surface appearance. In addition, such foams are applied on-site to the building of interest under a variety of environmental conditions, including cold winter temperatures. Typical physical foam blowing agents require heat to evaporate and expand. This becomes difficult at low temperatures when polyurethane polymerization catalysis slows, reducing the sole heat source on the surface of the spray area. Therefore, providing a means to efficiently lay and apply SPF under cold conditions would benefit the industry.

[0012] A common technique for preparing closed-cell PIR and polyurethane (PUR) foams with thermal insulation performance involves the use of a binary blowing agent blend containing a hydrochlorofluoroolefin, such as HCFO-1233zd, in combination with a hydrocarbon, such as isopentane, n-pentane, or cyclopentane. The present application discloses ternary blowing agent blends containing HCFO-1233zd in combination with a C5 hydrocarbon and a hydrofluoroolefin component (HFO-1336mzz-E), and it has been unexpectedly discovered that the blends described herein exhibit synergistic results, providing foams with improved thermal insulation performance and long-lasting effectiveness.

[0013] Definitions and Abbreviations As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent in such process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or," not an exclusive "or." For example, a 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).

[0014] As used herein, the term "consisting essentially of" is used to define compositions, methods, and compositions that include materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention, particularly the mechanism of action for achieving any desired result of the inventive process. The terms "consists essentially of" or "consisting essentially of" occupy a middle ground between "comprising" and "consisting of."

[0015] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that a different meaning is intended.

[0016] As used herein, the term "about" is meant to account for variation due to experimental error (e.g., plus or minus about 10% of the stated value). All measurements reported herein are understood to be modified by the term "about," unless otherwise specified, regardless of whether the term "about" is explicitly used.

[0017] As used herein, "C n The term "hydrocarbon" refers to a saturated hydrocarbon group having n carbons, which may be linear or branched.

[0018] When an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of upper and / or lower preferred values, this is to be understood as specifically disclosing all ranges formed from any pairing of any upper range value or preferred upper value and any lower range value or preferred lower value, whether or not the ranges are separately disclosed. When a range of numerical values ​​is recited herein, unless otherwise indicated, the range is intended to include its endpoints, and to include all integers and fractions within the range.

[0019] The following abbreviations may be used throughout this application: CFCs: Chlorofluorocarbons Cp: ​​Cyclopentane GWP: Global Warming Potential HCFO: Hydrochlorofluoroolefin HFC: Hydrofluorocarbon HFO: Hydrofluoroolefin HFO-1336mzz-E or 1336mzz(E):E-CF3CH=CHCF3 HCFO-1233zd(E) or 1233zd(E):E-CHCl=CHCF3 pcf: pounds force per cubic foot PIR: Polyisocyanurate pphp: parts per 100 parts of polyol PUR: Polyurethane SPF: Spray polyurethane foam TCPP: Tris(1-chloro-2-propyl) phosphate wt%: weight percent

[0020] Foamable composition and process for preparing foams In some embodiments, the present application provides a foamable composition comprising a blowing agent component, the blowing agent component comprising E-CFCH=CHCF (HFO-1336mzz-E), a C hydrocarbon, and E-CHCl=CHCF (HCFO-1233zd(E)). In some embodiments, the foamable compositions provided herein are useful in processes for forming foams.

[0021] In some embodiments, the blowing agent component is from about 5 to about 40 weight percent E-CFCH=CHCF(HFO-1336mzz-E), e.g., from about 5 to about 35 weight percent, from about 5 to about 30 weight percent, from about 5 to about 25 weight percent, from about 5 to about 20 weight percent, from about 5 to about 15 weight percent, from about 5 to about 10 weight percent, from about 10 to about 40 weight percent, from about 10 to about 35 weight percent, from about 10 to about 30 weight percent, from about 10 to about 25 weight percent, from about 10 to about 20 weight percent, from about 10 to about 15 weight percent, from about 15 to about 40 weight percent. about 15 to about 35 weight percent, about 15 to about 30 weight percent, about 15 to about 25 weight percent, about 15 to about 20 weight percent, about 20 to about 40 weight percent, about 20 to about 35 weight percent, about 20 to about 30 weight percent, about 20 to about 25 weight percent, about 25 to about 40 weight percent, about 25 to about 35 weight percent, about 25 to about 30 weight percent, about 30 to about 40 weight percent, about 30 to about 35 weight percent, or about 30 to about 40 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0022] In some embodiments, the blowing agent component comprises from about 10 to about 35 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises from about 10 to about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises from about 10 to about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0023] In some embodiments, the blowing agent component comprises about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 20 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 15 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 10 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0024] In some embodiments, the blowing agent component comprises about 8 to about 30 weight percent C5 hydrocarbons, e.g., about 8 to about 25 weight percent, about 8 to about 20 weight percent, about 8 to about 15 weight percent, about 8 to about 10 weight percent, about 10 to about 30 weight percent, about 10 to about 25 weight percent, about 10 to about 20 weight percent, about 10 to about 15 weight percent, about 15 to about 30 weight percent, about 15 to about 25 weight percent, about 15 to about 20 weight percent, about 20 to about 30 weight percent, about 20 to about 25 weight percent, or about 25 to about 30 weight percent C5 hydrocarbons.

[0025] In some embodiments, the blowing agent component comprises from about 10 to about 25 weight percent C5 hydrocarbons, hi some embodiments, the blowing agent component comprises from about 8 to about 12 weight percent C5 hydrocarbons.

[0026] In some embodiments, the C5 hydrocarbon is selected from n-pentane, isopentane, and cyclopentane.

[0027] In some embodiments, the C5 hydrocarbon is cyclopentane. In some embodiments, the blowing agent component comprises about 8 to about 12 weight percent cyclopentane. In some embodiments, the blowing agent component comprises about 10 weight percent cyclopentane.

[0028] In some embodiments, the C5 hydrocarbon is isopentane. In some embodiments, the blowing agent component comprises about 10 to about 25 weight percent isopentane. In some embodiments, the blowing agent component comprises about 25 weight percent isopentane. In some embodiments, the blowing agent component comprises about 20 weight percent isopentane. In some embodiments, the blowing agent component comprises about 10 weight percent isopentane.

[0029] In some embodiments, the blowing agent component is from about 40 to about 85 weight percent E-CHCl=CHCF3(HCFO-1233zd(E), e.g., from about 40 to about 80 weight percent, from about 40 to about 75 weight percent, from about 40 to about 70 weight percent, from about 40 to about 65 weight percent, from about 40 to about 60 weight percent, from about 40 to about 55 weight percent, from about 40 to about 50 weight percent, from about 40 to about 45 weight percent, from about 4 5 to about 85 weight percent, about 45 to about 80 weight percent, about 45 to about 75 weight percent, about 45 to about 70 weight percent, about 45 to about 65 weight percent, about 45 to about 60 weight percent, about 45 to about 55 weight percent, about 45 to about 50 weight percent, about 50 to about 85 weight percent, about 50 to about 80 weight percent, about 50 to about 75 weight percent, about 50 to about 70 weight percent, about 50 to about 65 weight percent , about 50 to about 60 weight percent, about 50 to about 55 weight percent, about 55 to about 85 weight percent, about 55 to about 80 weight percent, about 55 to about 75 weight percent, about 55 to about 70 weight percent, about 55 to about 65 weight percent, about 55 to about 60 weight percent, about 60 to about 85 weight percent, about 60 to about 80 weight percent, about 60 to about 75 weight percent, about 60 to about 70 weight percent, about 60 to about 65 weight percent, about 65 to about 85 weight percent, about 65 to about 80 weight percent, about 65 to about 75 weight percent, about 65 to about 70 weight percent, about 70 to about 85 weight percent, about 70 to about 80 weight percent, about 70 to about 75 weight percent, about 75 to about 85 weight percent, about 75 to about 80 weight percent, or about 80 to about 85 weight percent E-CHCl=CHCF3(HCFO-1233zd(E)).

[0030] In some embodiments, the blowing agent component comprises from about 65 to about 80 weight percent E-CHCl=CHCF3(HCFO-1233zd(E). In some embodiments, the blowing agent component comprises from about 45 to about 80 weight percent E-CHCl=CHCF3(HCFO-1233zd(E).

[0031] In some embodiments, the blowing agent component comprises about 45 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent component comprises about 60 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent component comprises about 65 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent component comprises about 70 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent component comprises about 75 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent component comprises about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0032] In some embodiments, the blowing agent component is about 5 to about 40 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 8 to about 30 weight percent C5 hydrocarbons; and about 40 to about 85 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0033] In some embodiments, the blowing agent component is about 10 to about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 10 to about 25 weight percent C5 hydrocarbons; and about 45 to about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0034] In some embodiments, the blowing agent component is about 10 to about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 10 weight percent C5 hydrocarbons; and about 65 to about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0035] In some embodiments, the blowing agent component is about 10 to about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 10 weight percent cyclopentane; and about 65 to about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0036] In some embodiments, the blowing agent component is about 10 to about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 10 to about 25 weight percent isopentane; and about 45 to about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0037] In some embodiments, the blowing agent component is about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 20 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 70 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 15 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 75 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 10 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 20 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 20 weight percent isopentane, and about 60 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 15 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent isopentane, and about 75 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or It contains about 10 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent isopentane, and about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0038] In some embodiments, the foamable composition further comprises one or more polyols. In some embodiments, the foamable composition described herein can include one or more additives. For example, the foamable composition can further include one or more additives, including, but not limited to, catalysts, surfactants, flame retardants, stabilizers, preservatives, chain extenders, crosslinkers, water, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, nucleating agents, smoke suppressants, and pigments.

[0039] 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.

[0040] In some embodiments, the foamable composition includes at least one polyol. In some embodiments, the polyol includes any ratio of polyester polyol to polyether polyol. One or more of each polyester polyol and polyether polyol may be used. In some embodiments, the polyol includes a weight ratio of polyester polyol to polyether polyol of about 1:1 to about 2:1. In some embodiments, the polyol includes a weight ratio of polyester polyol to polyether polyol of about 1:1. In some embodiments, the polyol includes a weight ratio of polyester polyol to polyether polyol of about 1:1. In some embodiments, the polyol includes a weight ratio of polyester polyol to polyether polyol of about 1:1.

[0041] In some embodiments, the polyol is a polyester polyol. Suitable polyester polyols include those prepared by reacting a carboxylic acid and / or its derivatives or a polycarboxylic acid anhydride with a polyhydric alcohol. The polycarboxylic acid can be any of the known aliphatic, cycloaliphatic, aromatic, and / or heterocyclic polycarboxylic acids, and can be substituted (e.g., with halogen atoms) and / or unsaturated. Examples of suitable polycarboxylic acids and anhydrides include 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, maleic acid, maleic anhydride, fumaric acid, and dimer and trimer fatty acids such as oleic acid, which may be in a mixture with monomeric fatty acids. Simple polycarboxylic acid esters such as terephthalic acid dimethyl ester, terephthalic acid bisglycol, and their extracts can also be used. Polyhydric alcohols suitable for preparing polyester polyols can be aliphatic, cycloaliphatic, aromatic, and / or heterocyclic. The polyhydric alcohol may optionally contain substituents that are inert during the reaction, such as chlorine and bromine substituents, and / or may be unsaturated. Suitable amino alcohols such as monoethanolamine and diethanolamine may also be used. Examples of suitable polyhydric alcohols include ethylene glycol, propylene glycol, polyoxyalkylene glycol di(such as diethylene glycol, polyethylene glycol, dipropylene glycol, and polypropylene glycol), glycerol, and trimethylolpropane.

[0042] Other suitable polyester polyols include, but are not limited to, aromatic polyester polyols, such as those made by transesterifying polyethylene terephthalate (PET) scrap with glycols such as diethylene glycol, or those made by reacting phthalic anhydride with glycols. 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.

[0043] In some embodiments, the polyester polyol has an average molecular weight of about 400 g / mol to about 500 g / mol, e.g., 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 about 200 to about 325, e.g., about 235 to about 265, about 230 to about 250, or about 295 to about 315.

[0044] Exemplary commercially available polyester polyols include polyester polyols Stepanpol® PS-2352 (Stepan Company, Chicago, IL), Stepanpol® PS-2502A (Stepan Company, Chicago, IL), Stepanpol® PS-2412 (Stepan Company, Chicago, IL), Stepanpol® PS-2520 (Stepan Company, Chicago, IL), Stepanpol® PS-3021 (Stepan Company, Chicago, IL), Stepanpol® PS-3024 (Stepan Company, Chicago, IL), Terol® 256 (Huntsman, The Woodlands, TX), and Terol® 925 (Huntsman, The Woodlands, TX). Woodlands, TX), Terol® 563 (Huntsman, The Woodlands, TX), Terol® 649 (Huntsman, The Woodlands, TX), Terol® 1465 (Huntsman, The Woodlands, TX), Isoexter® TB-305 (COIM, West Deptford, NJ), Isoexter® TB-306 (COIM, West Deptford, NJ), Terate® HT5510 (Invista), Terate® 5232 (Invista), Terate® 5100 (Invista), Terate® 5150 (Invista), Terate® 5170 (Invista), Carpol® PES-240 (Carpenter Co., Richmond, VA), Carpol® PES-265 (Carpenter Co., Richmond, VA), Co., Richmond, VA), Carpol® PES-305 (Carpenter Co.and Carpol® PES-295 (Carpenter Co., Richmond, VA).

[0045] 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, and mixed polyethylene-propylene oxides with terminal hydroxyl groups, among others. 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 present in polyhydroxy compounds, such as, for example, glycerol, pentaerythritol, and carbohydrates, such as sorbitol, glucose, and sucrose. Suitable polyether polyols can also include aliphatic or aromatic amine-based polyols. Exemplary commercially available polyether polyols include polyether polyols JEFFOL® PPG-400 (Huntsman, The Woodlands, TX), JEFFOL® PPG-1000 (Huntsman, The Woodlands, TX), JEFFOL® FX31-240 (Huntsman, The Woodlands, TX), JEFFOL® G31-28 (Huntsman, The Woodlands, TX), JEFFOL® R-425X (Huntsman, The Woodlands, TX), JEFFOL® R-470X (Huntsman, The Woodlands, TX), JEFFOL® S-490 (Huntsman, The Woodlands, TX), JEFFOL® SG-360 (Huntsman, The Woodlands, TX), JEFFOL® SG-522 (Huntsman, The Woodlands, TX), and others. Woodlands, TX), Carpol® PGP-400 (Carpenter Co., Richmond, VA), Carpol® PGP-1000 (Carpenter Co., Richmond, VA), Carpol® GP-700 (Carpenter Co., Richmond, VA), Carpol® GP-6015 (Carpenter Co., Richmond, VA)VA), Carpol® MX-425 (Carpenter Co., Richmond, VA), Carpol® MX-470 (Carpenter Co., Richmond, VA), Carpol® GSP-355 (Carpenter Co., Richmond, VA), Carpol® GSP-520 (Carpenter Co., Richmond, VA), Carpol® SP-477 (Carpenter Co., Richmond, VA), VORANOL® 220-260 (Dow Chemical, Midland, MI), VORANOL® 220-110 (Dow Chemical, Midland, MI), VORANOL® 230-238 (Dow Chemical, Midland, MI), VORANOL® 232-027 (Dow Chemical, Midland, MI), VORANOL® 470 (Dow Chemical, Midland, MI), VORANOL® 360 (Dow Chemical, Midland, MI), VORANOL® 520 (Dow Chemical, Midland, MI), VORANOL® 391 (Dow Chemical, Midland, MI), Pluracol® P410R (BASF, Lemforde, Germany), Pluracol® P1010 (BASF, Lemforde, Germany), Pluracol® GP730 (BASF, Lemforde, Germany), Pluracol® 220 (BASF, Lemforde, Germany), Lupranol® 3422 (BASF, Lemforde, Germany), Pluracol® SG-360 (BASF, Lemforde, Germany), Pluracol® 824 (BASF, Lemforde, Germany), Pluracol® 735 (BASF, Lemforde, Germany), ARCOL® PPG-425 (Covestro, Leverkusen, Germany)Germany), ARCOL® 1000 (Covestro, Leverkusen, Germany), ARCOL® LHT-240 (Covestro, Leverkusen, Germany), MULTRANOL® 9139 (Covestro, Leverkusen, Germany), MULTRANOL® 3901 (Covestro, Leverkusen, Germany), MULTRANOL® 4034 (Covestro, Leverkusen, Germany), Poly-G® 20-265 (Monument Chemical, Indianapolis, IN), Poly-G® 20-112 (Monument Chemical, Indianapolis, IN), Poly-G® 30-240 (Monument Chemical, Indianapolis, IN), Poly-G® 85-29 (Monument Chemical, Indianapolis, IN). Poly-G® 73-490 (Monument Chemical, Indianapolis, IN), Poly-G® 74-376 (Monument Chemical, Indianapolis, IN), and Poly-G® 74-532.

[0046] In some embodiments, the polyether polyol is a medium-functionality polyether polyol. For example, the polyether polyol has a functionality of about 4. In some embodiments, the polyether polyol is sucrose / glycerin initiated. In some embodiments, the polyether polyol is a Mannich polyether polyol. As used herein, the term "Mannich polyether polyol" refers to an aromatic polyol obtained by alkoxylation with propylene oxide and / or ethylene oxide of a Mannich base obtained by the classical Mannich reaction between a phenol (e.g., phenol, p-nonylphenol), formaldehyde, and an alkanolamine (diethanolamine, diisopropanolamine, monoethanolamine, monoisopropanolamine, etc.). Examples of commercially available polyether polyols include Voranol® 490 (Dow Chemical, Midland, MI), Carpol® MX-425 (Carpenter Co., Richmond, VA), and Carpol® MX-470 (Carpenter Co., Richmond, VA).

[0047] 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.

[0048] 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.

[0049] In some embodiments, the blowing agent components described herein, including E-CFCH=CHCF (HFO-1336mzz-E), C hydrocarbons, and E-CHCl=CHCF (HCFO-1233zd(E)), are soluble in the polyol blend. In some embodiments, solubility is measured by visual evaluation.

[0050] 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 tertiary amine compounds, e.g., amine-based compounds such as 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 is about 0.1 to about 5 parts by weight per 100 parts by weight of polyol. In some embodiments, the foamable composition includes a gel catalyst, e.g., a non-nucleophilic gel 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.

[0051] Exemplary catalysts are disclosed, for example, in U.S. Patent No. 5,164,419, the disclosure of which is incorporated herein by reference. Catalysts for the trimerization of polyisocyanates, such as alkali metal alkoxides, alkali metal carboxylates, or quaternary amine salts, may also be optionally used herein. Such catalysts are used in amounts that measurably increase the reaction rate of the polyisocyanates. Typical amounts of catalyst are about 0.1% to about 5% by weight, based on the total weight of all foaming ingredients. Non-limiting examples of catalysts include POLYCAT® 8, N, from Evonik Industries.N-dimethylcyclohexylamine, POLYCAT® 5 from Evonik Industries, pentamethyldiethylenetriamine, and CURITHANE® 52 from Evonik Industries, 2-methyl(n-methylamino b-acetic acid sodium nonylphenol), POLYCAT® 30 (Evonik Industries), POLYCAT® 36 (Evonik Industries), POLYCAT® 46 (Evonik Industries), POLYCAT® 77 (Evonik Industries), Dabco® 2039 (Evonik Industries), Dabco® 204 (Evonik Industries), Dabco® 2040 (Evonik Industries), Dabco® BL-19 (Evonik Industries), Dabco® BL-17 (Evonik Industries), Dabco® T (Evonik Industries), Dabco® T-125 (Evonik Industries), Industries), Dabco® K-15 (Evonik Industries), Dabco® TMR (Evonik Industries), Dabco® TMR-2 (Evonik Industries), Dabco® TMR-3 (Evonik Industries), Dabco® TMR-30 (Evonik Industries), Bicat® 8210 (The Shepard Chemical Company, Cincinnati, OH), Bicat® 8840 (The Shepard Chemical Company, Cincinnati, OH), Bicat® 8842 (The Shepard Chemical Company, Cincinnati, OH), K-Kat® XK 651 (King Industries, Norwalk, CT), K-Kat® 614 (King Industries, Norwalk, CT),CT), K-Kat® 672 (King Industries, Norwalk, CT), K-Kat® 604 (King Industries, Norwalk, CT), Niax® UL1 (Momentive Performance Materials Inc., Waterford, NY), Niax® UL22, Niax® UL1 (Momentive Performance Materials Inc., Waterford, NY), Jeffamine® D-230 (Huntsman, The Woodlands, TX), Jeffamine® T403 (Huntsman, The Woodlands, TX), Jeffamine® D2000 (Huntsman, The Woodlands, TX), Jeffamine® T5000 (Huntsman, The Woodlands, TX), Jeffcat® PMDETA (Huntsman, The Woodlands, TX), Jeffcat® DMCHA (Huntsman, The Examples include ZF20 (Huntsman, The Woodlands, TX), ZF54 (Huntsman, The Woodlands, TX), tin, dibutyltin mercaptide, potassium octanoate, potassium acetate, bismuth, and bismuth carboxylate mixtures.

[0052] In some embodiments, the foamable composition includes a surfactant. Suitable surfactants can include liquid or solid organosilicone compounds. Other surfactants include polyethylene glycol ethers of long-chain alcohols, long-chain alkyl acid sulfates, alkyl sulfonates, and tertiary amine or alkanolamine salts of alkylaryl 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 Dabco® DC5585. In some embodiments, the surfactant is Tegostab® B8871.

[0053] In some embodiments, the foamable composition includes a flame retardant. Useful 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, and bromine-containing 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 Saytex® RB-79 (Albemarle Corporation, Baton Rouge, LA), a reactive bromine-containing diester / ether diol of tetrabromophthalic anhydride. In some embodiments, the flame retardant is tris(1-chloro-2-propyl)phosphate (TCPP).

[0054] In some embodiments, the foamable composition includes a nucleating agent. The nucleating agent primarily functions to increase the cell count 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 resin. Typical nucleating agents include, among others, at least one member selected from the group consisting of talc, sodium bicarbonate-citric acid mixtures, calcium silicate, and carbon dioxide. In some embodiments, the foamable composition does not include a nucleating agent. In some embodiments, the processes provided herein are carried out in the absence of a nucleating agent. Examples of nucleating agents include, but are not limited to, talc, sodium bicarbonate-citric acid mixtures, calcium silicate, carbon dioxide, and the like.

[0055] In some embodiments, the foamable composition further comprises water.

[0056] In some embodiments, the present application further provides a process for forming a foam, comprising reacting or extruding a foamable composition provided herein under conditions effective to form a foam, wherein the foamable composition comprises a blowing agent component described herein.

[0057] In some embodiments, the process for forming a foam comprises (a) adding a foamable composition disclosed herein (e.g., a B-side composition) to a composition containing an isocyanate (e.g., an A-side composition), and (b) reacting the foamable composition under conditions effective to form a foam. The isocyanate or isocyanate-containing mixture can include isocyanates and auxiliary chemicals such as catalysts, surfactants, stabilizers, chain extenders, crosslinkers, water, flame retardants, smoke suppressants, pigments, coloring materials, and fillers. In some embodiments, the isocyanate is PAPI-27. Any of the methods well known in the art, such as those described in "Polyurethanes Chemistry and Technology," Vol. I, II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, incorporated herein by reference, can be used or adapted for use in accordance with the compositions disclosed herein.

[0058] In the process of making polyisocyanate-based foams, polyols, polyisocyanates, and other components are contacted and thoroughly mixed to allow expansion and curing into a cellular polymer. The specific mixing equipment is not critical, and a variety of mix heads and spray equipment are conveniently used. It is often convenient, but not necessary, to pre-blend certain ingredients prior to reaction of the polyisocyanate with the polyol. For example, it is often useful to prepare a foamable composition (e.g., a B-side composition) disclosed herein and then contact this composition with the polyisocyanate.

[0059] It is understood that the present application further provides the foamable compositions described herein for use in the processes for preparing the foams described herein. In some embodiments, the foamable compositions described herein are useful in one or more of the processes described herein.

[0060] foam The present application further provides foams prepared according to one or more processes provided herein (e.g., prepared according to one or more processes provided herein from one or more foamable compositions provided herein). The types of foams produced can include, for example, closed-cell foams, open-cell foams, rigid foams, flexible foams, and integral skins. In some embodiments, disclosed herein are foams prepared from the foamable compositions (e.g., B-side compositions) described herein. In some embodiments, the foam is a spray foam. In some embodiments, the foam is a thermoset foam.

[0061] 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, rigid closed-cell polyisocyanurate-based foams are useful for spray insulation, as foam-in-place appliance foam, rigid insulation board material, or in laminates.

[0062] In some embodiments, the foams disclosed herein can be used in a wide variety of applications, including, but not limited to, appliance foams, including refrigerator foam, freezer foam, refrigerator / freezer foam, panel foam, and other cold or cryogenic manufacturing applications. In some embodiments, foams formed from the compositions disclosed herein have exceptional thermal performance, which can be measured, for example, by K-factor. As used herein, "K-factor" refers to the thermal conductivity of a foam, i.e., its ability to conduct heat. K-factor is a measure of the heat that passes through one square foot of material that is one inch thick in one hour. Typically, the lower the K-factor, the better the thermal insulation.

[0063] In some embodiments, the foam has a viscosity of about 0.135 Btu in / ft at about 24°C. 2 h °C or less. In some embodiments, the foam has a K-factor of about 0.130 Btu in / ft at 24 °C. 2 h℃~approx. 0.135Btu in / ft 2 It has a K factor of h℃.

[0064] In some embodiments, the foam has a viscosity of about 0.124 Btu in / ft at about 10°C. 2 h °C or less. In some embodiments, the foam has a K-factor of about 0.118 Btu in / ft at 10 °C. 2 h℃ ~ approx. 0.124 Btu in / ft 2 It has a K factor of h℃.

[0065] In some embodiments, the foam has a thermal conductivity of about 0.118 Btu in / ft at about -6.7°C. 2 h °C or less. In some embodiments, the foam has a K-factor of about 0.110 Btu in / ft at about -6.7 °C. 2 h℃~approx. 0.118Btu in / ft 2 It has a K factor of h℃.

[0066] In some embodiments, the foam has a viscosity of about 0.135 Btu in / ft at about 24°C. 2 h°C or less, approximately 0.124 Btu in / ft at approximately 10°C 2 h°C or less, and approximately 0.118 Btu in / ft at approximately -6.7°C 2 It has a K factor of less than h℃.

[0067] In some embodiments, the foam has a viscosity of about 0.130 Btu in / ft at 24°C. 2 h℃~approx. 0.135Btu in / ft 2 h℃, approximately 0.118 Btu in / ft at 10℃ 2 h℃ ~ approx. 0.124 Btu in / ft 2 h°C, and approximately 0.110 Btu in / ft at -6.7°C 2h℃~approx. 0.118Btu in / ft 2 It has a K factor of h℃.

[0068] In some embodiments, the foam has a viscosity of about 0.142 Btu in / ft at about 24°C. 2 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℃~approx. 0.139 Btu in / ft 2 It has a K factor of h℃.

[0069] In some embodiments, the foam has a viscosity 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℃~approx. 0.129 Btu in / ft 2 It has a K factor of h℃.

[0070] In some embodiments, the foam has a thermal conductivity 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 about -6.7 °C. 2 h℃~about 0.120Btu in / ft 2 It has a K factor of h℃.

[0071] In some embodiments, the foam has a viscosity of about 0.142 Btu in / ft at about 24°C. 2 h°C or less, approximately 0.129 Btu in / ft at approximately 10°C 2 h°C or less, and approximately 0.120 Btu in / ft at approximately -6.7°C 2 It has a K factor of less than h℃.

[0072] In some embodiments, the foam has a viscosity of about 0.140 Btu in / ft at 24°C. 2 h℃~approx. 0.139 Btu in / ft 2 h℃, approximately 0.127 Btu in / ft at 10℃ 2h℃~approx. 0.129 Btu in / ft 2 h°C, and approximately 0.116 Btu in / ft at -6.7°C 2 h℃~about 0.120Btu in / ft 2 It has a K factor of h℃.

[0073] In some embodiments, the foam has a cream time of about 1 second to about 30 seconds, e.g., about 1 to about 25 seconds, about 1 to about 20 seconds, about 1 to about 15 seconds, about 1 to about 10 seconds, about 1 to about 5 seconds, about 5 to about 30 seconds, about 5 to about 25 seconds, about 5 to about 20 seconds, about 5 to about 15 seconds, about 5 to about 10 seconds, about 10 to about 30 seconds, about 10 to about 25 seconds, about 10 to about 20 seconds, about 10 to about 15 seconds, about 15 to about 30 seconds, about 15 to about 25 seconds, about 15 to about 20 seconds, about 20 to about 30 seconds, about 20 to about 25 seconds, or about 25 to about 30 seconds. In some embodiments, the present application provides a foam having a cream time of about 20 seconds to about 30 seconds. In some embodiments, the present application provides a foam having a cream time of about 5 seconds to about 12 seconds.

[0074] In some embodiments, the foam may be heated for about 30 to about 70 seconds, e.g., about 30 to about 65 seconds, about 30 to about 60 seconds, about 30 to about 55 seconds, about 30 to about 50 seconds, about 30 to about 45 seconds, about 30 to about 40 seconds, about 30 to about 35 seconds, about 35 to about 70 seconds, about 35 to about 65 seconds, about 35 to about 60 seconds, about 35 to about 55 seconds, about 35 to about 50 seconds, about 35 to about 45 seconds, about 35 to about 40 seconds, about 40 to about 70 seconds, about 40 to about 65 seconds, about 40 to about 65 seconds, about 40 to about 70 seconds, about 40 to about 65 seconds, about 40 to about 65 seconds, about 40 to about 4 ... The foam may have a gelation time of about 60 seconds, about 40 to about 55 seconds, about 40 to about 50 seconds, about 40 to about 45 seconds, about 45 to about 70 seconds, about 45 to about 65 seconds, about 45 to about 60 seconds, about 45 to about 55 seconds, about 45 to about 50 seconds, about 50 to about 70 seconds, about 50 to about 65 seconds, about 50 to about 60 seconds, about 50 to about 55 seconds, about 55 to about 70 seconds, about 55 to about 65 seconds, about 55 to about 60 seconds, about 60 to about 70 seconds, about 60 to about 65 seconds, or about 65 to about 70 seconds. In some embodiments, the foam has a gelation time of about 50 seconds to about 65 seconds. In some embodiments, the foam has a gelation time of about 35 seconds to about 45 seconds.

[0075] In some embodiments, the foam may be heated for about 85 to about 140 seconds, e.g., about 85 to about 135 seconds, about 85 to about 130 seconds, about 85 to about 125 seconds, about 85 to about 120 seconds, about 85 to about 115 seconds, about 85 to about 110 seconds, about 85 to about 105 seconds, about 85 to about 100 seconds, about 85 to about 95 seconds, about 85 to about 90 seconds, about 90 to about 140 seconds, about 90 to about 135 seconds, about 90 to about 130 seconds, about 90 to about 125 seconds, about 90 to about 120 seconds, about 90 ~115 seconds, 90~110 seconds, 90~105 seconds, 90~100 seconds, 90~95 seconds, 95~140 seconds, 95~135 seconds, 95~130 seconds, 95~125 seconds, 95~130 seconds 120 seconds, about 95 to about 115 seconds, about 95 to about 110 seconds, about 95 to about 105 seconds, about 95 to about 100 seconds, about 100 to about 140 seconds, about 100 to about 135 seconds, about 100 to about 130 seconds, about 100 to about 125 seconds, about 1 00~120 seconds, 100~115 seconds, 100~110 seconds, 100~105 seconds, 105~140 seconds, 105~135 seconds, 105~130 seconds, 105~125 seconds, 105~ Approximately 120 seconds, approximately 105 to approximately 115 seconds, approximately 105 to approximately 110 seconds, approximately 110 to approximately 140 seconds, approximately 110 to approximately 135 seconds, approximately 110 to approximately 130 seconds, approximately 110 to approximately 125 seconds, approximately 110 to approximately 120 seconds, approximately 110 to approximately 11 The foam may have a tack-free time of about 5 seconds, about 115 to about 140 seconds, about 115 to about 135 seconds, about 115 to about 130 seconds, about 115 to about 125 seconds, about 115 to about 120 seconds, about 120 to about 140 seconds, about 120 to about 135 seconds, about 120 to about 130 seconds, about 120 to about 125 seconds, about 125 to about 140 seconds, about 125 to about 135 seconds, about 125 to about 130 seconds, about 130 to about 140 seconds, about 130 to about 135 seconds, or about 135 to about 140 seconds. In some embodiments, the foam has a tack-free time of about 120 seconds to about 135 seconds. In some embodiments, the foam has a tack-free time of about 90 seconds to about 100 seconds.

[0076] In some embodiments, the foam has a density of about 2.5 to about 3.5 pcf. For example, the foam can have a density of about 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, or 3.5 pcf. In some embodiments, the present application provides a foam having a density of about 2.90 pcf to about 3.10 pcf. In some embodiments, the foam has a density of about 2.53 pcf to about 2.56 pcf.

[0077] In some embodiments, the foam has a closed cell content of 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 about 96% to about 99%. In some embodiments, the foam has a closed cell content of about 90% to about 95%. In some embodiments, the foam has a closed cell content of about 96% to about 99%.

[0078] Representative foam products that can be made according to the present disclosure include, for example, (1) polystyrene foam sheets for the production of single-use thermoformed packaging materials, as disclosed, for example, in U.S. Pat. No. 5,204,169; (2) foam sheets with cross-sectional areas of 0.17 to 3 square feet (0.016 to 0.28 square meters), lengths up to 27 feet (813 meters), and a density of about 1.5 to 10 pounds per cubic foot (pcf) (25 to 160 kilograms per cubic meter (kg / m)); 3 (3) Extruded polystyrene foam board for use as a sheathing and roofing material in residential and industrial applications, which may be about 0.5 to 6 inches (1.25 to 15 cm) thick, up to 4 feet (122 cm) wide, having a density of 1000 psi (0.19 to 0.74 m), a cross-sectional area of ​​about 2 to 8 square feet (0.19 to 0.74 m), and a modulus of 6 to 15 pcf (96 to 240 kg / m). 3and expandable foams in the form of large pieces that can be up to about 2 feet (61 cm) thick, often at least 1.5 feet (46 cm) thick, up to 4 feet (1.22 meters) wide, and up to 16 feet (4.8 meters) long, having a density of 1000 psi (0.1 psi). Such foam products are more fully described by Stockdopole and Welsh in Encyclopedia of Polymer Science and Engineering, vol. 16, pp. 193-205 (John Wiley & Sons, 1989), which is incorporated herein by reference. [Example]

[0079] The present disclosure is further defined in the following examples. It should be understood that these examples, while showing preferred embodiments, are provided for illustrative purposes only. From the above discussion and these examples, those skilled in the art can ascertain preferred features and make various changes and modifications to adapt to various uses and conditions without departing from the spirit and scope thereof.

[0080] The following components were used to prepare the example formulations:

[0081] The polyol is Stepanpol® PS-2352, which is an aromatic polyester polyol available from Stepan Company.

[0082] The stabilizer is Tegostab® B8871, a modified silicone stabilizer available from Evonik Industries, AG.

[0083] The amine catalyst is Polycat® 5, which is a tertiary amine catalyst available from Evonik Industries, AG.

[0084] The metal catalyst is Dabco® K-15, a potassium-based catalyst available from Evonik Industries.

[0085] The flame retardant is TCPP.

[0086] The isocyanate is PAPI-27, which is a polymethylene polyphenylisocyanate-containing MDI available from Dow DuPont Chemical Company.

[0087] Example 1. General Preparation of A-Side and B-Side Compositions The B-side components were weighed out as a masterbatch on a mass balance and mixed together in a 1 L plastic beaker, excluding the blowing agent. The masterbatch was then divided equally into three separate 1 L beakers, after which the blowing agents were added and mixed until fully incorporated. The blowing agents were added in order of decreasing solubility in the B-side system (e.g., HCFO-1233zd-E first, followed by isopentane, and then HFO-1336mzz-E last). The isocyanate (A-side), primarily PAPI27, was weighed out at an additional 15 wt% in a 500 mL plastic beaker and injected into the B-side mixture for sufficient headroom injection. The A+B mixture was placed in a mixhead and mixed at 4000 rpm for 3 seconds. After mixing, the combined A+B solution was quickly poured into a wax-coated cardboard box and a timer was started. The foam was then placed under an air hood for 24 hours to allow the polyurethane reaction to complete. The foam was then cut into 8" x 8" x 1.5" blocks. These foam blocks were tested for thermal conductivity using a heat flow meter per ASTM C-518.

[0088] Example 2. Ternary Blowing Agent Blend of HFO-1336mzz-E, Isopentane, and HCFO-1233zd-E Table 1 summarizes formulations (A-side and B-side formulations) containing a ternary blowing agent blend of HFO-1336mzz-E, isopentane, and HCFO-1233zd-E prepared according to the general procedure described in Example 1.

[0089] [Table 1]

[0090] The blowing agent components in Table 1, as weight percent (wt%) of the total amount of blowing agent, are as follows:

[0091] Control formulation: 90 wt. % HCFO-1233zd-E, 10 wt. % isopentane, and 0 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present in Side B.

[0092] Formulation 2A: 80 wt. % HCFO-1233zd-E, 10 wt. % isopentane, and 10 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present on the B-side.

[0093] Formulation 2B: 75 wt. % HCFO-1233zd-E, 10 wt. % isopentane, and 15 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present on side B.

[0094] Formulation 2C: 60 wt. % HCFO-1233zd-E, 20 wt. % isopentane, and 20 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present in the B-side.

[0095] Formulation 2D: 45 wt. % HCFO-1233zd-E, 25 wt. % isopentane, and 35 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present in side B.

[0096] After testing, data values ​​were collected for analysis and are shown in Table 2 below and in FIG.

[0097] [Table 2]

[0098] It was found that the highest k-factor performance was achieved in Foam 2B, which was prepared using a blowing agent component containing 75 wt. % HCFO-1233zd-E, 10 wt. % isopentane, and 15 wt. % HFO-1336mzz-E, based on the total mass of blowing agent present on Side B.

[0099] Theoretical calculations provided information about where these areas of improvement might lie. Figure 2 shows the ternary azeotrope predictions from the calculations, where darker colors indicate stronger azeotrope regions. Figure 2 illustrates the regions investigated for the foam synthesis described above. Notably, the best performance did not directly match the predicted azeotrope. Without being bound by theory, it is believed that other factors are involved, resulting in unexpected behavior.

[0100] When 1233zd is replaced with 1336E, a decrease in thermal conductivity is observed, which continues to improve up to about 15 weight percent. At about 20% 1336E, the trend reverses and thermal conductivity increases. This behavior is unexpected because the vapor thermal conductivity of 1336E is greater than that of 1233zd, and based on the thermal conductivity of gases, thermal conductivity would be expected to increase as 1336E replaces 1233zd.

[0101] Example 3. Ternary Blowing Agent Blend of HFO-1336mzz-E, Cyclopentane, and HCFO-1233zd-E Table 3 summarizes formulations (A-side and B-side formulations) containing a ternary blowing agent blend of HFO-1336mzz-E, cyclopentane, and HCFO-1233zd-E prepared according to the general procedure described in Example 1.

[0102] [Table 3]

[0103] The blowing agent components in Table 3, as weight percent (wt%) of the total amount of blowing agent, are as follows:

[0104] Control formulation: 90 wt. % HCFO-1233zd-E, 10 wt. % cyclopentane, and 0 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present on side B.

[0105] Formulation 3A: 80 wt. % HCFO-1233zd-E, 10 wt. % cyclopentane, and 10 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present on the B-side.

[0106] Formulation 3B: 75 wt. % HCFO-1233zd-E, 10 wt. % cyclopentane, and 15 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present on the B-side.

[0107] Formulation 3C: 70 wt. % HCFO-1233zd-E, 10 wt. % cyclopentane, and 20 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present in the B-side.

[0108] Formulation 3D: 65 wt. % HCFO-1233zd-E, 10 wt. % cyclopentane, and 25 wt. % HFO-1336mzz-E, based on the total mass of blowing agents present on side B.

[0109] After testing, data values ​​were collected for analysis and are shown in Table 4 below and in FIG.

[0110] [Table 4]

[0111] It was found that the highest k-factor performance was achieved in Foam 3B, which was prepared using a blowing agent component containing 75 wt. % HCFO-1233zd-E, 10 wt. % cyclopentane, and 15 wt. % HFO-1336mzz-E, based on the total mass of blowing agent present on Side B.

[0112] Theoretical calculations provided information about where these areas of improvement might lie. Figure 4 shows the ternary azeotrope predictions from the calculations, where darker colors indicate stronger azeotrope regions. Figure 4 illustrates the regions investigated for the foam synthesis described above. Notably, the best performance did not directly match the predicted azeotrope. Without being bound by theory, it is believed that other factors are involved, resulting in unexpected behavior.

[0113] Other embodiments 1. In some embodiments, the present application provides a process for forming a foam, comprising reacting or extruding a foamable composition under conditions effective to form a foam, wherein the foamable composition comprises: (i) about 5 to about 40 weight percent E-CFCH=CHCF (HFO-1336mzz-E); (ii) about 8 to about 30 weight percent C5 hydrocarbons; (iii) about 40 to about 85 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)),

[0114] 2. The process of embodiment 1, wherein the blowing agent component comprises from about 10 to about 35 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0115] 3. The process of embodiment 1, wherein the blowing agent component comprises from about 10 to about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0116] 4. The process of any one of embodiments 1-3, wherein the blowing agent component comprises from about 10 to about 25 weight percent C5 hydrocarbons.

[0117] 5. The process of any one of embodiments 1-3, wherein the blowing agent component comprises about 8 to about 12 weight percent C5 hydrocarbons.

[0118] 6. The process of any one of embodiments 1-5, wherein the C5 hydrocarbon is selected from n-pentane, isopentane, and cyclopentane.

[0119] 7. The process of any one of embodiments 1 to 5, wherein the C5 hydrocarbon is cyclopentane.

[0120] 8. The process of any one of embodiments 1-5, wherein the C5 hydrocarbon is cyclopentane.

[0121] 9. The process of any one of embodiments 1-8, wherein the blowing agent component comprises about 65 to about 80 weight percent E-CHCl=CHCF(HCFO-1233zd(E).

[0122] 10. The process of any one of embodiments 1-8, wherein the blowing agent component comprises about 45 to about 80 weight percent E-CHCl=CHCF(HCFO-1233zd(E).

[0123] 11. The blowing agent component is (i) about 10 to about 25 weight percent E-CFCH=CHCF (HFO-1336mzz-E); (ii) about 10 weight percent cyclopentane; (iii) about 65 to about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0124] 12. The process produces approximately 0.135 Btu in / ft at approximately 24°C. 2 12. The process of embodiment 1 or 11, forming a foam having a K-factor of h °C or less.

[0125] 13. The process produces approximately 0.130 Btu in / ft at approximately 24°C. 2 h℃~approx. 0.135Btu in / ft 2 12. The process of embodiment 1 or 11, forming a foam having a K-factor of h °C.

[0126] 14. The process produces approximately 0.124 Btu in / ft at approximately 10°C. 2 12. The process of embodiment 1 or 11, forming a foam having a K-factor of h °C or less.

[0127] 15. The process produces approximately 0.118 Btu in / ft at approximately 10°C. 2 h℃ ~ approx. 0.124 Btu in / ft 2 12. The process of embodiment 1 or 11, forming a foam having a K-factor of h °C.

[0128] 16. The process produces approximately 0.118 Btu in / ft at approximately -6.7°C. 2 12. The process of embodiment 1 or 11, forming a foam having a K-factor of h °C or less.

[0129] 17. The process produces approximately 0.110 Btu in / ft at approximately -6.7°C. 2 h℃~approx. 0.118Btu in / ft 2 12. The process of embodiment 1 or 11, forming a foam having a K-factor of h °C.

[0130] 18. The process produces approximately 0.135 Btu in / ft at approximately 24°C. 2 h°C or less, approximately 0.124 Btu in / ft at approximately 10°C 2 h°C or less, and approximately 0.118 Btu in / ft at approximately -6.7°C 2 12. The process of embodiment 1 or 11, forming a foam having a K-factor of h °C or less.

[0131] 19. The process produces approximately 0.130 Btu in / ft at 24°C. 2 h℃~approx. 0.135Btu in / ft 2 h℃, approximately 0.118 Btu in / ft at 10℃ 2 h℃ ~ approx. 0.124 Btu in / ft 2 h°C, and approximately 0.110 Btu in / ft at -6.7°C 2 h℃~approx. 0.118Btu in / ft 212. The process of embodiment 1 or 11, forming a foam having a K-factor of h °C.

[0132] 20. The process of any one of embodiments 1 and 11-19, wherein the process forms a foam having a cream time of about 20 seconds to about 30 seconds.

[0133] 21. The process of any one of embodiments 1 and 11-20, wherein the process forms a foam having a gel time of about 50 seconds to about 65 seconds.

[0134] 22. The process of any one of embodiments 1 and 11-21, wherein the process forms a foam having a tack-free time of about 120 seconds to about 135 seconds.

[0135] 23. The process of any one of embodiments 1 and 11-22, wherein the process forms a foam having a density of about 2.90 pcf to about 3.10 pcf.

[0136] 24. The process of any one of embodiments 1 and 11-23, wherein the process forms a foam having about 90% to about 95% closed cell content.

[0137] 25. The blowing agent component is about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 20 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 70 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 15 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 75 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or 25. The process of any one of embodiments 1 and 11-24, comprising about 10 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0138] 26. The blowing agent component is (i) about 10 to about 30 weight percent E-CFCH=CHCF (HFO-1336mzz-E); (ii) about 10 to about 25 weight percent isopentane; (iii) about 45 to about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0139] 27. The process produces approximately 0.142 Btu in / ft at approximately 24°C. 2 27. The process of embodiment 1 or 26, forming a foam having a K-factor of h °C or less.

[0140] Approximately 0.140 Btu in / ft at 28.24°C 2 h℃~approx. 0.139 Btu in / ft 2 27. The process of embodiment 1 or 26, forming a foam having a K-factor of h °C.

[0141] 29. The process produces approximately 0.129 Btu in / ft at approximately 10°C. 2 27. The process of embodiment 1 or 26, forming a foam having a K-factor of h °C or less.

[0142] 30. The process produces approximately 0.127 Btu in / ft at approximately 10°C. 2 h℃~approx. 0.129 Btu in / ft 2 27. The process of embodiment 1 or 26, forming a foam having a K-factor of h °C.

[0143] 31. The process produces approximately 0.120 Btu in / ft at approximately -6.7°C. 227. The process of embodiment 1 or 26, forming a foam having a K-factor of h °C or less.

[0144] 32. The process produces approximately 0.116 Btu in / ft at approximately -6.7°C. 2 h℃~about 0.120Btu in / ft 2 27. The process of embodiment 1 or 26, forming a foam having a K-factor of h °C.

[0145] 33. The process produces approximately 0.142 Btu in / ft at approximately 24°C. 2 h°C or less, approximately 0.129 Btu in / ft at approximately 10°C 2 h°C or less, and approximately 0.120 Btu in / ft at approximately -6.7°C 2 27. The process of embodiment 1 or 26, forming a foam having a K-factor of h °C or less.

[0146] 34. The process produces approximately 0.140 Btu in / ft at 24°C. 2 h℃~approx. 0.139 Btu in / ft 2 h℃, approximately 0.127 Btu in / ft at 10℃ 2 h℃~approx. 0.129 Btu in / ft 2 h°C, and approximately 0.116 Btu in / ft at -6.7°C 2 h℃~about 0.120Btu in / ft 2 Process V forms a foam having a K factor of h°C.

[0147] 35. The process of any one of embodiments 1 and 26-34, wherein the process forms a foam having a cream time of from about 5 seconds to about 12 seconds.

[0148] 36. The process of any one of embodiments 1 and 26-35, wherein the process forms a foam having a gel time of about 35 seconds to about 45 seconds.

[0149] 37. The process of any one of embodiments 1 and 26-36, wherein the process forms a foam having a tack-free time of about 90 seconds to about 100 seconds.

[0150] 38. The process of any one of embodiments 1 and 26-37, wherein the process forms a foam having a density of about 2.53 pcf to about 2.56 pcf.

[0151] 39. The process of any one of embodiments 1 and 26-38, wherein the process forms a foam having about 96% to about 99% closed cell content.

[0152] 40. The blowing agent component is about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 20 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 20 weight percent isopentane, and about 60 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 15 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent isopentane, and about 75 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or 40. The process of any one of embodiments 1 and 26-39, comprising about 10 weight percent E-CFCH=CHCF (HFO-1336mzz-E), about 10 weight percent isopentane, and about 80 weight percent E-CHCl=CHCF (HCFO-1233zd(E)).

[0153] 41. The process of any one of embodiments 1-40, 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.

[0154] 42. The process of any one of embodiments 1-40, wherein the foamable composition comprises at least one polyol.

[0155] 43. The process of embodiment 41 or 42, wherein the polyol is a polyester polyol.

[0156] 44. The process of any one of embodiments 1-40, wherein the foamable composition comprises at least one catalyst.

[0157] 45. The process of any one of embodiments 1-40, wherein the foamable composition comprises a metal catalyst and an amine catalyst.

[0158] 46. ​​The process of any one of embodiments 1-40, wherein the foamable composition comprises a surfactant.

[0159] 47. The process of embodiment 41 or 46, wherein the surfactant is a silicone surfactant.

[0160] 48. The process of any one of embodiments 1-40, wherein the foamable composition comprises water.

[0161] 49. The process of any one of embodiments 1-40, wherein the foamable composition comprises a flame retardant.

[0162] 50. The process of any one of embodiments 1-40, wherein the foamable composition comprises a nucleating agent.

[0163] 51. The process of any one of embodiments 1 to 40 and 42 to 49, wherein the process is carried out in the absence of a nucleating agent.

[0164] 52. The process of any one of embodiments 1-51, wherein the foam is a spray foam.

[0165] 53. The process of any one of embodiments 1-52, wherein the foam is a thermoset foam.

[0166] 54. The process of any one of embodiments 1 to 53, wherein the foam is a polyurethane foam or a polyisocyanurate foam.

[0167] 55. The process of any one of embodiments 1-54, wherein the foam is a closed-cell foam.

[0168] 56. A foamable composition comprising a blowing agent component: about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 20 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 70 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 15 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 75 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 10 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), and 10. The process of embodiment 1, comprising a blowing agent component comprising at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant.

[0169] 57. A foamable composition comprising a blowing agent component: about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 20 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 20 weight percent isopentane, and about 60 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 15 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent isopentane, and about 75 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), or about 10 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent isopentane, and about 80 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)), and 10. The process of embodiment 1, comprising a blowing agent component comprising at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant.

[0170] 58. A foamable composition comprising a blowing agent component, the blowing agent component comprising: (i) about 5 to about 40 weight percent E-CFCH=CHCF (HFO-1336mzz-E); (ii) about 8 to about 30 weight percent C5 hydrocarbons; (iii) about 40 to about 85 weight percent E-CHCl=CHCF3 (HCFO-1233zd(E)).

[0171] 59. A foam prepared according to the process of any one of embodiments 1 to 57.

[0172] 60. The foam of embodiment 59, which is a closed-cell polyisocyanurate foam.

[0173] 61. The foam of embodiment 59, which is a closed-cell polyurethane foam.

[0174] While the present invention has been described in conjunction with its detailed description, it should be understood that the foregoing description is intended to illustrate, but not limit, the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be understood by those skilled in the art to which this invention pertains that any of the features described herein with respect to any particular aspect and / or embodiment of the invention may be combined with any one or more of the other features of any other aspect and / or embodiment of the invention described herein, modified as appropriate to ensure compatibility of the combination. Such combinations are considered to be part of the invention contemplated by this disclosure.

Claims

1. 1. A process for forming a foam, comprising reacting or extruding a foamable composition under conditions effective to form a foam, said foamable composition comprising: about 5 to about 40 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E) and about 8 to about 30 weight percent C ５ Hydrocarbons, About 40 to about 85 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), The process includes a blowing agent component comprising:

2. The blowing agent component comprises from about 10 to about 35 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E).

3. The blowing agent component comprises from about 10 to about 25 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E).

4. The blowing agent component comprises from about 10 to about 25 weight percent C ５ 10. The process of claim 1, comprising a hydrocarbon.

5. The blowing agent component comprises from about 8 to about 12 weight percent C ５ 10. The process of claim 1, comprising a hydrocarbon.

6. Said C ５ 2. The process of claim 1, wherein the hydrocarbon is selected from n-pentane, isopentane, and cyclopentane.

7. Said C ５ 2. The process of claim 1, wherein the hydrocarbon is cyclopentane.

8. Said C ５ 10. The process of claim 1, wherein the hydrocarbon is isopentane.

9. the blowing agent component is from about 65 to about 80 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E).

10. the blowing agent component is from about 45 to about 80 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E).

11. The blowing agent component is about 10 to about 25 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E) and about 10 weight percent cyclopentane; About 65 to about 80 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), 2. The process of claim 1, comprising:

12. The process produces a pulverulent pulverulent solution of about 0.135 Btu in / ft at about 24°C. ２ 12. The process of claim 11, which produces a foam having a K factor of h°C or less.

13. The process produces a pulverulent pulverulent solution of about 0.130 Btu in / ft at about 24°C. ２ h℃~about 0.135Btu in / ft ２ 12. The process of claim 11, which produces a foam having a K factor of h°C.

14. The process produces a pulverulent pulverulent solution of about 0.124 Btu in / ft at about 10°C. ２ 12. The process of claim 11, which produces a foam having a K factor of h°C or less.

15. The process produces a pulverulent pulverulent solution of about 0.118 Btu in / ft at about 10°C. ２ h℃~about 0.124Btu in / ft ２ 12. The process of claim 11, which produces a foam having a K factor of h°C.

16. The process produces a pulp of about 0.118 Btu in / ft at about -6.7°C. ２ 12. The process of claim 11, which produces a foam having a K factor of h°C or less.

17. The process produces a pulverulent pulverulent solution of about 0.110 Btu in / ft at about -6.7°C. ２ h℃~about 0.118Btu in / ft ２ 12. The process of claim 11, which produces a foam having a K factor of h°C.

18. The process produces a pulverulent pulverulent solution of about 0.135 Btu in / ft at about 24°C. ２ h °C or less, about 0.124 Btu in / ft at about 10 °C ２ h °C or less, and about 0.118 Btu in / ft at about -6.7 °C ２ 12. The process of claim 11, which produces a foam having a K factor of h°C or less.

19. The process produces approximately 0.130 Btu in / ft at 24°C. ２ h℃~about 0.135Btu in / ft ２ h°C, approximately 0.118 Btu in / ft at 10°C ２ h℃~about 0.124Btu in / ft ２ h °C, and approximately 0.110 Btu in / ft at -6.7 °C ２ h℃~about 0.118Btu in / ft ２ 12. The process of claim 11, which produces a foam having a K factor of h°C.

20. 12. The process of claim 11, wherein the process forms a foam having a cream time of about 20 seconds to about 30 seconds.

21. 12. The process of claim 11, wherein the process forms a foam having a gel time of from about 50 seconds to about 65 seconds.

22. 12. The process of claim 11, wherein the process forms a foam having a tack-free time of from about 120 seconds to about 135 seconds.

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

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

25. The blowing agent component is About 25 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 20 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 70 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 15 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 75 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 10 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 80 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)) 2. The process of claim 1, comprising:

26. The blowing agent component is about 10 to about 30 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E) and about 10 to about 25 weight percent isopentane; About 45 to about 80 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), 2. The process of claim 1, comprising:

27. The process produces a carbon dioxide gas of about 0.142 Btu in / ft at about 24°C. ２ 27. The process of claim 26, which produces a foam having a K factor of h°C or less.

28. The process produces a pulverulent pulverulent solution of about 0.140 Btu in / ft at about 24°C. ２ h℃~about 0.139Btu in / ft ２ 27. The process of claim 26, which produces a foam having a K factor of h°C.

29. The process produces a pulverulent pulverulent solution of about 0.129 Btu in / ft at about 10°C. ２ 27. The process of claim 26, which produces a foam having a K factor of h°C or less.

30. The process produces a pulverulent pulverulent gas at about 10° C., with a pulverulent pulverulent gas content of about 0.127 Btu in / ft ２ h℃~about 0.129Btu in / ft ２ 27. The process of claim 26, which produces a foam having a K factor of h°C.

31. The process produces a pulverulent pulverulent solution of about 0.120 Btu in / ft at about -6.7°C. ２ 27. The process of claim 26, which produces a foam having a K factor of h°C or less.

32. The process produces a pulverulent pulverulent solution of about 0.116 Btu in / ft at about -6.7°C. ２ h℃~about 0.120Btu in / ft ２ 27. The process of claim 26, which produces a foam having a K factor of h°C.

33. The process produces a carbon dioxide gas 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 27. The process of claim 26, which produces a foam having a K factor of h°C or less.

34. The process produces approximately 0.140 Btu in / ft at 24°C. ２ h℃~about 0.139Btu in / ft ２ h°C, approximately 0.127 Btu in / ft at 10°C ２ h℃~about 0.129Btu in / ft ２ h °C, and approximately 0.116 Btu in / ft at -6.7 °C ２ h℃~about 0.120Btu in / ft ２ 27. The process of claim 26, which produces a foam having a K factor of h°C.

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

36. 27. The process of claim 26, wherein the process forms a foam having a gel time of from about 35 seconds to about 45 seconds.

37. 27. The process of claim 26, wherein the process forms a foam having a tack-free time of about 90 seconds to about 100 seconds.

38. 27. The process of claim 26, wherein the process forms a foam having a density of from about 2.53 pcf to about 2.56 pcf.

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

40. The blowing agent component is Approximately 30 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 20 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 20 weight percent isopentane, and about 60 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 15 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent isopentane, and about 75 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 10 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent isopentane, and about 80 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)) 2. The process of claim 1, comprising:

41. 10. The process of 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. 20. The process of claim 18, wherein the foamable composition comprises at least one polyol.

43. 20. The process of claim 19, wherein the polyol is a polyester polyol.

44. 20. The process of claim 18, wherein the foamable composition comprises at least one catalyst.

45. 24. The process of claim 23, wherein the foamable composition comprises a metal catalyst and an amine catalyst.

46. 20. The process of claim 18, wherein the foamable composition comprises a surfactant.

47. 26. The process of claim 25, wherein the surfactant is a silicone surfactant.

48. 20. The process of claim 18, wherein the foamable composition comprises water.

49. 20. The process of claim 18, wherein the foamable composition includes a flame retardant.

50. 20. The process of claim 18, wherein the foamable composition comprises a nucleating agent.

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

52. The process of claim 1 , wherein the foam is a spray foam.

53. The process of claim 3 wherein the foam is a thermoset foam.

54. 4. The process of claim 3, wherein the foam is a polyurethane foam or a polyisocyanurate foam.

55. The process of claim 3 wherein the foam is a closed-cell foam.

56. The foamable composition comprises a blowing agent component, About 25 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 20 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 70 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 15 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 75 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 10 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 80 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), and at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant 10. The process of claim 1, comprising a blowing agent component comprising:

57. The blowing agent component is Approximately 30 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 20 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 20 weight percent isopentane, and about 60 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 15 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent isopentane, and about 75 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), or About 10 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E), about 10 weight percent isopentane, and about 80 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)), and at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant 2. The process of claim 1, comprising:

58. 1. A foamable composition comprising a blowing agent component, the blowing agent component comprising: about 5 to about 40 weight percent E-CF ３ CH=CHCF ３ (HFO-1336mzz-E) and about 8 to about 30 weight percent C ５ Hydrocarbons, About 40 to about 85 weight percent E-CHCl═CHCF ３ (HCFO-1233zd(E)).

59. 10. A foam prepared according to the process of claim 1.

60. 60. The foam of claim 59 which is a closed-cell polyisocyanurate foam.

61. 60. The foam of claim 59 which is a closed-cell polyurethane foam.

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