EP4665787A1

EP4665787A1 - Process of preparing foams from ternary blowing agent

Info

Publication number: EP4665787A1
Application number: EP24713799.5A
Authority: EP
Inventors: Ernest Byron Wysong; Luke David SIMONI
Original assignee: Chemours Co FC LLC
Current assignee: Chemours Co FC LLC
Priority date: 2023-02-17
Filing date: 2024-02-15
Publication date: 2025-12-24
Also published as: WO2024173629A1; CN120344599A; JP2026505309A; MX2025008336A; KR20250150587A

Abstract

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

Description

TITLE

PROCESS OF PREPARING FOAMS FROM TERNARY BLOWING AGENT

TECHNICAL FIELD

[0001] This invention relates to processes of preparing foams from compositions comprising a ternary blowing agent component.

BACKGROUND

[0002] Closed-cell polyisocyanate-based foams are widely used for insulation purposes, for example, in building construction and in the manufacture of energy efficient electrical appliances. In the construction industry, polyurethane (polyisocyanurate) board stock is used in roofing and siding for its insulation and load-carrying capabilities. Poured and sprayed polyurethane foams are widely used for a variety of applications including insulating roofs, insulating large structures such as storage tanks, insulating appliances such as refrigerators and freezers, insulating refrigerated trucks and railcars, etc.

[0003] All of these various types of polyurethane foams require blowing (expansion) agents for their manufacture. Insulating foams depend on the use of halocarbon blowing agents, not only to foam the polymer, but also for their low vapor thermal conductivity, a very important characteristic for insulation value. Historically, polyurethane foams used CFCs (chlorofluorocarbons, for example CFC-1 1 , trichlorofluoromethane), HCFCs (hydrochlorofluorocarbons, for example HCFC-141 b, 1 , 1 -dichloro-1 -fluoroethane), and HFCs (hydrofluorocarbons, for example, HFC-245fa, HFC-365mfc) as the primary blowing agents.

[0004] In general, CFCs produce foams exhibiting good thermal insulation, low flammability, and excellent dimensional stability. However, despite these advantages, CFCs have fallen into disfavor due to the implication of chlorine- containing molecules in the destruction of stratospheric ozone. Further, the production and use of CFCs has been restricted by the Montreal Protocol. HCFCs have been proposed as CFC substitutes, and are currently employed as foam blowing agents. However, HCFCs have also been shown to contribute to the depletion of stratospheric ozone, and as a result their use has come under scrutiny. The widespread use of HCFCs is scheduled for eventual phase out under the Montreal Protocol.

SUMMARY

[0005] The present application provides, inter alia, processes of forming a foam, comprising reacting or extruding a foamable composition under conditions effective to form a foam, wherein the foamable composition comprises a blowing agent component comprising: about 5 to about 40 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 8 to about 30 weight percent Cs hydrocarbon; and about 40 to about 85 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E)).

[0006] The present application provides, foam blowing compositions comprising a blowing agent component comprising: about 5 to about 40 weight percent E-CFsCH^CHCFs (HFO-1336mzz-E); about 8 to about 30 weight percent Cs hydrocarbon; and about 40 to about 85 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E)).

[0007] The present application further provides a foam (e.g., polyisocyanurate or a polyurethane) prepared from a foam able composition according to a process 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 are described herein for use in the present invention; other, suitable methods and materials known in the art can 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 by reference in their entirety. In case of conflict, the present specification, including definitions, will control.

DESCRIPTION OF DRAWINGS

[0009] FIG. 1 shows the measured thermal performance (K-factor) of a foam prepared from a B-side compositions 2A-2D compared to a control composition, as described in Example 2, where “1150” refers to HFO-1336mzz-E.

[0010] FIG. 2 shows ternary azeotrope predictions from calculations for a blend of HFO-1336mzz-E, isopentane, and HCFO-1233ze(E). Darker colors indicate stronger azeotrope areas.

[0011] FIG. 3 shows the measured thermal performance (K-factor) of a foam prepared from a B-side compositions 3A-3D compared to a control composition, as described in Example 3.

[0012] FIG. 4 shows ternary azeotrope predictions from calculations for a blend of HFO-1336mzz-E, cyclopentane, and HCFO-1233ze(E). Darker colors indicate stronger azeotrope areas.

DETAILED DESCRIPTION

[0013] Polyisocyanurate (PIR) foam is a growing important market segment in the rigid insulation industry due to its excellent thermal performance and fire classification capability. The predominate blowing agents used for PIR panel foams are Cs hydrocarbons, such as cyclopentane, n-pentane, isopentane, or mixtures thereof. Although these Cs blowing agents can provide adequate thermal insulation performance for current requirements, increasingly stringent energy efficiency regulations are driving further improvements. Hydrofluoroolefins (HFOs) represent a class of compounds being used as blowing agents in polyurethane and related foams. Further, many HFOs react and decompose in the atmosphere relatively quickly. Thus, many HFOs have no or very low global warming potential (GWP) and do not contribute to the depletion of stratospheric ozone and global warming. HFOs have been shown to have improved insulation performance in comparison to Cs hydrocarbons, but are considerably more expensive. Therefore, a need for adding a minimum amount of HFO to C5 hydrocarbons to deliver a maximum improvement in insulation performance is needed.

[0014] Spray polyurethane foam (SPF) is a growing important market segment in the rigid insulation industry due to its excellent thermal performance and building envelope sealing capability. When applied, the speed and quality of the applied layers is critical for effective application and efficiency of performance parameters, including density and surface appearance. In addition, such foams are applied in situ in the buildings of interest under a variety of environmental conditions, including cold winter time temperatures. Typical physical foam expansion agents require heat to evaporate and expand. This becomes difficult in cold temperatures when the catalysis of the polyurethane polymerization is slowed, thus diminishing the only source of heat on the surface of the sprayed area. Therefore, providing a means of applying SPF with efficient lay down and under cold conditions represents a benefit for the industry.

[0015] Common techniques for preparing closed cell PIR and polyurethane (PUR) foam insulation performance involve the use of binary blowing agent blends containing, for example, hydrochlorofluoroolefins such as HCFO-1233zd in combination with hydrocarbons 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 was unexpectedly found that the blends described herein exhibited synergistic results and provided foams with improved insulation performance and long lived effects.

Definitions and Abbreviations

[0016] 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 comprises a list of elements is not necessarily limited to only 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 an inclusive or and not to 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 not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0017] As used herein, the term “consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term “consists essentially of’ or “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.

[0018] Also, use of “a” or “an” are employed 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 read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0019] As used herein, the term “about” is meant to account for variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value). All measurements reported herein are understood to be modified by the term “about”, whether or not the term is explicitly used, unless explicitly stated otherwise.

[0020] As used herein, the term “C_n hydrocarbon”, refers to a saturated hydrocarbon group that may be straight-chain or branched, having n carbons.

[0021] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and/or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

[0022] The following abbreviations may be used throughout the present application:

CFC: chlorofluorocarbon

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-CHCI=CHCF₃ pcf: pound-force per cubic foot

PIR: polyisocyanurate pphp: parts per hundred parts of polyol

PUR: polyurethane

SPF: spray polyurethane foam

TCPP: tris(1 -chloro-2-propyl) phosphate wt%: weight percent

Foamable Compositions and Process of Preparing a Foam

[0023] 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 Cs hydrocarbon, and E-CHCI=CHCF₃ (HCFO-1233zd(E)). In some embodiments, the foamable composition provided herein is useful in processes of forming a foam. [0024] In some embodiments, the blowing agent component comprises about 5 to about 40 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), for example, about 5 to about 35 weight percent, about 5 to about 30 weight percent, about 5 to about 25 weight percent, about 5 to about 20 weight percent, about 5 to about 15 weight percent, about 5 to about 10 weight percent, about 10 to about 40 weight percent, about 10 to about 35 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 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).

[0025] In some embodiments, the blowing agent component comprises about 10 to about 35 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 10 to about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E). In some embodiments, the blowing agent component comprises about 10 to about 25 weight percent E- CF₃CH=CHCF₃ (HFO-1336mzz-E).

[0026] 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- CFsCF CHCFs (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).

[0027] In some embodiments, the blowing agent component comprises about 8 to about 30 weight percent Cs hydrocarbon, for example, 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 Cs hydrocarbon.

[0028] In some embodiments, the blowing agent component comprises about 10 to about 25 weight percent Cs hydrocarbon. In some embodiments, the blowing agent component comprises about 8 to about 12 weight percent Cs hydrocarbon.

[0029] In some embodiments, the Cs hydrocarbon is selected from n- pentane, isopentane, and cyclopentane.

[0030] In some embodiments, the Cs 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.

[0031] In some embodiments, the Cs 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. [0032] In some embodiments, the blowing agent component comprises about 40 to about 85 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E), for example, about 40 to about 80 weight percent, about 40 to about 75 weight percent, about 40 to about 70 weight percent, about 40 to about 65 weight percent, about 40 to about 60 weight percent, about 40 to about 55 weight percent, about 40 to about 50 weight percent, about 40 to about 45 weight percent, about 45 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-CHCI=CHCF3 (HCFO- 1233zd(E).

[0033] In some embodiments, the blowing agent component comprises about 65 to about 80 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E). In some embodiments, the blowing agent component comprises about 45 to about 80 weight percent E-CHCI=CHCF₃ (HCFO-1233zd(E). [0034] In some embodiments, the blowing agent component comprises about 45 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent component comprises about 60 weight percent E- CHCI=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent component comprises about 65 weight percent E-CHCI=CHCF3 (HCFO- 1233zd(E)). In some embodiments, the blowing agent component comprises about 70 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent component comprises about 75 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E)). In some embodiments, the blowing agent component comprises about 80 weight percent E-CHCI=CHCF3 (HCFO- 1233zd(E)).

[0035] In some embodiments, 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 Cs hydrocarbon; and about 40 to about 85 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E)).

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

[0037] In some embodiments, the blowing agent component comprises: about 10 to about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 10 weight percent Cs hydrocarbon; and about 65 to about 80 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E)).

[0038] In some embodiments, the blowing agent component comprises: 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-CHCI=CHCF3 (HCFO-1233zd(E)). [0039] In some embodiments, the blowing agent component comprises: 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-CHCI=CHCF3 (HCFO-1233zd(E)). [0040] In some embodiments, the blowing agent component comprises: about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCI=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-CHC CHCFs (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-CHCI=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-CHCI=CHCF3 (HCFO-1233zd(E)); or about 30 weight percent E-CFsCH^CHCFs (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHCI=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-CHCI=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-CHCI=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-CHCI=CHCF3 (HCFO-1233zd(E)).

[0041] In some embodiments, the foamable composition further comprises one or more polyols. In some embodiments, one or more additives can be included in the foamable compositions described herein. For example, the foamable compositions can further comprise one or more additives that include, but are not limited to, catalysts, surfactants, flame retardants, stabilizers, preservatives, chain extenders, cross-linkers, water, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, nucleating agents, smoke suppressants, and pigments.

[0042] 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 agent, and at least one nucleating agent.

[0043] In some embodiments, the foamable composition comprises at least one polyol. In some embodiments, the polyol comprises 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 comprises a weight ratio of about 1 : 1 to about 2:1 polyester polyol to polyether polyol. In some embodiments, the polyol comprises a weight ratio of about 1 :1 polyester polyols to polyether polyols. In some embodiments, the polyol comprises a weight ratio of about 1 : 1 polyester polyol to polyether polyol.

[0044] In some embodiments, the polyol is a polyester polyol. Suitable polyester polyols include those prepared by reacting a carboxylic acid and/or a derivative thereof or a polycarboxylic anhydride with a polyhydric alcohol. The polycarboxylic acids 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 acid anhydride, pyromellitic dianhydride, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride acid, maleic acid, maleic acid anhydride, fumaric acid, and dimeric and trimeric fatty acids, such as those of oleic acid which may be in admixture with monomeric fatty acids. Simple esters of polycarboxylic acids can also be used, such as terephthalic acid dimethylester, terephthalic acid bisglycol and extracts thereof. The polyhydric alcohols suitable for the preparation of polyester polyols can be aliphatic, cycloaliphatic, aromatic, and/or heterocyclic. The polyhydric alcohols optionally can include substituents which are inert in the reaction, for example, chlorine and bromine substituents, and/or may be unsaturated. Suitable amino alcohols, such as monoethanolamine, diethanolamine or the like can also be used. Examples of suitable polyhydric alcohols include ethylene glycol, propylene glycol, polyoxyalkylene glycols (such as diethylene glycol, polyethylene glycol, dipropylene glycol and polypropylene glycol), glycerol, and trimethylolpropane.

[0045] Other suitable polyester polyols include, but are not limited to, aromatic polyester polyols, e.g., those made by transesterifying polyethylene terephthalate (PET) scrap with a glycol such as diethylene glycol, or made by reacting phthalic anhydride with a glycol. The resulting polyester polyols can be reacted further with ethylene and/or propylene oxide to form an extended polyester polyol containing additional internal alkyleneoxy groups.

[0046] 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 with an average hydroxyl number of from about 200 to about 325, such as from about 235 to about 265, or about 230 to about 250, or about 295 to about 315.

[0047] Exemplary polyester polyols that are commercially available include the 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), Terol® 250 (Huntsman, The Woodlands, TX), Terol® 305 (Huntsman, The 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), Carpol® PES- 305 (Carpenter Co., Richmond, VA), Carpol® PES-295 (Carpenter Co., Richmond, VA),

[0048] In some embodiments, the foamable composition comprises one or more polyether polyols. Examples of suitable polyether polyols include, but are not limited to, polyethylene oxides, polypropylene oxides, mixed polyethylenepropylene oxides with terminal hydroxyl groups, among others. Other suitable polyols can be prepared by reacting ethylene and/or propylene oxide with an initiator having 2 to 16 or 3 to 8 hydroxyl groups as present, for example, in glycerol, pentaerythritol and carbohydrates such as sorbitol, glucose, sucrose and the like polyhydroxy compounds. Suitable polyether polyols can also include aliphatic or aromatic amine-based polyols. Exemplary polyether polyols that are commercially available include the 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), 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), 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, Ml), VORANOL® 220-110 (Dow Chemical, Midland, Ml), VORANOL® 230-238 (Dow Chemical, Midland, Ml), VORANOL® 232-027 (Dow Chemical, Midland, Ml), VORANOL® 470 (Dow Chemical, Midland, Ml), VORANOL® 360 (Dow Chemical, Midland, Ml), VORANOL® 520 (Dow Chemical, Midland, Ml), VORANOL® 391 (Dow Chemical, Midland, Ml), 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), 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.

[0049] In some embodiments, the polyether polyol is a medium functional polyether polyol. For example, the polyether polyol has a functionality of about four. In some embodiments, the polyether polyol is sucrose/glycerin 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 alkoxylation with propylene oxide and/or ethylene oxide of the Mannich bases obtained by classical Mannich reaction between phenols (e.g., phenol, p-nonylphenol), formaldehyde and alkanolamines (diethanolamine, diisopropanolamine, monoethanolamine, monoisopropanolamine, etc.). Exemplary commercially available polyether polyols include Voranol® 490 (Dow Chemical, Midland, Ml), Carpol® MX-425 (Carpenter Co., Richmond, VA), and Carpol® MX-470 (Carpenter Co., Richmond, VA).

[0050] 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.

[0051] 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.

[0052] In some embodiments, the blowing agent component comprising E- CF₃CH=CHCF₃ (HFO-1336mzz-E), C₅ hydrocarbon, and E-CHCI=CHCF₃ (HCFO-1233zd(E)) described herein is soluble in the polyol blend. In some embodiments, solubility is measured by visual assessment.

[0053] In some embodiments, the foamable composition comprises at least one catalyst for the reaction of the polyol with the polyisocyanate (/.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-dimethylamino ethyl) ether, and organometallic compounds. Such catalysts are used in an amount which increases the rate of reaction of the polyisocyanate. By way of example, typical amounts of catalyst used are about 0.1 to about 5 parts of catalyst per 100 parts by weight of polyol. In some embodiments, the foamable compositions comprise a gel catalyst, such as a non-nucleophilic gel catalyst. In some embodiments, the foamable compositions comprise a blow catalyst. In some embodiments, the foamable compositions comprise a metal catalyst. In some embodiments, the foamable composition comprises a metal catalyst and an amine catalyst.

[0054] Exemplary catalysts are disclosed, for example, in U.S. Pat. No.

5,164,419, which disclosure is incorporated herein by reference. For example, a catalyst for the trimerization of polyisocyanates, such as an alkali metal alkoxide, alkali metal carboxylate, or quaternary amine salts, may also optionally be employed herein. Such catalysts are used in an amount which measurably increases the rate of reaction of the polyisocyanate. Typical amounts of catalysts 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,N- dimethylcyclohexylamine from Evonik Industries, POLYCAT® 5, pentamethyldiethylenetriamine from Evonik Industries, and CURITHANE® 52, 2- methyl(n-methyl amino b-sodium acetate nonyl phenol) from Evonik Industries, 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), 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), 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 Woodlands, TX), ZF20 (Huntsman, The Woodlands, TX), ZF54 (Huntsman, The Woodlands, TX), tin, dibutyltin mercaptide, potassium octoate, potassium acetate, bismuth, bismuth carboxylate mixtures, and the like. [0055] In some embodiments, the foamable composition comprises a surfactant. Suitable surfactants can comprise a liquid or solid organosilicone compound. Other surfactants include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl acid sulfate esters, alkyl sulfonic esters, and alkyl arylsulfonic 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 .

[0056] In some embodiments, the foamable composition comprises a flame retardant agent. Useful flame retardant agents 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, brominecontaining diester/ether diols of tetrabromophthalic anhydride, such as a mixed ester of tetrabromophthalic anhydride with diethylene glycol and propylene glycol. Exemplary commercially available flame retardant agents include Saytex® RB-79, a reactive bromine-containing diester/ether diol of tetrabromophthalic anhydride (Albemarle Corporation, Baton Rouge, LA). In some embodiments, the flame retardant agent is tris(1-chloro-2-propyl) phosphate (TCPP).

[0057] In some embodiments, the foamable composition comprises a nucleating agent. Nucleating agents serve primarily to increase cell count and decrease 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 comprise at least one member selected from the group consisting of talc, sodium bicarbonate-citric acid mixtures, calcium silicate, and carbon dioxide, among others. In some embodiments, the foamable composition does not comprise a nucleating agent. In some embodiments, the processes provided herein are performed in the absence of a nucleating agent. Exemplary nucleating agents include, but art not limited to, talc, sodium bicarbonate-citric acid mixtures, calcium silicate, carbon dioxide, and the like.

[0058] In some embodiments, the foamable composition further comprises water.

[0059] In some embodiments, the present application further provides a process of 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.

[0060] In some embodiments, the process of forming a foam comprises: (a) adding a foamable composition disclosed herein (e.g., a B-side composition) to a composition comprising an isocyanate (e.g., an A-side composition); and (b) reacting the compositions under conditions effective to form a foam. The isocyanate or isocyanate-containing mixture can include the isocyanate and auxiliary chemicals, like catalysts, surfactants, stabilizers, chain extenders, crosslinkers, water, fire retardants, smoke suppressants, pigments, coloring materials, fillers, etc. 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,” Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporated herein by reference, can be used or adapted for use in accordance with the compositions disclosed herein.

[0061] In the process of making a polyisocyanate-based foam, the polyol(s), polyisocyanate, and other components are contacted, thoroughly mixed, and permitted to expand and cure into a cellular polymer. The particular mixing apparatus is not critical, and various types of mixing head and spray apparatus are conveniently used. It is often convenient, but not necessary, to pre-blend certain of the raw materials prior to reacting the polyisocyanate and polyols. For example, it is often useful to prepare the foamable composition (e.g., the B-side composition) disclosed herein, and then contact this composition with the polyisocyanate.

[0062] It is understood that the present application further provides a foamable composition as described herein for use in a process of preparing a foam as described herein. In some embodiments, the foamable composition described herein is useful in one or more of the processes described herein.

Foams

[0063] The present application further provides a foam 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 foam produced can include, for example, closed cell foams, open cell foams, rigid foams, flexible foams, and integral skin. In some embodiments, disclosed herein are foams prepared from the foamable compositions described herein (e.g., B-side compositions). In some embodiments, the foam is a spray foam. In some embodiments, the foam is a thermoset foam.

[0064] 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 celled polyisocyanate-based foams are useful in spray insulation, as foam-in-place appliance foams, rigid insulating board stock, or in laminates.

[0065] 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 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 exceptional thermal performance, such as can be measured by the K-factor. “K- factor,” as used herein, represents the foam’s thermal conductivity or ability to conduct heat. The K-factor is a measure of 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 insulation.

[0066] In some embodiments, the foam has a K-factor of about 0.135 Btu in/ft²h°C or less at about 24°C. In some embodiments, the foam has a K-factor of from about 0.130 Btu in/ft²h°C to about 0.135 Btu in/ft²h°C at 24°C.

[0067] In some embodiments, the foam has a K-factor of about 0.124 Btu in/ft²h°C or less at about 10°C. In some embodiments, the foam has a K-factor of from about 0.118 Btu in/ft²h°C to about 0.124 Btu in/ft²h°C at 10°C.

[0068] In some embodiments, the foam has a K-factor of about 0.118 Btu in/ft²h°C or less at about -6.7°C. In some embodiments, the foam has a K-factor of from about 0.110 Btu in/ft²h°C to about 0.118 Btu in/ft²h°C at -6.7°C.

[0069] In some embodiments, the foam has a K-factor of about 0.135 Btu in/ft²h°C or less at about 24°C, about 0.124 Btu in/ft²h°C or less at about 10°C, and about 0.118 Btu in/ft²h°C or less at about -6.7°C.

[0070] In some embodiments, the foam has a K-factor of from about 0.130 Btu in/ft²h°C to about 0.135 Btu in/ft²h°C at 24°C, from about 0.118 Btu in/ft²h°C to about 0.124 Btu in/ft²h°C at 10°C, and from about 0.110 Btu in/ft²h°C to about 0.118 Btu in/ft²h°C at -6.7°C.

[0071] In some embodiments, the foam has a K-factor of about 0.142 Btu in/ft²h°C or less at about 24°C. In some embodiments, the foam has a K-factor of from about 0.140 Btu in/ft²h°C to about 0.139 Btu in/ft²h°C at 24°C.

[0072] In some embodiments, the foam has a K-factor of about 0.129 Btu in/ft²h°C or less at about 10°C. In some embodiments, the foam has a K-factor of from about 0.127 Btu in/ft²h°C to about 0.129 Btu in/ft²h°C at 10°C. [0073] In some embodiments, the foam has a K-factor of about 0.120 Btu in/ft²h°C or less at about -6.7°C. In some embodiments, the foam has a K-factor of from about 0.116 Btu in/ft²h°C to about 0.120 Btu in/ft²h°C at -6.7°C.

[0074] In some embodiments, the foam has a K-factor of about 0.142 Btu in/ft²h°C or less at about 24°C, about 0.129 Btu in/ft²h°C or less at about 10°C, and about 0.120 Btu in/ft²h°C or less at about -6.7°C.

[0075] In some embodiments, the foam has a K-factor of from about 0.140 Btu in/ft²h°C to about 0.139 Btu in/ft²h°C at 24°C, from about 0.127 Btu in/ft²h°C to about 0.129 Btu in/ft²h°C at 10°C, and from about 0.116 Btu in/ft²h°C to about 0.120 Btu in/ft²h°C at -6.7°C.

[0076] In some embodiments, the foam has a cream time of from about 1 seconds to about 30 seconds, for example, 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 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.

[0077] In some embodiments, the foam has a gel time of from about 30 to about 70 seconds, for example, 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 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 gel time of from about 50 seconds to about 65 seconds. In some embodiments, the foam has a gel time of from about 35 seconds to about 45 seconds.

[0078] In some embodiments, the foam has a tack free time of from about 85 seconds to about 140 seconds, for example, 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 to about 115 seconds, about 90 to about 110 seconds, about 90 to about 105 seconds, about 90 to about 100 seconds, about 90 to about 95 seconds, about 95 to about 140 seconds, about 95 to about 135 seconds, about 95 to about 130 seconds, about 95 to about 125 seconds, about 95 to about 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 100 to about 120 seconds, about 100 to about 115 seconds, about 100 to about 110 seconds, about 100 to about 105 seconds, about 105 to about 140 seconds, about 105 to about 135 seconds, about 105 to about 130 seconds, about 105 to about 125 seconds, about 105 to about 120 seconds, about 105 to about 115 seconds, about 105 to about 110 seconds, about 110 to about 140 seconds, about 110 to about 135 seconds, about 110 to about 130 seconds, about 110 to about 125 seconds, about 110 to about 120 seconds, about 110 to about 115 seconds, about 115 to about 1 0 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 from about 120 seconds to about 135 seconds.

In some embodiments, the foam has a tack free time of from about 90 seconds to about 100 seconds.

[0079] In some embodiments, the foam has a density of from 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 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.

[0080] 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%.

[0081] Representative foamed products that can be made in accordance with the present disclosure include, for example: (1 ) polystyrene foam sheet for the production of disposable thermoformed packaging materials, e.g., as disclosed in U.S. Patent No. 5,204,169; (2) extruded polystyrene foam boards for use as residential and industrial sheathing and roofing materials, which may be from about 0.5 to 6 inches (1 .25 to 15 cm) thick, up to 4 feet (122 cm) wide, with cross-sectional areas of from 0.17 to 3 square feet (0.016 to 0.28 square meter), and up to 27 feet (813 meters) long, with densities of from about 1.5 to 10 pounds per cubic foot (pcf) (25 to 160 kilograms per cubic meter (kg/m³); (3) expandable foams in the form of large billets which may 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, up to 16 feet (4.8 meters) long, having a cross-sectional area of about 2 to 8 square feet (0.19 to 0.74 square meter) and a density of from 6 to 15 pcf (96 to 240 kg/m³). Such foamed products are more fully described by Stockdopole and Welsh in the Encyclopedia of Polymer Science and Engineering, vol. 16, pages 193-205, John Wiley & Sons, 1989; hereby incorporated by reference.

EXAMPLES

[0082] 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, one skilled in the art can ascertain the preferred features, and without departing from the spirit and scope thereof, can make various changes and modifications to adapt it to various uses and conditions.

[0083] The following components were used to prepare formulations of the Examples:

[0084] Polyol is Stepanpol® PS-2352, is an aromatic polyester polyol available from Stepan Company.

[0085] Stabilizer is Tegostab® B 8871 , a modified silicone stabilizer, available from Evonik Industries, AG. [0086] Amine Catalyst is Polycat® 5, is a tertiary amine catalyst, available from Evonik Industries, AG.

[0087] Metal Catalyst is Dabco® K-15, is a potassium-based catalyst, available from Evonik Industries.

[0088] Flame retardant is TCPP.

[0089] Isocyanate is PAPI-27 is a polymethylene polyphenylisocyanate containing MDI, available from DowDuPont Chemical Company.

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

The B-side components were weighed as a master batch on a mass balance and mixed together in a 1 L plastic beaker, excluding the blowing agents. The master batch was then divided equally across three separate 1 L beakers, before adding the blowing agent and mixing until fully incorporated. The blowing agents were added in the order of decreasing solubility in the B-side system (e.g., first HCFO-1233zd-E, followed by isopentane, before lastly adding HFO- 1336mzz-E). The isocyanate (A-side), primarily PAPI 27, was weighed in a 500 mL plastic beaker with an extra 15 wt% for sufficient head-room pouring, and poured into the B-side mixture. The A+B mixture was placed into a mixing head and mixed for 3 s at 4000 rpm. After mixing, the mixed A+B solution was quickly poured into a wax coated cardboard box and a timer was started. The resulting foams were placed under an air-hood for 24 hours to complete the polyurethane reaction. The foam was then cut into 8”x8”x1 .5” blocks. The foam blocks were tested for thermal conductivity utilizing a heat flow meter per ASTM C-518.

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

[0090] Table 1 shows a summary of formulations (A-side and B-side formulations) comprising a ternary blowing agent blend of HFO-1336mzz-E, Isopentane, and HCFO-1233zd-E, which were prepared according to the general procedures described in Example 1.

TABLE 1.

[0091] The blowing agent components of Table 1 , as weight percent (wt%) of the total amount of blowing agent, are as follows:

[0092] Control formulation: 90 wt% HCFO-1233zd-E, 10 wt% isopentane, and 0 wt% HFO-1336mzz-E relative to the total mass of blowing agent present in the B-side.

[0093] Formulation 2A: 80 wt% HCFO-1233zd-E, 10 wt% isopentane, and 10 wt% HFO-1336mzz-E relative to the total mass of blowing agent present in the B- side.

[0094] Formulation 2B: 75 wt% HCFO-1233zd-E, 10 wt% isopentane, and 15 wt% HFO-1336mzz-E relative to the total mass of blowing agent present in the B- side. [0095] Formulation 2C: 60 wt% HCFO-1233zd-E, 20 wt% isopentane, and 20 wt% HFO-1336mzz-E relative to the total mass of blowing agent present in the B- side.

[0096] Formulation 2D: 45 wt% HCFO-1233zd-E, 25 wt% Isopentane, and 35 wt% HFO-1336mzz-E relative to the total mass of blowing agent present in the 13- side.

[0097] After testing, data values were compiled for analysis and are shown below in Table 2 and FIG. 1 .

TABLE 2.

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

[0100] Theoretical calculations provided information on where these improvement areas may lie. FIG. 2 shows ternary azeotrope predictions from calculations, where darker colors indicate stronger azeotrope areas. FIG. 2 illustrates the region explored for the foam synthesis described above. Notably, the best performance did not align directly with the predicted azeotrope. Without being bound by theory, it is believed that other factors are involved thereby resulting in the unexpected behavior.

[0101] As we replace the 1233zd with 1336E, a decrease in thermal conductivity is observed, and continues to improve through about 15 weight percent. At about 20% 1336E the trend reverses, and the thermal conductivity increases. This behavior is unexpected as the vapor thermal conductivity of 1336E is greater than 1233zd, based on the thermal conductivity of the gases, it is expected that the thermal conductivity would increase as the 1336E replaces the 1233zd.

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

[0102] Table 3 shows a summary of formulations (A-side and B-side formulations) comprising a ternary blowing agent blend of HFO-1336mzz-E, cyclopentane, and HCFO-1233zd-E, which were prepared according to the general procedures described in Example 1.

TABLE 3.

[0103] The blowing agent components of 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 relative to the total mass of blowing agent present in the B-side.

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

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

[0107] Formulation 3C: 70 wt% HCFO-1233zd-E, 10 wt% cyclopentane, and 20 wt% HFO-1336mzz-E relative to the total mass of blowing agent present in the B-side. [0108] Formulation 3D: 65 wt% HCFO-1233zd-E, 10 wt% cyclopentane, and 25 wt% HFO-1336mzz-E relative to the total mass of blowing agent present in the B-side.

[0109] After testing, data values were compiled for analysis and are shown below in Table 4 and FIG. 3.

TABLE 4.

[0110] It was found that the greatest k-factor performance was achieved in Foam 3B, prepared using a blowing agent component containing 75 wt% HCFO- 1233zd-E, 10 wt% cyclopentane, and 15 wt% HFO-1336mzz-E relative to the total mass of blowing agent present in the B-side.

[0111] Theoretical calculations provided information on where these improvement areas may lie. FIG. 4 show ternary azeotrope predictions from calculations, where darker colors indicate stronger azeotrope areas. FIG. 4 illustrates the region explored for the foam synthesis described above. Notably, the best performance did not align directly with the predicted azeotrope. Without being bound by theory, it is believed that other factors are involved thereby resulting in the unexpected behavior.

OTHER EMBODIMENTS

[0112] 1. In some embodiments, the present application provides a process of forming a foam, comprising reacting or extruding a foamable composition under conditions effective to form a foam, wherein the foamable composition comprises a blowing agent component comprising:

(i) about 5 to about 40 weight percent E-CF3CH=CHCF3 (HFO- 1336mzz-E);

(ii) about 8 to about 30 weight percent Cs hydrocarbon; and

(iii) about 40 to about 85 weight percent E-CHCI=CHCF3 (HCFO- 1233zd(E)).

[0113] 2. The process of embodiment 1 , wherein the blowing agent component comprises about 10 to about 35 weight percent E-CFsCH^CHCFs (HFO-1336mzz-E).

[0114] 3. The process of embodiment 1 , wherein the blowing agent component comprises about 10 to about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E).

[0115] 4. The process of any one of embodiments 1 to 3, wherein the blowing agent component comprises about 10 to about 25 weight percent Cs hydrocarbon.

[0116] 5. The process of any one of embodiments 1 to 3, wherein the blowing agent component comprises about 8 to about 12 weight percent Cs hydrocarbon.

[0117] 6. The process of any one of embodiments 1 to 5, wherein the Cs hydrocarbon is selected from n-pentane, isopentane, and cyclopentane.

[0118] 7. The process of any one of embodiments 1 to 5, wherein the Cs hydrocarbon is cyclopentane.

[0119] 8. The process of any one of embodiments 1 to 5, wherein the Cs hydrocarbon is isopentane.

[0120] 9. The process of any one of embodiments 1 to 8, wherein the blowing agent component comprises about 65 to about 80 weight percent E- CHCI=CHCF₃ (HCFO-1233zd(E). [0121] 10. The process of any one of embodiments 1 to 8, wherein the blowing agent component comprises about 45 to about 80 weight percent E- CHCI=CHCF₃ (HCFO-1233zd(E).

[0122] 11 . The process of embodiment 1 , wherein the blowing agent component comprises:

(i) about 10 to about 25 weight percent E-CF3CH=CHCF3 (HFO- 1336mzz-E);

(ii) about 10 weight percent cyclopentane; and

(iii) about 65 to about 80 weight percent E-CHCI=CHCF3 (HCFO- 1233zd(E)).

[0123] 12. The process of embodiment 1 or 11 , wherein the process forms a foam having a K-factor of about 0.135 Btu in/ft²h°C or less at about 24°C.

[0124] 13. The process of embodiment 1 or 11 , wherein the process forms a foam having a K-factor of from about 0.130 Btu in/ft²h°C to about 0.135 Btu in/ft²h°C at 24°C.

[0125] 14. The process of embodiment 1 or 11 , wherein the process forms a foam having a K-factor of about 0.124 Btu in/ft²h°C or less at about 10°C.

[0126] 15. The process of embodiment 1 or 11 , wherein the process forms a foam having a K-factor of from about 0.118 Btu in/ft²h°C to about 0.124 Btu in/ft²h°C at 10°C.

[0127] 16. The process of embodiment 1 or 11 , wherein the process forms a foam having a K-factor of about 0.118 Btu in/ft²h°C or less at about -6.7°C.

[0128] 17. The process of embodiment 1 or 11 , wherein the process forms a foam having a K-factor of from about 0.110 Btu in/ft²h°C to about 0.118 Btu in/ft²h°C at -6.7°C.

[0129] 18. The process of embodiment 1 or 11 , wherein the process forms a foam having a K-factor of about 0.135 Btu in/ft²h°C or less at about 24°C, about 0.124 Btu in/ft²h°C or less at about 10°C, and about 0.118 Btu in/ft²h°C or less at about -6.7°C.

[0130] 19. The process of embodiment 1 or 11 , wherein the process forms a foam having a K-factor of from about 0.130 Btu in/ft²h°C to about 0.135 Btu in/ft²h°C at 24°C, from about 0.118 Btu in/ft²h°C to about 0.124 Btu in/ft²h°C at 10°C, and from about 0.110 Btu in/ft²h°C to about 0.118 Btu in/ft²h°C at -6.7°C.

[0131] 20. The process of any one of embodiments 1 and 11 to 19, wherein the process forms a foam having a cream time of from about 20 seconds to about 30 seconds.

[0132] 21 . The process of any one of embodiments 1 and 11 to 20, wherein the process forms a foam having a gel time of from about 50 seconds to about 65 seconds.

[0133] 22. The process of any one of embodiments 1 and 11 to 21 , wherein the process forms a foam having a tack free time of from about 120 seconds to about 135 seconds.

[0134] 23. The process of any one of embodiments 1 and 11 to 22, wherein the process forms a foam having a density of from about 2.90 pcf to about 3.10 pcf.

[0135] 24. The process of any one of embodiments 1 and 11 to 23, wherein the process forms a foam having a close cell content of from about 90% to about 95%.

[0136] 25. The process of any one of embodiments 1 and 11 to 24, wherein the blowing agent component comprises: about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCI=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-CHCI=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-CHCI=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-CHC CHCFs (HCFO-1233zd(E)).

[0137] 26. The process of embodiment 1 , wherein the blowing agent component comprises:

(i) about 10 to about 30 weight percent E-CF3CH=CHCF3 (HFO- 1336mzz-E);

(ii) about 10 to about 25 weight percent isopentane; and

(iii) about 45 to about 80 weight percent E-CHCI=CHCF3 (HCFO- 1233zd(E)).

[0138] 27. The process of embodiment 1 or 26, wherein the process forms a foam having a K-factor of about 0.142 Btu in/ft²h°C or less at about 24°C.

[0139] 28. The process of embodiment 1 or 26, wherein the process forms a foam having a K-factor of from about 0.140 Btu in/ft²h°C to about 0.139 Btu in/ft²h°C at 24°C.

[0140] 29. The process of embodiment 1 or 26, wherein the process forms a foam having a K-factor of about 0.129 Btu in/ft²h°C or less at about 10°C.

[0141] 30. The process of embodiment 1 or 26, wherein the process forms a foam having a K-factor of from about 0.127 Btu in/ft²h°C to about 0.129 Btu in/ft²h°C at 10°C.

[0142] 31 . The process of embodiment 1 or 26, wherein the process forms a foam having a K-factor of about 0.120 Btu in/ft²h°C or less at about -6.7°C. [0143] 32. The process of embodiment 1 or 26, wherein the process forms a foam having a K-factor of from about 0.116 Btu in/ft²h°C to about 0.120 Btu in/ft²h°C at -6.7°C.

[0144] 33. The process of embodiment 1 or 26, wherein the process forms a foam having a K-factor of about 0.142 Btu in/ft²h°C or less at about 24°C, about 0.129 Btu in/ft²h°C or less at about 10°C, and about 0.120 Btu in/ft²h°C or less at about -6.7°C.

[0145] 34. The process V, wherein the process forms a foam having a K- factor of from about 0.140 Btu in/ft²h°C to about 0.139 Btu in/ft²h°C at 24°C, from about 0.127 Btu in/ft²h°C to about 0.129 Btu in/ft²h°C at 10°C, and from about 0.116 Btu in/ft²h°C to about 0.120 Btu in/ft²h°C at -6.7°C.

[0146] 35. The process of any one of embodiments 1 and 26 to 34, wherein the process forms a foam having a cream time of from about 5 seconds to about 12 seconds.

[0147] 36. The process of any one of embodiments 1 and 26 to 35, wherein the process forms a foam having a gel time of from about 35 seconds to about 45 seconds.

[0148] 37. The process of any one of embodiments 1 and 26 to 36, wherein the process forms a foam having a tack free time of from about 90 seconds to about 100 seconds.

[0149] 38. The process of any one of embodiments 1 and 26 to 37, wherein the process forms a foam having a density of from about 2.53 pcf to about 2.56 pcf.

[0150] 39. The process of any one of embodiments 1 and 26 to 38, wherein the process forms a foam having a close cell content of from about 96% to about 99%.

[0151] 40. The process of any one of embodiments 1 and 26 to 39, wherein the blowing agent component comprises: about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHCI=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-CHCI=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-CHC CHCFs (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-CHCI=CHCF3 (HCFO-1233zd(E)).

[0152] 41 . The process of 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 agent, and at least one nucleating agent.

[0153] 42. The process of any one of embodiments 1 to 40, wherein the foamable composition comprises at least one polyol.

[0154] 43. The process of embodiment 41 or 42, wherein the polyol is a polyester polyol.

[0155] 44. The process of any one of embodiments 1 to 40, wherein the foamable composition comprises at least one catalyst.

[0156] 45. The process of any one of embodiments 1 to 40, wherein the foamable composition comprises a metal catalyst and an amine catalyst.

[0157] 46. The process of any one of embodiments 1 to 40, wherein the foamable composition comprises a surfactant.

[0158] 47. The process of embodiment 41 or 46, wherein the surfactant is a silicone surfactant. [0159] 48. The process of any one of embodiments 1 to 40, wherein the foamable composition comprises water.

[0160] 49. The process of any one of embodiments 1 to 40, wherein the foamable composition comprises a flame retardant agent.

[0161] 50. The process of any one of embodiments 1 to 40, wherein the foamable composition comprises a nucleating agent.

[0162] 51 . The process of any one of embodiments 1 to 40 and 42 to 49, wherein the process is performed in the absence of a nucleating agent.

[0163] 52. The process of any one of embodiments 1 to 51 , wherein the foam is a spray foam.

[0164] 53. The process of any one of embodiments 1 to 52, wherein the foam is a thermoset foam.

[0165] 54. The process of any one of embodiments 1 to 53, wherein the foam is a polyurethane foam or a polyisocyanurate foam.

[0166] 55. The process of any one of embodiments 1 to 54, wherein the foam is a closed cell foam.

[0167] 56. The process of embodiment 1 , wherein the foamable composition comprises a blowing agent component comprising: about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCI=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-CHCI=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-CHCI=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-CHCI=CHCF3 (HCFO-1233zd(E)); and at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant agent.

[0168] 57. The process of embodiment 1 , wherein the foamable composition comprises a blowing agent component comprising: about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHC CHCFs (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-CHCI=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-CHCI=CHCF3 (HCFO-1233zd(E)); or about 10 weight percent E-CFsCH^CHCFs (HFO-1336mzz-E), about 10 weight percent isopentane, and about 80 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E)); and at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant agent.

[0169] 58. A foamable composition comprising a blowing agent component, wherein the blowing agent component comprises:

(i) about 5 to about 40 weight percent E-CF3CH=CHCF3 (HFO- 1336mzz-E);

(ii) about 8 to about 30 weight percent Cs hydrocarbon; and

(iii) about 40 to about 85 weight percent E-CHCI=CHCF3 (HCFO- 1233zd(E)). [0170] 59. A foam, prepared according to the process of any one of embodiments 1 to 57.

[0171] 60. The foam of embodiment 59, which is a closed cell polyisocyanurate foam.

[0172] 61 . The foam of embodiment 59, which is a closed cell polyurethane foam.

[0173] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and 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 appreciated by those persons having ordinary skill in the art(s) to which the present invention relates that any of the features described herein in respect of any particular aspect and/or embodiment of the present invention can be combined with one or more of any of the other features of any other aspects and/or embodiments of the present invention described herein, with modifications as appropriate to ensure compatibility of the combinations. Such combinations are considered to be part of the present invention contemplated by this disclosure.

Claims

WHAT IS CLAIMED IS:

1 . A process of forming a foam, comprising reacting or extruding a foamable composition under conditions effective to form a foam, wherein the foamable composition comprises a blowing agent component comprising: about 5 to about 40 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E); about 8 to about 30 weight percent Cs hydrocarbon; and about 40 to about 85 weight percent E-CHC CHCFs (HCFO-1233zd(E)).

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

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

4. The process of claim 1 , wherein the blowing agent component comprises about 10 to about 25 weight percent Cs hydrocarbon.

5. The process of claim 1 , wherein the blowing agent component comprises about 8 to about 12 weight percent Cs hydrocarbon.

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

7. The process of claim 1 , wherein the Cs hydrocarbon is cyclopentane.

8. The process of claim 1 , wherein the Cs hydrocarbon is isopentane.

9. The process of claim 1 , wherein the blowing agent component comprises about 65 to about 80 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E).

10. The process of claim 1 , wherein the blowing agent component comprises about 45 to about 80 weight percent E-CHCI=CHCF3 (HCFO-1233zd(E).

11 . The process of claim 1 , wherein the blowing agent component comprises: 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-CHC CHCFs (HCFO-1233zd(E)).

12. The process of claim 11 , wherein the process forms a foam having a K- factor of about 0.135 Btu in/ft²h°C or less at about 24°C.

13. The process of claim 11 , wherein the process forms a foam having a K- factor of from about 0.130 Btu in/ft²h°C to about 0.135 Btu in/ft²h°C at 24°C.

14. The process of claim 11 , wherein the process forms a foam having a K- factor of about 0.124 Btu in/ft²h°C or less at about 10°C.

15. The process of claim 11 , wherein the process forms a foam having a K- factor of from about 0.118 Btu in/ft²h°C to about 0.124 Btu in/ft²h°C at 10°C.

16. The process of claim 11 , wherein the process forms a foam having a K- factor of about 0.118 Btu in/ft²h°C or less at about -6.7°C.

17. The process of claim 11 , wherein the process forms a foam having a K- factor of from about 0.110 Btu in/ft²h°C to about 0.118 Btu in/ft²h°C at -6.7°C.

18. The process of claim 11 , wherein the process forms a foam having a K- factor of about 0.135 Btu in/ft²h°C or less at about 24°C, about 0.124 Btu in/ft²h°C or less at about 10°C, and about 0.118 Btu in/ft²h°C or less at about - 6.7°C.

19. The process of claim 11 , wherein the process forms a foam having a K- factor of from about 0.130 Btu in/ft²h°C to about 0.135 Btu in/ft²h°C at 24°C, from about 0.118 Btu in/ft²h°C to about 0.124 Btu in/ft²h°C at 10°C, and from about 0.110 Btu in/ft²h°C to about 0.118 Btu in/ft²h°C at -6.7°C.

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

21 . 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. 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. 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 close cell content of from about 90% to about 95%.

25. The process of claim 1 , wherein the blowing agent component comprises: about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCI=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-CHCI=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-CHCI=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-CHCI=CHCF3 (HCFO-1233zd(E)).

26. The process of claim 1 , wherein the blowing agent component comprises: 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-CHCI=CHCF3 (HCFO-1233zd(E)).

27. The process of claim 26, wherein the process forms a foam having a K- factor of about 0.142 Btu in/ft²h°C or less at about 24°C.

28. The process of claim 26, wherein the process forms a foam having a K- factor of from about 0.140 Btu in/ft²h°C to about 0.139 Btu in/ft²h°C at 24°C.

29. The process of claim 26, wherein the process forms a foam having a K- factor of about 0.129 Btu in/ft²h°C or less at about 10°C.

30. The process of claim 26, wherein the process forms a foam having a K- factor of from about 0.127 Btu in/ft²h°C to about 0.129 Btu in/ft²h°C at 10°C.

31 . The process of claim 26, wherein the process forms a foam having a K- factor of about 0.120 Btu in/ft²h°C or less at about -6.7°C.

32. The process of claim 26, wherein the process forms a foam having a K- factor of from about 0.116 Btu in/ft²h°C to about 0.120 Btu in/ft²h°C at -6.7°C.

33. The process of claim 26, wherein the process forms a foam having a K- factor of about 0.142 Btu in/ft²h°C or less at about 24°C, about 0.129 Btu in/ft²h°C or less at about 10°C, and about 0.120 Btu in/ft²h°C or less at about - 6.7°C.

34. The process of claim 26, wherein the process forms a foam having a K- factor of from about 0.140 Btu in/ft²h°C to about 0.139 Btu in/ft²h°C at 24°C, from about 0.127 Btu in/ft²h°C to about 0.129 Btu in/ft²h°C at 10°C, and from about 0.116 Btu in/ft²h°C to about 0.120 Btu in/ft²h°C at -6.7°C.

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

38. 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. The process of claim 26, wherein the process forms a foam having a close cell content of from about 96% to about 99%.

40. The process of claim 1 , wherein the blowing agent component comprises: about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHCI=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-CHCI=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-CHCI=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-CHC CHCFs (HCFO-1233zd(E)).

41 . 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 agent, and at least one nucleating agent.

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

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

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

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

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

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

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

49. The process of claim 18, wherein the foamable composition comprises a flame retardant agent.

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

51 . The process of claim 3, wherein the process is performed 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. 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 process of claim 1 , wherein the foamable composition comprises a blowing agent component comprising: about 25 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 10 weight percent cyclopentane, and about 65 weight percent E-CHCI=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-CHCI=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-CHCI=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-CHCI=CHCF3 (HCFO-1233zd(E)); and at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant agent.

57. The process of claim 1 , wherein the blowing agent component comprises: about 30 weight percent E-CF3CH=CHCF3 (HFO-1336mzz-E), about 25 weight percent isopentane, and about 45 weight percent E-CHCI=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-CHCI=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-CHCI=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-CHCI=CHCF3 (HCFO-1233zd(E)); and at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant agent.

58. A foamable composition comprising a blowing agent component, 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 Cs hydrocarbon; and about 40 to about 85 weight percent E-CHC CHCFs (HCFO-1233zd(E)).

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

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

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