Foams improved in thermal insulation performance

Abstract

To provide foams improved in thermal insulation and thermal performance, and methods of forming the foams.SOLUTION: A method of forming foam comprises reacting or extruding a foamable composition under conditions effective for forming the foam. The composition comprises either: about 3.0 to about 4.0% of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3 and about 13.0 to about 14.0% of cyclopentane; about 10.0 to about 11.0% of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3 and about 9.0 to about 10.0% of cyclopentane; or about 14.0 to about 15.0% of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3 and about 7.0 to about 8.0% of cyclopentane. The composition further comprises one or more additional components selected from at least one polyol, at least one catalyst, at least one surfactant, water, flame retardants, and at least one nucleating agent.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 62 / 667,192, filed May 4, 2018, the disclosure of which is incorporated herein by reference in its entirety.

[0002] FIELD OF THEINVENTION The present invention relates to foams with improved insulation and thermal performance, methods for forming the foams, and foamable compositions useful for preparing the foams. The methods described herein include reacting or extruding a foamable composition comprising (i) a compound selected from E-CHCl=CHCF3, Z-CF3CH=CHCF3, and E-CF3CH=CHCF3, or any mixture thereof, and (2) a C5 hydrocarbon (e.g., cyclopentane) under conditions effective to form a foam. [Background technology]

[0003] Closed-cell polyisocyanate-based foams are widely used for insulation purposes, for example, in the construction of buildings and in the manufacture of energy-efficient appliances. In the construction industry, polyurethane (polyisocyanurate) boards are used in roofing and siding for their insulating and load-bearing properties. Injected and sprayed polyurethane foams are widely used in a variety of applications, including insulating roofing, insulating large structures such as storage tanks, insulating equipment such as refrigerators and freezers, insulating refrigerated trucks and rail cars, and the like.

[0004] All of these different types of polyurethane foams require a blowing (expansion) agent for their production. 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 feature of insulating value. Historically, polyurethane foams have used CFCs (chlorofluorocarbons, e.g., CFC-11, trichlorofluoromethane), HCFCs (hydrochlorofluorocarbons, e.g., HCFC-141b, 1,1-dichloro-1-fluoroethane), and HFCs (hydrofluorofluorocarbons, e.g., HFC-245fa, HFC-365mfc) as the primary blowing agents.

[0005] CFCs generally produce foams with good thermal insulation, low flammability, and excellent dimensional stability. However, despite these advantages, CFCs have been disadvantaged due to the presumed contribution of chlorine-containing molecules to stratospheric ozone depletion. Furthermore, the manufacture and use of CFCs has been restricted by the Montreal Protocol. HCFCs have been proposed as replacements for CFCs and are currently employed as blowing agents in foams. However, HCFCs also contribute to stratospheric ozone depletion, and as a result, their use is also under scrutiny. The Montreal Protocol is intended to eventually phase out the widespread use of HCFCs. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Provisional Patent Application No. 62 / 667,192 Summary of the Invention [Means for solving the problem]

[0007] The present application provides, inter alia, a foam foaming composition comprising: i) about 0.3 to about 16.5 wt. % E-CF3CH=CHCF3; and ii) about 6.5 to about 15.5 wt. % cyclopentane.

[0008] The present application further provides a method of forming a foam comprising reacting or extruding the foamable composition described herein under conditions effective to form a foam.

[0009] The present application further provides foams (e.g., polyisocyanurates, or polyurethanes) prepared from the foamable compositions according to the methods described herein.

[0010] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. Methods and materials for use in the present invention are described herein, and other suitable methods and materials known in the art may be used. The materials, methods, and examples are merely illustrative 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 description of the drawings]

[0011] [Figure 1] Measured thermal performance (K-factor at 75° F., 24° C.) of the foams is shown as a function of the amount of HFO or HCFO used to prepare the B-side composition. The mole % shown is based on the total amount of HFO or HCFO, cyclopentane, and water used to prepare the B-side composition. [Diagram 2] Figure 1 shows the improvement in measured thermal performance (K-factor at 75°F, 24°C) of the foam as a function of the amount of HFO or HCFO used to prepare the B-side composition. The mole % shown is based on the combined amount of HFO or HCFO, cyclopentane, and water used to prepare the B-side composition. [Diagram 3]Measured thermal performance (K-factor at 20° F., -6.7° C.) of foams as a function of the amount of HFO or HCFO used to prepare the B-side composition. The mole % shown is based on the combined amount of HFO or HCFO, cyclopentane, and water used to prepare the B-side composition. [Figure 4] Figure 1 shows the improvement in foam thermal performance (K-factor at 20°F, -6.7°C) as a function of the amount of HFO or HCFO used to prepare the B-side composition. The mole % shown is based on the combined amount of HFO or HCFO, cyclopentane, and water used to prepare the B-side composition. [Diagram 5] 1 shows comparative thermal performance (K-factor at 75° F., 24° C.) of foams prepared from B-side compositions containing 0.37 wt. % HFO or HCFO and cyclopentane, isopentane, or n-pentane. [Figure 6] 1 shows comparative thermal performance (K-factor at 50° F., 10° C.) of foams prepared from B-side compositions containing 0.37 wt. % HFO or HCFO and cyclopentane, isopentane, or n-pentane. [Figure 7] 1 shows comparative thermal performance (K-factor at 20° F., −6.7° C.) of foams prepared from B-side compositions containing 0.37 wt. % HFO or HCFO and cyclopentane, isopentane, or n-pentane. [Figure 8] FIG. 1 shows comparative thermal performance at 75° F. (24° C.), 50° F. (10° C.), and 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 0.37 wt. % HFO or HCFO and cyclopentane. [Figure 9] FIG. 1 shows comparative thermal performance at 75° F. (24° C.), 50° F. (10° C.), and 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 0.37 wt. % HFO or HCFO and isopentane. [Figure 10] FIG. 1 shows comparative thermal performance at 75° F. (24° C.), 50° F. (10° C.), and 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 0.37 wt. % HFO or HCFO and n-pentane. [Figure 11A] FIG. 11A shows comparative thermal performance at 75° F. (24° C.) of foams prepared from B-side compositions containing 10 mol % HFO or HCFO and cyclopentane (FIG. 11A). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 11B] FIG. 11B shows comparative thermal performance at 75° F. (24° C.) of foams prepared from B-side compositions containing 10 mol % HFO or HCFO and isopentane (FIG. 11B). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 11C] FIG. 11C shows comparative thermal performance at 75° F. (24° C.) of foams prepared from B-side compositions containing 10 mol % HFO or HCFO and n-pentane (FIG. 11C). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 12A] FIG. 12A shows comparative thermal performance at 75° F. (24° C.) of foams prepared from B-side compositions containing 30 mol % HFO or HCFO and cyclopentane (FIG. 12A). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 12B] FIG. 12B shows comparative thermal performance at 75° F. (24° C.) of foams prepared from B-side compositions containing 30 mol % HFO or HCFO and isopentane (FIG. 12B). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 12C] FIG. 12C shows comparative thermal performance at 75° F. (24° C.) of foams prepared from B-side compositions containing 30 mol % HFO or HCFO and n-pentane (FIG. 12C). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 13A] FIG. 13A shows comparative thermal performance at 75° F. (24° C.) of foams prepared from B-side compositions containing 50 mol % HFO or HCFO and cyclopentane (FIG. 13A). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 13B]FIG. 13B shows comparative thermal performance at 75° F. (24° C.) of foams prepared from B-side compositions containing 50 mol % HFO or HCFO and isopentane (FIG. 13B). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 13C] FIG. 13C shows comparative thermal performance at 75° F. (24° C.) of foams prepared from B-side compositions containing 50 mol % HFO or HCFO and n-pentane (FIG. 13C). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 14A] FIG. 14A shows comparative thermal performance at 50° F. (10° C.) of foams prepared from B-side compositions containing 10 mol % HFO or HCFO and cyclopentane (FIG. 14A). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 14B] FIG. 14B shows comparative thermal performance at 50° F. (10° C.) of foams prepared from B-side compositions containing 10 mol % HFO or HCFO and isopentane (FIG. 14B). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 14C] FIG. 14C shows comparative thermal performance at 50° F. (10° C.) of foams prepared from B-side compositions containing 10 mol % HFO or HCFO and n-pentane (FIG. 14C). Initial thermal performance and after aging at 70° C. for 7 days are shown. [Figure 15A] FIG. 15A shows comparative thermal performance at 50° F. (10° C.) of foams prepared from B-side compositions containing 30 mol % HFO or HCFO and cyclopentane (FIG. 15A). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 15B] FIG. 15B shows comparative thermal performance at 50° F. (10° C.) of foams prepared from B-side compositions containing 30 mol % HFO or HCFO and isopentane (FIG. 15B). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 15C]FIG. 15C shows comparative thermal performance at 50° F. (10° C.) of foams prepared from B-side compositions containing 30 mol % HFO or HCFO and n-pentane (FIG. 15C). Initial thermal performance and after aging at 70° C. for 7 days are shown. [Figure 16A] FIG. 16A shows comparative thermal performance at 50° F. (10° C.) of foams prepared from B-side compositions containing 50 mol % HFO or HCFO and cyclopentane (FIG. 16A). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 16B] FIG. 16B shows comparative thermal performance at 50° F. (10° C.) of foams prepared from B-side compositions containing 50 mol % HFO or HCFO and isopentane (FIG. 16B). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 16C] FIG. 16C shows comparative thermal performance at 50° F. (10° C.) of foams prepared from B-side compositions containing 50 mol % HFO or HCFO and n-pentane (FIG. 16C). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 17A] FIG. 17A shows comparative thermal performance at 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 10 mol % HFO or HCFO and cyclopentane (FIG. 17A). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 17B] FIG. 17B shows comparative thermal performance at 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 10 mol % HFO or HCFO and isopentane (FIG. 17B). Initial thermal performance and after aging at 70° C. for 7 days are shown. [Figure 17C] FIG. 17C shows comparative thermal performance at 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 10 mol % HFO or HCFO and n-pentane (FIG. 17C). Initial thermal performance and after aging at 70° C. for 7 days are shown. [Figure 18A]FIG. 18A shows comparative thermal performance at 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 30 mol % HFO or HCFO and cyclopentane (FIG. 18A). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 18B] FIG. 18B shows comparative thermal performance at 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 30 mol % HFO or HCFO and isopentane (FIG. 18B). Initial thermal performance and after aging at 70° C. for 7 days are shown. [Figure 18C] FIG. 18C shows comparative thermal performance at 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 30 mol % HFO or HCFO and n-pentane (FIG. 18C). Initial thermal performance and after aging at 70° C. for 7 days are shown. [Figure 19A] FIG. 19A shows comparative thermal performance at 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 50 mol % HFO or HCFO and cyclopentane (FIG. 19A). Shown are initial thermal performance and thermal performance after aging at 70° C. for 7 days. [Figure 19B] FIG. 19B shows comparative thermal performance at 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 50 mol % HFO or HCFO and isopentane (FIG. 19B). Initial thermal performance and thermal performance after aging at 70° C. for 7 days are shown. [Figure 19C] FIG. 19C shows comparative thermal performance at 20° F. (−6.7° C.) of foams prepared from B-side compositions containing 50 mol % HFO or HCFO and n-pentane (FIG. 19C). Initial thermal performance and after aging at 70° C. for 7 days are shown. [Figure 20A] The thermal performance of representative foams prepared from the B-side composition described in Example 3 is shown as a function of aging at 70° C. for 14 days. The data is shown as percent improvement compared to foams prepared using cyclopentane as the blowing agent. Thermal performance was analyzed at 75° F. (FIG. 20A). [Figure 20B]The thermal performance of representative foams prepared from the B-side composition described in Example 3 is shown as a function of aging at 70° C. for 14 days. The data is shown as percent improvement compared to foams prepared using cyclopentane as the blowing agent. Thermal performance was analyzed at 50° F. (FIG. 20B). [Figure 20C] The thermal performance of representative foams prepared from the B-side composition described in Example 3 is shown as a function of aging at 70° C. for 14 days. Data is shown as percent improvement compared to foams prepared using cyclopentane as the blowing agent. Thermal performance was analyzed at 20° F. (FIG. 20C). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Polyisocyanurate (PIR) foams are an important and growing market segment in the rigid insulation industry due to their superior 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. Thus, many HFOs have no or very low global warming potential (GWP) and do not contribute to stratospheric ozone loss and global warming. HFOs have been shown to have improved insulation performance compared to C5 hydrocarbons, but are significantly more expensive. Thus, there is a need to add a minimum amount of HFO to C5 hydrocarbons to maximize the improvement in insulation performance.

[0013] Spray polyurethane foam (SPF) is an important and growing 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 important for efficient application and performance parameters, including density and surface appearance, are important. Such foams are also applied in situ to the structure of interest under a variety of environmental conditions, including cold winter temperatures. Typical physical foam expansion agents require heat to evaporate and expand. This becomes difficult at low temperatures when catalysis of polyurethane polymerization slows down, 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.

[0014] Foamable composition and method for preparing foam The present application provides a method of forming a foam comprising reacting or extruding a foamable composition comprising: i) a compound selected from E-CF3CH=CHCF3 (HFO-1336mzz-E), Z-CF3CH=CHCF3 (HFO-1336mzz-Z), and E-CHCl=CHCF3 (HCFO-1233zd-E), or any mixture thereof; and ii) a C5 hydrocarbon, under conditions effective to form a foam.

[0015] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) E-CF3CH=CHCF3 (HFO-1336mzz-E); and ii) a C5 hydrocarbon, under conditions effective to form a foam.

[0016] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) Z-CFCH=CHCF (HFO-1336mzz-Z); and ii) a C hydrocarbon, under conditions effective to form a foam.

[0017] In some embodiments, the method comprises reacting or extruding a foamable composition comprising i) a mixture of Z-CF3CH=CHCF3 (HFO-1336mzz-Z) and E-CF3CH=CHCF3 (HFO-1336mzz-E) and ii) a C5 hydrocarbon under conditions effective to form a foam.

[0018] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) E-CHCl=CHCF3 (HCFO-1233zd-E); and ii) a C5 hydrocarbon under conditions effective to form a foam.

[0019] In some embodiments, the method comprises reacting or extruding a foamable composition comprising i) a mixture of Z-CF3CH=CHCF3 (HFO-1336mzz-Z) and E-CHCl=CHCF3 (HCFO-1233zd-E) and ii) a C5 hydrocarbon under conditions effective to form a foam.

[0020] In some embodiments, the method comprises reacting or extruding a foamable composition comprising i) a mixture of E-CF3CH=CHCF3 (HFO-1336mzz-E) and E-CHCl=CHCF3 (HCFO-1233zd-E) and ii) a C5 hydrocarbon under conditions effective to form a foam.

[0021] In some embodiments, the C5 hydrocarbon is a C5 alkane. In some embodiments, the C5 hydrocarbon is selected from cyclopentane, isopentane, and n-pentane. In some embodiments, the C5 hydrocarbon is cyclopentane. In some embodiments, the C5 hydrocarbon is isopentane. In some embodiments, the C5 hydrocarbon is n-pentane.

[0022] In some embodiments, the present application provides a method of forming a foam comprising reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt. % of a compound selected from E-CF3CH=CHCF3 (HFO-1336mzz-E), Z-CF3CH=CHCF3 (HFO-1336mzz-Z), and E-CHCl=CHCF3 (HCFO-1233zd-E), or any mixture thereof; and ii) about 6.5 to about 14.0 wt. % of a C5 hydrocarbon under conditions effective to form a foam.

[0023] In some embodiments, the application provides a method of forming a foam comprising: i) reacting or extruding a foamable composition comprising about 3.0 to about 15.0 wt. % of a mixture of (a) E-CF3CH=CHCF3 (HFO-1336mzz-E), or Z-CF3CH=CHCF3 (HFO-1336mzz-Z), and (b) E-CHCl=CHCF3 (HCFO-1233zd-E); and ii) about 6.5 to about 14.0 wt. % of a C5 hydrocarbon under conditions effective to form a foam.

[0024] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.5 to about 16.5 wt. % of a mixture of E-CF3CH=CHCF3, and Z-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt. % of a C5 hydrocarbon under conditions effective to form a foam.

[0025] In some embodiments, the foamable composition comprises about 3.5 to about 16.25 wt % of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3, such as about 3.5 to about 10.2 wt %, about 10.2 to about 16.5 wt %, or about 10.2 to about 16.25 wt % of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3.

[0026] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt.% of a C5 hydrocarbon under conditions effective to form a foam.

[0027] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, such as about 3.0 to about 14.8 wt.%, about 3.0 to about 9.0 wt.%, about 9.0 to about 15.0 wt.%, or about 9.0 to about 14.8 wt.% of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3.

[0028] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt. % of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt. % of a C5 hydrocarbon under conditions effective to form a foam.

[0029] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt % of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, such as about 3.0 to about 14.8 wt %, about 3.0 to about 9.0 wt %, about 9.0 to about 15.0 wt %, or about 9.0 to about 14.8 wt % of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3.

[0030] In some embodiments, the foamable composition comprises about 6.5 to about 14.0 wt% cyclopentane, e.g., about 6.5 to about 13.8 wt%, about 6.5 to about 10.5 wt%, about 6.5 to about 10.1 wt%, about 6.5 to about 7.0 wt%, about 7.0 to about 14.0 wt%, about 7.0 to about 13.8 wt%, about 7.0 to about 10.5 wt%, about 7.0 to about 10.1 wt%, about 10.1 to about 14.0 wt%, about 10.1 to about 13.8 wt%, about 10.1 to about 10.5 wt%, about 10.5 to about 14.0 wt%, about 10.5 to about 13.8 wt%, or about 13.8 to about 14.0 wt% cyclopentane.

[0031] In some embodiments, the foamable composition comprises from about 6.5 to about 14.0 wt% isopentane, e.g., from about 6.5 to about 13.8 wt%, from about 6.5 to about 10.5 wt%, from about 6.5 to about 10.1 wt%, from about 6.5 to about 7.0 wt%, from about 7.0 to about 14.0 wt%, from about 7.0 to about 13.8 wt%, from about 7.0 to about 10.5 wt%, from about 7.0 to about 10.1 wt%, from about 10.1 to about 14.0 wt%, from about 10.1 to about 13.8 wt%, from about 10.1 to about 10.5 wt%, from about 10.5 to about 14.0 wt%, from about 10.5 to about 13.8 wt%, or from about 13.8 to about 14.0 wt% isopentane.

[0032] In some embodiments, the foamable composition comprises about 6.5 to about 14.0 wt% n-pentane, e.g., about 6.5 to about 13.8 wt%, about 6.5 to about 10.5 wt%, about 6.5 to about 10.1 wt%, about 6.5 to about 7.0 wt%, about 7.0 to about 14.0 wt%, about 7.0 to about 13.8 wt%, about 7.0 to about 10.5 wt%, about 7.0 to about 10.1 wt%, about 10.1 to about 14.0 wt%, about 10.1 to about 13.8 wt%, about 10.1 to about 10.5 wt%, about 10.5 to about 14.0 wt%, about 10.5 to about 13.8 wt%, or about 13.8 to about 14.0 wt% n-pentane.

[0033] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.5 to about 16.5 wt.% of a mixture of E-CF3CH=CHCF3, and Z-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt.% cyclopentane under conditions effective to form a foam.

[0034] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.5 to about 16.5 weight percent of a mixture of E-CF3CH=CHCF3, and Z-CF3CH=CHCF3; and ii) about 6.9 to about 13.5 weight percent cyclopentane under conditions effective to form a foam.

[0035] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.5 to about 16.5 wt.% of a mixture of E-CF3CH=CHCF3, and Z-CF3CH=CHCF3; and ii) about 7.1 to about 13.8 wt.% of isopentane under conditions effective to form a foam.

[0036] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.5 to about 16.5 wt.% of a mixture of E-CF3CH=CHCF3, and Z-CF3CH=CHCF3; and ii) about 7.1 to about 13.5 wt.% of n-pentane under conditions effective to form a foam.

[0037] In some embodiments, the foamable composition comprises: about 3.4 to about 3.6 weight percent of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3, and about 13.4 to about 13.6 weight percent cyclopentane; or about 10.1 to about 10.2% by weight of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3 and about 10.0 to about 10.1% by weight of cyclopentane, or about 16.2 to about 16.3% by weight of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3 and about 6.9 to about 7.0% by weight of cyclopentane, or about 3.4 to about 3.6 weight percent of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3, and about 13.7 to about 13.9 weight percent isopentane; or about 10.1 to about 10.2% by weight of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3, and about 10.3 to about 10.4% by weight of isopentane; or about 16.2 to about 16.3 weight percent of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3, and about 7.1 to about 7.2 weight percent isopentane; or about 3.4 to about 3.6 weight percent of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3, and about 13.4 to about 13.6 weight percent n-pentane; or about 10.1 to about 10.2 weight percent of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3, and about 10.3 to about 10.4 weight percent n-pentane; or It contains about 16.2 to about 16.3 weight percent of a mixture of E-CF3CH=CHCF3 and Z-CF3CH=CHCF3, and about 7.1 to about 7.2 weight percent of n-pentane.

[0038] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 0.3 to about 16.5 wt. % E-CF3CH=CHCF3; and ii) about 6.5 to about 15.5 wt. % cyclopentane under conditions effective to form a foam.

[0039] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt.% cyclopentane under conditions effective to form a foam.

[0040] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 4.0 wt. % of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 13.0 to about 14.0 wt. % cyclopentane under conditions effective to form a foam.

[0041] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 10.0 to about 11.0 wt. % of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 9.0 to about 10.0 wt. % cyclopentane under conditions effective to form a foam.

[0042] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 14.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 7.0 to about 8.0 wt.% cyclopentane under conditions effective to form a foam.

[0043] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt.% of isopentane under conditions effective to form a foam.

[0044] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 4.0 wt. % of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 13.0 to about 14.0 wt. % of isopentane under conditions effective to form a foam.

[0045] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 10.0 to about 11.0 wt. % of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 9.0 to about 10.0 wt. % of isopentane under conditions effective to form a foam.

[0046] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 14.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 7.0 to about 8.0 wt.% of isopentane under conditions effective to form a foam.

[0047] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt.% of n-pentane under conditions effective to form a foam.

[0048] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 4.0 wt. % of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 13.0 to about 14.0 wt. % of n-pentane under conditions effective to form a foam.

[0049] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 10.0 to about 11.0 wt. % of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 9.0 to about 10.0 wt. % of n-pentane under conditions effective to form a foam.

[0050] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 14.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and Z-CF3CH=CHCF3; and ii) about 7.0 to about 8.0 wt.% of n-pentane under conditions effective to form a foam.

[0051] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt.% cyclopentane under conditions effective to form a foam.

[0052] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 4.0 wt. % of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 13.0 to about 14.0 wt. % cyclopentane under conditions effective to form a foam.

[0053] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 10.0 to about 11.0 wt. % of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 9.0 to about 10.0 wt. % cyclopentane under conditions effective to form a foam.

[0054] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 14.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 7.0 to about 8.0 wt.% cyclopentane under conditions effective to form a foam.

[0055] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt.% of isopentane under conditions effective to form a foam.

[0056] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 4.0 wt. % of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 13.0 to about 14.0 wt. % of isopentane under conditions effective to form a foam.

[0057] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 10 to about 11 weight percent of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 9.0 to about 10.0 weight percent isopentane under conditions effective to form a foam.

[0058] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 14.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 7.0 to about 8.0 wt.% of isopentane under conditions effective to form a foam.

[0059] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt. % of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 6.5 to about 14.0 wt. % of n-pentane under conditions effective to form a foam.

[0060] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 3.0 to about 4.0 wt. % of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 13.0 to about 14.0 wt. % of n-pentane under conditions effective to form a foam.

[0061] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 10 to about 11 weight percent of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 9.0 to about 10.0 weight percent n-pentane under conditions effective to form a foam.

[0062] In some embodiments, the method comprises reacting or extruding a foamable composition comprising: i) about 14.0 to about 15.0 wt.% of a mixture of E-CHCl=CHCF3, and E-CF3CH=CHCF3; and ii) about 7.0 to about 8.0 wt.% of n-pentane under conditions effective to form a foam.

[0063] In some embodiments, the foamable composition comprises: about 3.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 6.5 to about 14.0% by weight of cyclopentane; or about 3.0 to about 4.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 13.0 to about 14.0% by weight of cyclopentane; or about 10.0 to about 11.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 9.0 to about 10.0% by weight of cyclopentane; or about 14.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 7.0 to about 8.0% by weight of cyclopentane; or about 3.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 6.5 to about 14.0% by weight of isopentane; or about 3.0 to about 4.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 13.0 to about 14.0% by weight of isopentane; or about 10 to about 11 weight percent of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 9.0 to about 10.0 weight percent isopentane; or about 14.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 7.0 to about 8.0% by weight of isopentane; or about 3.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 6.5 to about 14.0% by weight of n-pentane; or about 3.0 to about 4.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 13.0 to about 14.0% by weight of n-pentane; or about 10 to about 11 weight percent of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 9.0 to about 10.0 weight percent n-pentane; or about 14.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and Z-CF3CH=CHCF3, and about 7.0 to about 8.0% by weight of n-pentane; or about 3.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 6.5 to about 14.0% by weight of cyclopentane; or about 3.0 to about 4.0% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 13.0 to about 14.0% by weight of cyclopentane; or about 10 to about 11% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 9.0 to about 10.0% by weight of cyclopentane; or about 14.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 7.0 to about 8.0% by weight of cyclopentane; or % by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3; and about 6.5 to about 14.0% by weight of isopentane; or about 3.0 to about 4.0% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 13.0 to about 14.0% by weight of isopentane; or about 10 to about 11% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 9.0 to about 10.0% by weight of isopentane; or about 14.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 7.0 to about 8.0% by weight of isopentane; or about 3.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 6.5 to about 14.0% by weight of n-pentane; or about 3.0 to about 4.0% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 13.0 to about 14.0% by weight of n-pentane; or about 10 to about 11% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 9.0 to about 10.0% by weight of n-pentane; or It contains about 14.0 to about 15.0% by weight of a mixture of E-CHCl=CHCF3 and E-CF3CH=CHCF3, and about 7.0 to about 8.0% by weight of n-pentane.

[0064] In some embodiments, the foamable composition comprises from about 0.37 to about 16.25 wt.% E-CF3CH=CHCF3, e.g., from about 0.37 to about 10.1 wt.%, from about 0.37 to about 3.5 wt.%, from about 3.5 to about 16.25 wt.%, or from about 3.5 to about 10.1 wt.% E-CF3CH=CHCF3.

[0065] In some embodiments, the foamable composition comprises about 3.5 to about 16.5 wt.% E-CF3CH=CHCF3.

[0066] In some embodiments, the foamable composition comprises about 0.3 to about 10.1 wt % E-CF3CH=CHCF3.

[0067] In some embodiments, the foamable composition comprises about 0.3 to about 0.4 wt % E-CF3CH=CHCF3.

[0068] In some embodiments, the foamable composition comprises about 3.5 to about 3.6 wt.% E-CF3CH=CHCF3.

[0069] In some embodiments, the foamable composition comprises about 10.1 to about 10.2 wt.% E-CF3CH=CHCF3.

[0070] In some embodiments, the foamable composition comprises about 16.2 to about 16.3 wt.% E-CF3CH=CHCF3.

[0071] In some embodiments, the foamable composition includes from about 6.9 to about 15.5 wt.% cyclopentane, e.g., from about 6.9 to about 13.5 wt.%, from about 6.9 to about 10.1 wt.%, from about 10.1 to about 15.5 wt.%, from about 10.1 to about 13.5 wt.%, or from about 13.5 to about 15.5 wt.% cyclopentane.

[0072] In some embodiments, the foamable composition comprises about 6.9 to about 13.5 weight percent cyclopentane.

[0073] In some embodiments, the foamable composition comprises about 10.1 to about 13.5 weight percent cyclopentane.

[0074] In some embodiments, the foamable composition comprises from about 3.5 to about 16.5 wt.% E-CF3CH=CHCF3 and from about 6.9 to about 13.5 wt.% cyclopentane.

[0075] In some embodiments, the foamable composition comprises from about 0.3 to about 10.1 wt.% E-CF3CH=CHCF3 and from about 10.1 to about 13.5 wt.% cyclopentane.

[0076] In some embodiments, the foamable composition comprises: about 0.3 to about 0.4 weight percent E-CF3CH=CHCF3 and about 15.1 to about 15.2 weight percent cyclopentane; or about 3.5 to about 3.6 weight percent E-CF3CH=CHCF3 and about 13.5 to about 13.6 weight percent cyclopentane; or about 10.1 to about 10.2 weight percent E-CF3CH=CHCF3 and about 10.1 to about 10.2 weight percent cyclopentane; or It contains about 16.2 to about 16.3 weight % E-CF3CH=CHCF3 and about 6.9 to about 7.0 weight % cyclopentane.

[0077] In some embodiments, the foams prepared according to the methods provided herein have a cream time of from about 3 seconds to about 30 seconds.

[0078] In some embodiments, the foams prepared according to the methods provided herein have a cream time of about 20 seconds to about 30 seconds.

[0079] In some embodiments, the foams prepared according to the methods provided herein have a gel time of from about 25 seconds to about 80 seconds.

[0080] In some embodiments, the foams prepared according to the methods provided herein have a gel time of about 30 seconds to about 40 seconds.

[0081] In some embodiments, the foams prepared according to the methods provided herein have a rise time of from about 50 seconds to about 140 seconds.

[0082] In some embodiments, the foams prepared according to the methods provided herein have a rise time of about 50 to about 80 seconds.

[0083] In some embodiments, the foams prepared according to the methods provided herein have a rise time of about 70 seconds to about 80 seconds.

[0084] In some embodiments, the foams prepared according to the methods provided herein have a tack time of about 50 seconds to about 100 seconds.

[0085] In some embodiments, the foams prepared according to the methods provided herein have a tack time of about 70 to about 80 seconds.

[0086] In some embodiments, the foamable composition further comprises one or more polyols. In some embodiments, the foamable composition described herein may further comprise one or more additives. For example, the foamable composition may further comprise one or more additives, including, but not limited to, catalysts, surfactants, flame retardants, stabilizers, preservatives, chain extenders, crosslinkers, water, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, nucleating agents, smoke suppressants, and pigments.

[0087] 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.

[0088] In some embodiments, the foamable composition comprises at least one polyol. In some embodiments, the polyol comprises a polyester polyol in any ratio to a polyether polyol. One or more of each polyester polyol and polyether polyol can be used. In some embodiments, the polyol comprises a polyester polyol in a weight ratio of about 1:1 to about 2:1 to the polyether polyol. In some embodiments, the polyol comprises a polyester polyol in a weight ratio of about 1:1 to the polyether polyol. In some embodiments, the polyol comprises a polyester polyol in a weight ratio of about 1:1 to the polyether polyol. In some embodiments, the polyol comprises a polyester polyol in a weight ratio of about 1:1 to the polyether polyol.

[0089] In some embodiments, the polyol is a polyester polyol. Suitable polyester polyols include those prepared by reacting carboxylic acids and / or their derivatives or polycarboxylic anhydrides with polyhydric alcohols. 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 esters of polycarboxylic acids can also be used, such as terephthalic acid dimethyl ester, terephthalic acid bisglycol, and their extracts. The 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, diethanolamine, etc. 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.

[0090] Other suitable polyester polyols include, but are not limited to, aromatic polyester polyols, such as those made by transesterifying polyethylene terephthalate (PET) scrap with a glycol, such as diethylene glycol, or those made by reacting phthalic anhydride with a glycol. The resulting polyester polyols can be further reacted with ethylene oxide and / or propylene oxide to form extended polyester polyols containing additional internal alkyleneoxy groups.

[0091] 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.

[0092] Examples of 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), Terol® 250 (Huntsman, The Woodlands, TX)). (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) 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)(Richmond, VA)), Carpol® PES-295 (Carpenter Co., Richmond, VA).

[0093] In some embodiments, the foamable composition comprises one or more polyether polyols. Examples of suitable polyether polyols include, but are not limited to, polyethylene oxide, polypropylene oxide, mixed polyethylene-propylene oxide with terminal hydroxyl groups, among others. Other suitable polyols can be prepared by reacting ethylene oxide and / or propylene oxide with initiators having 2-16, or 3-8 hydroxyl groups present in polyhydroxy compounds, such as, for example, glycerol, pentaerythritol, and carbohydrates, such as sorbitol, glucose, sucrose, etc. Suitable polyether polyols can also include aliphatic or aromatic amine-based polyols. Examples of 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-36 ... (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)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 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 (Lemfoerde, Germany)), Pluracol® P1010 (BASF (Lemfoerde, Germany)), Pluracol® GP730 (BASF (Lemfoerde, Germany)), Pluracol® 220 (BASF (Lemfoerde, Germany)), Luprano ARCOL® 3422 (BASF, Lemfoerde, Germany), Pluracol® SG-360 (BASF, Lemfoerde, Germany), Pluracol® 824 (BASF, Lemfoerde, Germany), Pluracol® 735 (BASF, Lemfoerde, 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 Poly-G® 73-490 (Monument Chemical, Indianapolis, IN) Poly-G® 74-376 (Monument Chemical, Indianapolis, IN) and Poly-G® 74-532.

[0094] In some embodiments, the polyether polyol is a medium-functional polyether polyol. For example, the polyether polyol has a functionality of about 4. In some embodiments, the polyether polyol is initiated with sucrose / glycerin. In some embodiments, the polyether polyol is a Mannich-based polyether polyol. As used herein, the term "Mannich-based polyether polyol" refers to an aromatic polyol obtained by alkoxylation with propylene oxide and / or ethylene oxide of a Mannich base obtained by conventional Mannich reaction between phenol (e.g., phenol, p-nonylphenol), formaldehyde, and 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).

[0095] 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.

[0096] 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.

[0097] In some embodiments, (i) E-CF3CH=CHCF3 (HFO-1336mzz-E), Z-CF3CH=CHCF3 (HFO-1336mzz-Z), E-CHCl=CHCF3 (HCFO-1233zd-E), or any mixture thereof, and ii) C5 hydrocarbons, as described herein, are soluble in the polyol blend. In some embodiments, solubility is measured by visual evaluation.

[0098] In some embodiments, the mixture of (i) E-CFCH=CHCF (HFO-1336mzz-E) and ii) C5 hydrocarbons described herein is soluble in the polyol blend. In some embodiments, the solubility is measured by visual evaluation.

[0099] In some embodiments, the mixture of (i) Z-CFCH=CHCF (HFO-1336mzz-Z) and ii) C5 hydrocarbons described herein is soluble in the polyol blend. In some embodiments, the solubility is measured by visual evaluation.

[0100] In some embodiments, the mixture of (i) E-CHCl=CHCF3 (HCFO-1233zd-E) and ii) C5 hydrocarbons described herein is soluble in the polyol blend. In some embodiments, the solubility is measured by visual evaluation.

[0101] In some embodiments, the mixture of (i) E-CFCH=CHCF (HFO-1336mzz-E) and Z-CFCH=CHCF (HFO-1336mzz-Z) and ii) C5 hydrocarbons described herein are soluble in the polyol blend. In some embodiments, solubility is measured by visual evaluation.

[0102] In some embodiments, (i) a mixture of Z-CFCH=CHCF (HFO-1336mzz-Z) and E-CHCl=CHCF (HCFO-1233zd-E) and ii) a C5 hydrocarbon as described herein are soluble in the polyol blend. In some embodiments, solubility is measured by visual evaluation.

[0103] In some embodiments, (i) a mixture of E-CFCH=CHCF (HFO-1336mzz-E) and E-CHCl=CHCF (HCFO-1233zd-E) and ii) C5 hydrocarbons as described herein are soluble in the polyol blend. In some embodiments, solubility is measured by visual evaluation.

[0104] 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 rate of reaction 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.

[0105] 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, for example, alkali metal alkoxides, alkali metal carboxylates, or quaternary amine salts, may also be optionally used herein. Such catalysts are used in amounts that provide some increase in the reaction rate of the polyisocyanates. 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 (Evonik Industries), POLYCAT® 5, pentamethyldiethylenetriamine (Evonik Industries), and CURITHANE® 52, 2-Methyl (n-methylamino b-sodium acetate nonylphenol) (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), 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, Ohio), Bicat® 8840 (The Shepard Chemical Company, Cincinnati, Ohio), Bicat® 8842 (The Shepard Chemical Company, Cincinnati, Ohio), K-Kat® XK651 (King Industries, Norwalk, Conn.), 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 Examples of suitable tin esters include tin, dibutyltin mercaptide, potassium octoate, potassium acetate, bismuth, and bismuth carboxylate mixtures.

[0106] In some embodiments, the foamable composition includes a surfactant. Suitable surfactants may 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.

[0107] 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, bromine-containing diester / ether diols of tetrabromophthalic anhydride, such as mixed esters of tetrabromophthalic anhydride with diethylene glycol and propylene glycol. Examples of commercially available flame retardants include Saytex® RB-79, reactive bromine-containing diester / ether diols of tetrabromophthalic anhydride (Albemarle Corporation, Baton Rouge, LA). In some embodiments, the flame retardant is tris(1-chloro-2-propyl) phosphate (TCPP).

[0108] In some embodiments, the foamable composition includes a nucleating agent. Nucleating agents function primarily to increase the number of bubbles and reduce the bubble 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. Exemplary nucleating agents include at least one member selected from the group consisting of talc, sodium bicarbonate-citric acid mixture, calcium silicate, and carbon dioxide, among others. In some embodiments, the foamable composition does not include a nucleating agent. In some embodiments, the methods 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 mixture, calcium silicate, carbon dioxide, and the like.

[0109] In some embodiments, the foamable composition comprises water. In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, cyclopentane, and water.

[0110] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, cyclopentane, and water, and the E-CF3CH=CHCF3 is present in about 1 mol % to about 50 mol %, e.g., about 1 mol % to about 30 mol %, about 1 mol % to about 10 mol %, about 10 mol % to about 50 mol %, about 10 mol % to about 30 mol %, or about 30 mol % to about 50 mol % of the total amount of E-CF3CH=CHCF3, cyclopentane, and water present in the foamable composition.

[0111] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, cyclopentane, and water, wherein the E-CF3CH=CHCF3 is present in about 10 mol % to about 50 mol % of the total amount of E-CF3CH=CHCF3, cyclopentane, and water present in the foamable composition.

[0112] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, cyclopentane, and water, wherein E-CF3CH=CHCF3 is present in about 1 mol % to about 30 mol % of the total amount of E-CF3CH=CHCF3, cyclopentane, and water present in the foamable composition.

[0113] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, cyclopentane, and water, wherein the E-CF3CH=CHCF3 is present in an amount from about 10 mol % to about 30 mol % of the total amount of E-CF3CH=CHCF3, cyclopentane, and water present in the foamable composition.

[0114] In some embodiments, the foamable composition comprises from about 0.3 to about 16.5 wt. % E-CF3CH=CHCF3, from about 6.9 to about 13.5 wt. % cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent, as described herein.

[0115] In some embodiments, the foamable composition comprises from about 0.3 to about 16.5 wt.% E-CF3CH=CHCF3, from about 6.9 to about 13.5 wt.% cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant as described herein.

[0116] In some embodiments, the foamable composition comprises about 3.5 to about 16.5 wt.% E-CF3CH=CHCF3, about 6.9 to about 13.5 wt.% cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent, as described herein.

[0117] In some embodiments, the foamable composition comprises about 3.5 to about 16.5 wt.% E-CF3CH=CHCF3, about 6.9 to about 13.5 wt.% cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant as described herein.

[0118] In some embodiments, the foamable composition provided herein includes about 3.5 to about 16.5 wt. % E-CF3CH=CHCF3, about 6.9 to about 13.5 wt. % cyclopentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0119] In some embodiments, the foamable compositions provided herein include about 3.5 to about 16.25 wt % of a mixture of E-CF3CH=CHCF3, and Z-CF3CH=CHCF3, about 6.9 to about 13.5 wt % of cyclopentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0120] In some embodiments, the foamable compositions provided herein include about 3.5 to about 16.25 wt % mixture of E-CF3CH=CHCF3, and Z-CF3CH=CHCF3, about 6.5 to about 14.0 wt % isopentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0121] In some embodiments, the foamable compositions provided herein include about 3.5 to about 16.25 wt % of a mixture of E-CF3CH=CHCF3, and Z-CF3CH=CHCF3, about 6.5 to about 14.0 wt % n-pentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0122] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water, and comprises about 1 mol % to about 50 mol %, e.g., about 1 mol % to about 30 mol %, about 1 mol % to about 10 mol %, about 10 mol % to about 50 mol %, about 10 mol % to about 30 mol %, or about 30 mol % to about 50 mol %, of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water present in the foamable composition.

[0123] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water, and comprises about 10 mol % to about 50 mol % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water present in the foamable composition.

[0124] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water, and comprises about 1 mol % to about 30 mol % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water present in the foamable composition.

[0125] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water, and comprises about 10 mol % to about 30 mol % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water present in the foamable composition.

[0126] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water, and comprises about 10 mol % to about 50 mol % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water present in the foamable composition.

[0127] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water, and comprises from about 1 mol % to about 30 mol % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water present in the foamable composition.

[0128] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water, and comprises about 10 mol % to about 30 mol % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water present in the foamable composition.

[0129] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water, and comprises about 10 mol % to about 50 mol % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water present in the foamable composition.

[0130] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water, and comprises about 1 mol % to about 30 mol % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water present in the foamable composition.

[0131] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water, and comprises about 10 mol % to about 30 mol % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of E-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water present in the foamable composition.

[0132] In some embodiments, the foamable composition comprises Z-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water, and comprises about 1 mol % to about 50 mol %, e.g., about 1 mol % to about 30 mol %, about 1 mol % to about 10 mol %, about 10 mol % to about 50 mol %, about 10 mol % to about 30 mol %, or about 30 mol % to about 50 mol %, of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water present in the foamable composition.

[0133] In some embodiments, the foamable composition comprises Z-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water, and comprises about 10 mol % to about 50 mol % of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water present in the foamable composition.

[0134] In some embodiments, the foamable composition comprises Z-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water, and comprises about 1 mol % to about 30 mol % of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water present in the foamable composition.

[0135] In some embodiments, the foamable composition comprises Z-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water, and comprises about 10 mol % to about 30 mol % of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, cyclopentane, and water present in the foamable composition.

[0136] In some embodiments, the foamable composition comprises Z-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water, and comprises about 10 mol % to about 50 mol % of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water present in the foamable composition.

[0137] In some embodiments, the foamable composition comprises Z-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water, and the mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3 is from about 1 mol % to about 30 mol % of the mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water present in the foamable composition.

[0138] In some embodiments, the foamable composition comprises Z-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water, and comprises about 10 mol % to about 30 mol % of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, isopentane, and water present in the foamable composition.

[0139] In some embodiments, the foamable composition comprises E-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water, and comprises about 10 mol % to about 50 mol % of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water present in the foamable composition.

[0140] In some embodiments, the foamable composition comprises Z-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water, and comprises about 1 mol % to about 30 mol % of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water present in the foamable composition.

[0141] In some embodiments, the foamable composition comprises Z-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water, and comprises about 10 mol % to about 30 mol % of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, based on the total amount of Z-CF3CH=CHCF3, E-CHCl=CHCF3, n-pentane, and water present in the foamable composition.

[0142] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt. % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt. % of cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent, as described herein.

[0143] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt.% of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant, as described herein.

[0144] In some embodiments, the foamable compositions provided herein include 3.0 to about 15.0 wt.% of a mixture of E-CF3CH=CHCF3, and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of cyclopentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0145] In some embodiments, the foamable composition includes about 3.0 to about 15.0 wt.% of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of isopentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent, as described herein.

[0146] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt.% of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of isopentane, at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant, as described herein.

[0147] In some embodiments, the foamable composition provided herein includes 3.0 to about 15.0 wt.% of a mixture of E-CF3CH=CHCF3, and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of isopentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0148] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt. % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt. % of n-pentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent, as described herein.

[0149] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt. % of a mixture of E-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt. % of n-pentane, at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant, as described herein.

[0150] In some embodiments, the foamable composition provided herein includes 3.0 to about 15.0 wt.% of a mixture of E-CF3CH=CHCF3, and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of n-pentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0151] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt.% of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent, as described herein.

[0152] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt.% of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant, as described herein.

[0153] In some embodiments, the foamable compositions provided herein include 3.0 to about 15.0 wt.% of a mixture of E-CF3CH=CHCF3, and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of cyclopentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0154] In some embodiments, the foamable composition includes about 3.0 to about 15.0 wt.% of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of isopentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent, as described herein.

[0155] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt.% of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of isopentane, at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant, as described herein.

[0156] In some embodiments, the foamable composition provided herein includes 3.0 to about 15.0 wt.% of a mixture of Z-CF3CH=CHCF3, and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of isopentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0157] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt.% of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of n-pentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent, as described herein.

[0158] In some embodiments, the foamable composition comprises about 3.0 to about 15.0 wt.% of a mixture of Z-CF3CH=CHCF3 and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% of n-pentane, at least one polyol, at least one catalyst, at least one surfactant, water, and at least one flame retardant, as described herein.

[0159] In some embodiments, the foamable compositions provided herein include 3.0 to about 15.0 wt.% of a mixture of Z-CF3CH=CHCF3, and E-CHCl=CHCF3, about 6.5 to about 14.0 wt.% n-pentane, Stepanpol® PS-2352 polyol, Dabco® DC5585 surfactant, Polycat® 36 amine catalyst, Dabco® TMR-20 metal catalyst, and TCPP flame retardant.

[0160] In some embodiments, a method of forming a foam includes (a) adding a foamable composition disclosed herein (e.g., B-side composition) to a composition containing an isocyanate (e.g., A-side composition) and (b) reacting the composition under conditions effective to form a foam. The isocyanate or isocyanate-containing mixture may include isocyanate 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 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, may be used or adapted in accordance with the compositions disclosed herein.

[0161] In the process of making polyisocyanate-based foams, the polyol, polyisocyanate, and other ingredients are contacted and thoroughly mixed to allow expansion and curing into a cellular polymer. The particular 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., B-side composition) disclosed herein and then contact this composition with the polyisocyanate.

[0162] In some embodiments, the foamable compositions (e.g., B-side compositions) disclosed herein can be used to foam thermoplastic foams, such as polystyrene, polyethylene foams, including low density polyethylene foams, or polypropylene foams. Any of a wide variety of conventional methods for foaming such thermoplastic foams can be adapted for use herein. Thus, disclosed herein are thermoplastic foams, such as polystyrene, polyethylene (PE), e.g., low density PE, or polypropylene (PP), formed using the foamable compositions disclosed herein.

[0163] Thermoplastic foam bodies can be made using conventional equipment comprising an extruder and associated means for: (1) melting a resin; (2) forming a plasticized mass at non-foaming temperature and pressure by intimately blending a foamable composition described herein (e.g., a B-side composition) with the melt; (3) passing the plasticized mass through an expansion zone at controlled speed, temperature, and pressure and through a die having a desired shape, for example, a slip die for producing a rectangular slab of foam board having a desired thickness and surface area; (4) foaming the extrudate in an expansion zone that can be maintained at a suitable temperature and low pressure; (5) maintaining the expanding extrudate at such temperature and pressure for a time sufficient to increase the viscosity of the extrudate such that the foam cell size and density remain substantially unchanged at ambient temperature, e.g., 25° C., and atmospheric pressure, and that there remain substantially no bubbles that burst; and (6) recovering the extruded foam body.

[0164] It is understood that the present application further provides a foamable composition as described herein. In some embodiments, the foamable composition as described herein is useful in one or more of the methods described herein.

[0165] Foam The present application further provides foams prepared according to one or more of the methods provided herein. Types of foams made can include, for example, closed cell foams, open cell foams, rigid foams, flexible foams, and integral skins. In some embodiments, foams prepared from foamable compositions (e.g., B-side compositions) are disclosed herein. In some embodiments, the foam is a spray foam. In some embodiments, the foam is a thermoset foam.

[0166] 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 polyisocyanurate based foams are useful for spray insulation, as foam in place equipment foams, rigid insulation board materials, or in laminates.

[0167] 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, 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 insulation.

[0168] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.120 Btu in / ft at 20° F.2 Has a K-factor of less than or equal to ·h·°F.

[0169] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.120 Btu in / ft at 20° F. 2 h°F to approx. 0.110 Btu in / ft 2 It has a K factor of ·h·°F.

[0170] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.137 Btu in / ft at 75° F. (24° C.). 2 Has a K-factor of less than or equal to ·h·°F.

[0171] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.137 Btu in / ft at 75° F. (24° C.). 2 ·h·°F ~ approx. 0.131Btu·in / ft 2 It has a K factor of ·h·°F.

[0172] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.130 Btu in / ft at 75° F. (24° C.). 2 Has a K-factor of less than or equal to ·h·°F.

[0173] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.130 to about 0.126 Btu in / ft at 75° F. (24° C.). 2 It has a K factor of ·h·°F.

[0174] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.124 Btu in / ft at 50° F. (10° C.). 2 Has a K-factor of less than or equal to ·h·°F.

[0175] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.124 to about 0.117 Btu in / ft at 50° F. (10° C.). 2 It has a K factor of ·h·°F.

[0176] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.119 Btu in / ft at 20° F. 2 Has a K-factor of less than or equal to ·h·°F.

[0177] In some embodiments, the foams prepared according to the methods provided herein have a viscosity of about 0.119 to about 0.110 Btu in / ft at 20° F. 2 It has a K factor of ·h·°F.

[0178] In some embodiments, foams prepared according to the methods provided herein may be compared to similar foams prepared using only C5 hydrocarbons (e.g., cyclopentane, isopentane, or n-pentane) as blowing agents (i.e., foams prepared using the same A-side+B-side mixture, where the B-side mixture is E-CF3CH=CHCF3 (HFO-1336mzz-E), Z-CF3CH=CHCF3 (HFO-1336mzz-E),

[0036] In some embodiments, the HCFO-1233zd-E or E-CHCl═CHCF3 (HCFO-1233zd-Z), E-CHCl═CHCF3 (HCFO-1233zd-E), or any mixture thereof does not contain an improved K-factor of about 4% to about 30%, e.g., about 4% to about 20%, about 4% to about 15%, about 4% to about 10%, about 10% to about 30%, about 10% to about 20%, about 10% to about 15%, about 15% to about 30%, about 15% to about 20%, or about 20% to about 30%, as compared to a HCFO-1233zd-E or E-CHCl═CHCF3 (HCFO-1233zd-Z), E-CHCl═CHCF3 (HCFO-1233zd-E), or any mixture thereof.

[0179] In some embodiments, foams made from the foamable compositions disclosed herein have a foam density of about 2.5 to about 3.5 g / cm 3 For example, the foam has a density of about 2.5 g / cm 3 , 2.6g / cm 3 , 2.7g / cm 3 , 2.8g / cm 3 , 2.9g / cm3 , 3.0g / cm 3 .3.1g / cm 3 , 3.2g / cm 3 , 3.3g / cm 3 , 3.4g / cm 3 , or 3.5 g / cm 3 The density of the powder may be 0.01 to 0.01.

[0180] Representative foam products that can be made according to the present disclosure include, for example, (1) polystyrene foam sheets for making single-use thermoformed packaging materials, as disclosed, for example, in U.S. Pat. No. 5,204,169; and (2) foamed polystyrene sheets having thicknesses of about 0.5 to 6 inches (1.25 to 15 cm), widths of up to 4 feet (122 cm), cross-sectional areas of 0.17 to 3 square feet (0.016 to 0.28 square meters), lengths of up to 27 feet (813 meters), and elastic modulus 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 boards used as residential and industrial sheathing and roofing materials, which may have a density of 1000 to 2000 mm (0.19 to 0.74 m) and a thickness of up to about 2 feet (61 cm), often at least 1.5 feet (46 cm), a width of up to 4 feet (1.22 m), a length of up to 16 feet (4.8 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). 3 and expandable foams in the form of large pieces that may have a density of 1000 to 2000 mm. 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. EXAMPLES

[0181] The present disclosure will be further specified in the following examples. It should be understood that these examples show preferred embodiments, but are provided for illustrative purposes only. From the above description and these examples, those skilled in the art can ascertain preferred features, and can make various changes and modifications to accommodate various applications and conditions without departing from the spirit and scope of the present invention.

[0182] The following ingredients were used in the examples: The polyol is Stepanpol® PS-2352, which is an aromatic polyester polyol available from Stepan Company.

[0183] The surfactant is Dabco® DC5585, which is a silicone polyether surfactant available from Evonik Industries.

[0184] The amine catalyst is Polycat® 36, which is a tertiary amine catalyst available from Evonik Industries, AG.

[0185] The metal catalyst is Dabco® TMR-20, which is a potassium-based catalyst available from Evonik Industries.

[0186] The flame retardant is TCPP.

[0187] The isocyanate is PAPI-27, which is a polymethylene polyphenylisocyanate-containing MDI available from Dow DuPont Chemical Company.

[0188] The following "Control" composition is referenced throughout the examples and was used as a benchmark for the comparative analysis described in Example 4.

[0189] [Table 1]

[0190] Example 1. General Preparation of A-Side and B-Side Compositions The formulations described in the examples were prepared using the parts per hundred polyol (pphp) method (i.e., parts by weight (pbw)). The blends prepared had an ISO index of 300 and a pbw to weight ratio of 0.85, and the adjusted blowing agent blend was held constant on a total molar basis.

[0191] The B-side ingredients were weighed on a mass balance and mixed together in a 1 L plastic beaker, then the physical blowing agents (e.g., HFOs and C5 hydrocarbons) were cooled below their respective boiling points. After cooling, the blowing agents were added to the B-side mixture until fully incorporated.

[0192] The isocyanate (side A), primarily PAPI27, was weighed into a 500 mL plastic beaker with an additional 15 weight percent (wt%) to allow for sufficient headspace for injection. After the sides A and B were weighed, the side A was poured into the side B mixture.

[0193] Tables 1-5 summarize the formulations (A-side and B-side formulations) prepared as described above.

[0194] [Table 2] a Compositions 1A-1E contain 0, 0.37, 3.51, 10.12, and 16.25% by weight of HFO-1336mzz-Z, based on the total of the B-side and blowing agent, respectively, which correspond to 0, 1, 10, 30, and 50 mol % of HFO, based on the total moles of HFO+cyclopentane+water used to prepare each composition.

[0195] [Table 3] aCompositions 2A-2E contain 0, 0.37, 3.51, 10.12, and 16.25% by weight of HFO-1336mzz-E, based on the total of the B-side and blowing agent, respectively, which correspond to 0, 1, 10, 30, and 50 mol % of HFO, based on the total moles of HFO+cyclopentane+water used to prepare each composition.

[0196] [Table 4] a Compositions 3A-3E contain 0, 0.37, 2.81, 8.22, 13.37, and 16.58 weight percent HCFO-1233zd-E, based on the total of the B-side and blowing agent, respectively, which correspond to 0, 1, 10, 30, 50, and 63 mole percent HCFO, based on the total moles of HFO+cyclopentane+water used to prepare each composition.

[0197] [Table 5] a Compositions 4A-6C contain 0.37% by weight of HFO or HCFO, based on the total of the B-side and the blowing agent.

[0198] [Table 6] a Compositions 7A-9C contain 10, 30, and 50 mol% blends of HFO-1336mzz-Z+HFO-1336mzz-E, based on the total moles of HFO+C5 alkane+water used to prepare each composition. Compositions 7A-7C contain 3.51 wt% HFO based on the combined weight of B-side and blowing agent, Compositions 8A-8C contain 10.13 wt% HFO based on the combined weight of B-side and blowing agent, and Compositions 9A-9C contain 16.25 wt% HFO based on the combined weight of B-side and blowing agent.

[0199] Example 2. Analysis of foam properties The resulting A+B mixtures described in Example 1 (i.e., A+B mixtures 1A-9C as described in Tables 1-5) were placed into a mix head and mixed for 3 seconds at 4000 rpm. After mixing, the mixed A+B solutions were quickly poured into a wax coated cardboard box. A timer was started and the cream time, gel time, rise time, and tack free time of the resulting foam were recorded. The data obtained for compositions 4A-6C are shown in Table 6 below.

[0200] [Table 7]

[0201] The foams were placed under an air hood for 24 hours to allow the polyurethane reaction to fully complete. Samples were cut into 6" x 6" x 1.5" blocks with a band saw. These foam blocks were tested for thermal conductivity utilizing a heat flow meter per ASTM C-518. After testing, data values ​​were collected for analysis and are shown below in Tables 7-10.

[0202] [Table 8] N / A = Data not applicable

[0203] [Table 9] N / A = Data not applicable

[0204] [Table 10] N / A = Data not applicable

[0205] [Table 11]

[0206] As shown in Tables 7-10 and Figures 1-10, B-side mixtures prepared using a combination of HFO-1336mzz-E and cyclopentane as a physical blowing agent resulted in foams with unexpectedly low K-factors. Specifically, foams prepared using B-side compositions containing 3.51 wt. % and 10.12 wt. % HFO-1336mzz-E exhibited 4.8% and 6.6% improvements in thermal performance at 75° F., as measured by K-factor, respectively, compared to corresponding foams prepared in the absence of HFO / HCFO physical blowing agents (i.e., 0 wt. % HFO / HCFO) (see Figures 1-2). Additionally, foams prepared with B-side compositions containing 3.51 wt%, 10.12 wt%, and 16.25 wt%, exhibited 11.0%, 16.7%, and 16.7% improvements in thermal performance at 20° F., as measured by K-factor, respectively, compared to corresponding foams prepared in the absence of HFO / HCFO physical blowing agents (i.e., 0 wt% HFO / HCFO) (see Figures 3-4).

[0207] It was also observed that foams prepared with low loadings of HFO-1336mzz-E (0.37 wt.% relative to the combined B-side and blowing agent) showed improved thermal performance at 75° F., as measured by K-factor, compared to corresponding foams prepared from B-side compositions prepared with HFO-1336mzz-Z / cyclopentane or HCFO-1233zd / cyclopentane at the same HFO / HCFO loading of 0.37 wt.% relative to the combined B-side and blowing agent (see FIGS. 5-10).

[0208] Finally, foams prepared using blends of HFO-1336mzz-Z and HFO-1336mzz-E in combination with cyclopentane (i.e., foams prepared from A+B Compositions 7A, 8A, and 9A) showed improved thermal performance at 20° F., 50° F., and 75° F. as measured by K-factor compared to corresponding foams prepared in the absence of HFO-1336mzz-Z and HFO-1336mzz-E physical blowing agents (i.e., 0 wt. % HFO).

[0209] Example 3. Additional A-side / B-side Compositions Tables 11-16 summarize the compositions (ie, A-side and B-side formulations) prepared as described according to the general procedure of Example 1.

[0210] [Table 12] a Compositions 10A-12A contain 10 mole % of the HFO or HCFO blend, based on the total moles of HFO or HCFO + C5 alkane + water used to prepare each composition. Compositions 10A-11C contain 3.5 weight % of HFO, based on the total of B-side and blowing agent. Composition 12A contains 2.8 weight % of HCFO, based on the total of B-side and blowing agent.

[0211] [Table 13] a Compositions 13A-15A contain 30 mole % of the HFO or HCFO blend, based on the total moles of HFO or HCFO + C5 alkane + water used to prepare each composition. Compositions 13A-14C contain 10 weight % HFO, based on the total of B-side and blowing agent. Composition 15A contains 8.2 weight % HCFO, based on the total of B-side and blowing agent.

[0212] [Table 14] a Compositions 16A-18A contain 50 mole % of a blend of HFOs or HCFOs based on the total moles of HFOs or HCFOs + C5 alkane + water used to prepare each composition. Compositions 16A-17C contain 16.2 weight % HFOs based on the combined weight of B-side and blowing agent. Composition 18A contains 13.4 weight % HCFOs based on the combined weight of B-side and blowing agent.

[0213] [Table 15] a Compositions 19-23 contain 10 mol% combined HFO and HCFO components based on the total moles of HFO+HCFO+C5 alkane+water used to prepare each composition. For example, composition 19 contains 10 mol% combined HFO-1336mzz(Z)+HFO-1336mzz(E) based on the total moles of HFO-1336mzz(Z)+HFO-1336mzz(E)+cyclopentane+water. Compositions 19, 22, and 23 contain 3.5 wt% HFO based on the combined B-side and blowing agent. Compositions 20 and 21 contain 3.2 wt% HFO / HCFO based on the combined B-side and blowing agent.

[0214] [Table 16] a Compositions 24-28 contain 30 mol% combined HFO and HCFO components based on the total moles of HFO+HCFO+C5 alkane+water used to prepare each composition. For example, composition 24 contains 30 mol% combined HFO-1336mzz(Z)+HFO-1336mzz(E) based on the total moles of HFO-1336mzz(Z)+HFO-1336mzz(E)+cyclopentane+water. Compositions 25, 27, and 28 contain 10 wt% HFO based on the combined B-side and blowing agent. Compositions 25 and 26 contain 9.2 wt% HFO / HCFO based on the combined B-side and blowing agent.

[0215] [Table 17] aCompositions 29-33 contain 50 mol% combined HFO and HCFO components based on the total moles of HFO+HCFO+C5 alkane+water used to prepare each composition. For example, composition 29 contains 50 mol% combined HFO-1336mzz(Z)+HFO-1336mzz(E) based on the total moles of HFO-1336mzz(Z)+HFO-1336mzz(E)+cyclopentane+water. Compositions 29, 32, and 33 contain 16.2 wt% HFO based on the combined B-side and blowing agent. Compositions 30 and 31 contain 14.8 wt% HFO / HCFO based on the combined B-side and blowing agent.

[0216] Example 4. Analysis of foam properties The resulting A+B mixtures described in Example 3 (i.e., A+B mixtures 10A-33 as described in Tables 11-16) were placed into the mix head and mixed for 3 seconds at 4000 rpm. After mixing, the mixed A+B solution was quickly poured into a wax coated cardboard box. A timer was started and the cream time, gel time, rise time, and tack free time of the resulting foam were recorded.

[0217] The foam was placed under an air hood for 24 hours to allow for full completion of the polyurethane reaction. Samples were cut into 6" x 6" x 1.5" blocks with a band saw. These foam blocks were tested for thermal conductivity utilizing a heat flow meter per ASTM C-518. After testing, data values ​​were collected for analysis and are shown below in Tables 17-23, with Table 17 showing data obtained using the C5 alkane control composition above.

[0218] [Table 18]

[0219] [Table 19]

[0220] [Table 20]

[0221] [Table 21]

[0222] [Table 22]

[0223] [Table 23]

[0224] [Table 24]

[0225] The exemplary foams of Example 3 were further analyzed for thermal conductivity (at 75° F., 50° F., and 20° F.) after aging for 14 days at 70° C. The results of the aging analysis studies are shown below in Tables 24-26 and in Figures 11A-20C as % improvement in K-factor over foams prepared with the control mixture.

[0226] [Table 25]

[0227] [Table 26]

[0228] [Table 27]

[0229] Other embodiments 1. In some embodiments, the application provides a method of forming a foam comprising reacting or extruding a foamable composition comprising: i) about 3.0 to about 15.0 wt. % of a compound selected from E-CF3CH=CHCF3 (HFO-1336mzz-E), Z-CF3CH=CHCF3 (HFO-1336mzz-Z), and E-CHCl=CHCF3 (HCFO-1233zd-E), or any mixture thereof; and ii) about 6.5 to about 14.0 wt. % of a C5 hydrocarbon under conditions effective to form a foam. 2. In some embodiments, the application provides a method of forming a foam comprising: i) reacting or extruding a foamable composition comprising about 3.0 to about 15.0 wt. % of a mixture of (a) E-CF3CH=CHCF3 (HFO-1336mzz-E), or Z-CF3CH=CHCF3 (HFO-1336mzz-Z), and (b) E-CHCl=CHCF3 (HCFO-1233zd-E); and ii) about 6.5 to about 14.0 wt. % of a C5 hydrocarbon under conditions effective to form a foam. 3. In some embodiments, the application provides a method of forming a foam comprising reacting or extruding a foamable composition comprising: i) about 0.3 to about 16.5 wt. % E-CF3CH=CHCF3; and ii) about 6.5 to about 15.5 wt. % cyclopentane under conditions effective to form a foam. 4. The foam has a thermal conductivity of approximately 0.120 Btu in / ft at 20°F. 2 4. The method of any one of claims 1 to 3, having a K-factor of no more than 1. 5. The foam has a thermal conductivity of approximately 0.120 Btu in / ft at 20°F. 2 h°F to approx. 0.110 Btu in / ft 2 4. The method of any one of claims 1 to 3, having a K-factor of .deg..times ... 6. The method of any one of the preceding embodiments, wherein the foamable composition comprises from about 3.5 to about 16.5 wt.% E-CF3CH=CHCF3. 7. The method of any one of the preceding embodiments, wherein the foamable composition comprises from about 6.9 to about 13.5% by weight of cyclopentane. 8. The method of any one of the preceding embodiments, wherein the foamable composition comprises from about 3.5 to about 16.5 wt.% E-CF3CH=CHCF3 and from about 6.9 to about 13.5 wt.% cyclopentane. 9. The foam has a thermal conductivity of approximately 0.137 Btu in / ft at 75°F. 2 4. The method of any one of claims 1 to 3, having a K-factor of no more than 1. 10. The foam has a thermal conductivity of approximately 0.137 Btu in / ft at 75°F. 2 ·h·°F ~ approx. 0.131Btu·in / ft 2 4. The method of any one of claims 1 to 3, having a K-factor of .deg..times ... 11. The method of any one of embodiments 1-3, 9, and 10, wherein the foamable composition comprises about 0.3 to about 10.1 wt.% E-CF3CH=CHCF3. 12. The method of any one of embodiments 1-3, 9, and 10, wherein the foamable composition comprises about 10.1 to about 13.5 wt.% cyclopentane. 13. The method of any one of embodiments 1-3, 9, and 10, wherein the foamable composition comprises about 0.3 to about 10.1 wt.% E-CF3CH=CHCF3 and about 10.1 to about 13.5 wt.% cyclopentane. 14. The method of any one of the preceding embodiments, wherein the foam has a cream time of about 20 seconds to about 30 seconds. 15. The method of any one of the preceding embodiments, wherein the foam has a gel time of about 30 seconds to about 40 seconds. 16. The method of any one of the preceding embodiments, wherein the foam has a rise time of about 70 seconds to about 80 seconds. 17. The method of any one of the preceding embodiments, wherein the foam has a tack time of about 70 seconds to about 80 seconds. 18. The method of any one of the preceding embodiments, 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. 19. The method of any one of the preceding embodiments, wherein the foamable composition further comprises at least one polyol. 20. The method of embodiment 18 or 19, wherein the polyol is a polyester polyol. 21. The method of any one of embodiments 18 to 20, wherein the polyol is a polyester polyol having a hydroxyl number of from about 200 mg KOH / g to about 300 mg KOH / g. 22. The method of any one of embodiments 18-20, wherein the polyol is a polyester polyol having a hydroxyl number of from about 230 mg KOH / g to about 250 mg KOH / g. 23. The method of any one of the preceding embodiments, wherein the foamable composition further comprises at least one catalyst. 24. The method of any one of the preceding embodiments, wherein the foamable composition comprises a metal catalyst and an amine catalyst. 25. The method of any one of the preceding embodiments, wherein the foamable composition further comprises a surfactant. 26. The method of any one of embodiments 18 to 25, wherein the surfactant is a silicone surfactant. 27. The method of any one of the preceding embodiments, wherein the foamable composition further comprises water. 28. The method of any one of the preceding embodiments, wherein the foamable composition comprises a flame retardant. 29. The method of any one of embodiments 18-27, wherein the flame retardant is tris(chloropropyl)phosphate. 30. The method of any one of the preceding embodiments, wherein the foamable composition comprises a nucleating agent. 31. The method of any one of the preceding embodiments, carried out in the absence of a nucleating agent. 32. The method of any one of the preceding embodiments, wherein the foam is a spray foam. 33. The method of any one of the preceding embodiments, wherein the foam is a thermoset foam. 34. The method of any one of the preceding embodiments, wherein the foam is a polyurethane foam or a polyisocyanurate foam. 35. The method of any one of the preceding embodiments, wherein the foam is a closed-cell foam. 36. A foamable composition comprising: about 0.3 to about 0.4 weight percent E-CF3CH=CHCF3 and about 15.1 to about 15.2 weight percent cyclopentane; or about 3.5 to about 3.6 weight percent E-CF3CH=CHCF3 and about 13.5 to about 13.6 weight percent cyclopentane; or about 10.1 to about 10.2% by weight of E-CF3CH=CHCF3 and about 10.1 to about 10.2% by weight of cyclopentane; or About 16.2 to about 16.3% by weight of E-CF3CH=CHCF3 and about 6.9 to about 7.0% by weight of cyclopentane, The method according to any one of embodiments 1 to 3. 37. The method of any one of embodiments 1-3, wherein the foamable composition comprises about 0.3 to about 16.5 wt.% E-CF3CH=CHCF3, about 6.9 to about 13.5 wt.% cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent. 38. The method of any one of embodiments 1-3, wherein the foamable composition comprises about 3.5 to about 16.5 wt.% E-CF3CH=CHCF3, about 6.9 to about 13.5 wt.% cyclopentane, at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent. 39. A foamable composition comprising: about 0.3 to about 0.4 weight percent E-CF3CH=CHCF3 and about 15.1 to about 15.2 weight percent cyclopentane; or about 3.5 to about 3.6 weight percent E-CF3CH=CHCF3 and about 13.5 to about 13.6 weight percent cyclopentane; or about 10.1 to about 10.2% by weight of E-CF3CH=CHCF3 and about 10.1 to about 10.2% by weight of cyclopentane; or About 16.2 to about 16.3% by weight of E-CF3CH=CHCF3 and about 6.9 to about 7.0% by weight of cyclopentane, The method according to embodiment 37 or 38. 40. A foam prepared according to the method of any one of embodiments 1 to 39. 41. A closed-cell polyisocyanurate foam prepared according to the method of any one of embodiments 1 to 39. 42. A closed-cell polyurethane foam prepared according to the method of any one of embodiments 1 to 39.

[0230] Although the present invention has been described in conjunction with its detailed description, it should be understood that the foregoing description is intended to illustrate and not to limit the scope of the invention as defined by 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 that the present invention can be combined with any of the features described herein with respect to any particular aspect and / or embodiment of the present invention, with one or more of the other features of any of the other aspects and / or embodiments of the present invention described herein, and can be modified appropriately to ensure compatibility of the combination. Such combinations are considered to be part of the invention contemplated by this disclosure.

Claims

1. 1. A method of forming a foam comprising reacting or extruding a foamable composition under conditions effective to form a foam, comprising: The foamable composition comprises: About 3.0 to about 4.0 wt. % of E-CHCl=CHCF 3 and E-CF 3 CH=CHCF 3 and about 13.0 to about 14.0 weight percent cyclopentane; or About 10.0 to about 11.0 wt. % of E-CHCl=CHCF 3 and E-CF 3 CH=CHCF 3 and about 9.0 to about 10.0 weight percent cyclopentane; or About 14.0 to about 15.0 wt. % of E-CHCl=CHCF 3 and E-CF 3 CH=CHCF 3 and about 7.0 to about 8.0 weight percent cyclopentane, 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.

2. The method of claim 1 , wherein the foam has a cream time of about 20 seconds to about 30 seconds.

3. The method of claim 1 , wherein the foam has a gel time of about 30 seconds to about 40 seconds.

4. The method of claim 1 , wherein the foam has a rise time of about 70 seconds to about 80 seconds.

5. The method of claim 1 , wherein the foam has a tack time of about 70 seconds to about 80 seconds.

6. The method of claim 1 , wherein the foamable composition comprises at least one polyol.

7. The method of claim 6 wherein the polyol is a polyester polyol.

8. The method of claim 7, wherein the polyol is a polyester polyol having a hydroxyl number of about 200 mg KOH / g to about 300 mg KOH / g.

9. The method of claim 1 , wherein the foamable composition comprises at least one catalyst.

10. 10. The method of claim 9, wherein the foamable composition comprises a metal catalyst and an amine catalyst.

11. The method of claim 1 , wherein the foamable composition comprises a surfactant.

12. The method of claim 11 , wherein the surfactant is a silicone surfactant.

13. The method of claim 1 , wherein the foamable composition comprises water.

14. The method of claim 1 , wherein the foamable composition comprises a flame retardant.

15. 15. The method of claim 14, wherein the flame retardant is tris(chloropropyl) phosphate.

16. The method of claim 1 , wherein the foamable composition comprises a nucleating agent.

17. The process of claim 1 carried out in the absence of a nucleating agent.

18. 10. The method of claim 1, wherein the foamable composition comprises at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent.

19. 13. A foam prepared according to the method of claim 1.

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