Method for Producing Froth Foam

Abstract

The present disclosure provides a method for producing a polyurethane foam froth using storage-stable components, the method comprising: preparing an A component comprising an isocyanate; preparing a B component comprising an isocyanate-reactive compound; and producing a foam by mixing the A component and the B component at low pressure, wherein the A component, the B component, or both further comprise a blowing agent comprising E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a).

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 411,878, filed September 30, 2022, the disclosure of which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION Disclosed are compositions and methods for foaming polyurethane (PUR) or polyisocyanurate (PIR) using low-pressure equipment. In one aspect, the invention is a low-pressure method for foaming polyurethane or polyisocyanurate using a low global warming potential (GWP) blowing agent comprising E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz). In another aspect, the invention is directed to a foam foam kit using the low-GWP blowing agent. [Background technology]

[0003] In polyurethane or polyisocyanurate foam applications, the foamable composition is provided in a two-component formulation: an A component (containing an isocyanate) and a B component (containing an isocyanate-reactive compound such as a polyol).

[0004] Certain applications, such as floss kit foam, require the use of a gaseous blowing agent incorporated into both the A and B components to enhance the foamability of the A and B component mixture and to enhance mixing of these components in a low-pressure mixing device. Each reactive component is stored in a separate container under pressure, and additional ingredients to assist in foam production, such as catalyst, water, and inert gas, are present in each container. These two components are then mixed to produce a froth foam, which is discharged through an applicator nozzle. After discharge, the polyurethane stream, the froth foam, can be sprayed onto a target to provide sealing and insulation.

[0005] Historically, blowing agents have included hydrochlorofluorocarbons such as HCFC-22 (chlorodifluoromethane) and hydrofluorocarbons such as HFC-134a (1,1,1,2-tetrafluoroethane). These blowing agents (HCFC-22 and HFC-134a) have a high global warming potential (GWP).

[0006] Low-GWP compounds such as E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze) and E-1-chloro-3,3,3-trifluoropropene (E-HFO-1233zd) have been proposed for use as blowing agents in polyurethane foams because they have suitable boiling points and properties. However, it has been found that certain low-GWP blowing agents degrade over time in the foamable composition. For example, E-HFO-1234ze is known to decompose to produce HF when used in the presence of an amine catalyst used to produce foam, and E-HFO-1233zd is susceptible to decomposition to corrosive chlorine compounds, including HCl. Despite safety concerns, the presence of HF or HCl in the blowing agent significantly reduces foam reactivity and quality and prolongs cure time. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] U.S. Provisional Patent Application No. 63 / 411,878 Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, a need exists for new blowing agent formulations and compositions for froth foam kits and methods for producing froth foam. [Means for solving the problem]

[0009] The present invention provides a way to fill the need for sustainable blowing agents, specifically low-pressure spray polyurethane or polyisocyanurate foams, with low global warming potential (GWP) and zero ozone depleting potential (ODP).

[0010] The present invention provides a method for producing foam, comprising: (a) preparing an A component comprising an isocyanate; (b) preparing a B component comprising an isocyanate-reactive compound; and (c) producing foam by mixing the A component and the B component at low pressure, wherein the A component, the B component, or both further comprise a blowing agent comprising E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a), and the low pressure is at least about 50 psi and at most about 500 psi (at least about 0.34 to at most about 3.4 MPa).

[0011] In one embodiment, the A component comprises a blowing agent comprising E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze) and the B component comprises a blowing agent comprising E-HFO-1336mzz. In this embodiment, the A and B components are provided in separate pressurized cylinders, and the amount of blowing agent added to each cylinder is sufficient to equalize the pressure in both cylinders.

[0012] In some embodiments, one or more butane and / or pentane isomers are added to component A or component B. The butane isomer is preferably isobutane. Pentane isomers include n-pentane, isopentane, and cyclopentane.

[0013] In some embodiments, methyl formate or water is added to the A component, the B component, or both.

[0014] The present invention provides a polyurethane froth foam kit comprising: (a) a cylinder containing an A component including an isocyanate; (b) a cylinder containing a B component including an isocyanate-reactive compound; and (c) a low-pressure mixer having a mixing chamber and a spray nozzle, wherein E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a) are added to the A component, the B component, or both.

[0015] The present disclosure also provides polyurethane or polyisocyanurate foams prepared by the methods disclosed herein. The present disclosure also provides polyurethane or polyisocyanurate foams prepared using the polyurethane froth foam kits disclosed herein.

[0016] The present disclosure provides a foamable composition. The combination of Components A and B is referred to herein as the "foamable composition." The foamable composition includes (a) a blowing agent including E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), (b) one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a), (c) an isocyanate, (d) a polyol, (e) a catalyst, and (f) a surfactant. DETAILED DESCRIPTION OF THE INVENTION

[0017] Unless otherwise stated, all parts and percentages are by weight.

[0018] The present disclosure provides a method for producing foam, comprising: (a) preparing an A component comprising an isocyanate; (b) preparing a B component comprising an isocyanate-reactive compound; and (c) mixing the A component and the B component at low pressure to produce a foam, wherein the A component, the B component, or both further comprise a blowing agent comprising E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a), and the low pressure is at least about 50 psi and up to about 500 psi (at least about 0.34 to up to about 3.4 MPa). The pressure is preferably at least 100 psi, more preferably at least 150 psi, and most preferably at least 200 psi.

[0019] In some embodiments, the amount of E-HFO-1336mzz added to Component B is from about 0% to about 20% by weight of Component B. The amount of E-HFO-1336mzz added to Component B can be, for example, from about 5% to about 20%, from about 5% to about 15%, from about 5% to about 10%, or from about 10% to about 15%.

[0020] For clarity, if the amount of E-HFO-1336mzz added to Component B is 0%, then Component A must contain E-HFO-1336mzz. The amount of E-HFO-1336mzz added to Component A is from about 0% to about 15% by weight of Component A. The amount of E-HFO-1336mzz added to Component A can be, for example, from about 5% to about 15%, or from about 5% to about 10%.

[0021] One embodiment of the present disclosure is a polyurethane froth foam kit comprising: (a) a cylinder containing an A component comprising an isocyanate; (b) a cylinder containing a B component comprising an isocyanate-reactive compound; and (c) a low-pressure mixer having a mixing chamber and a spray nozzle, wherein the A component, the B component, or both comprise E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a), and the A component and the B component are supplied in separate pressurized cylinders.

[0022] It should be noted that "froth foam kit" is synonymous with "polyurethane froth foam kit" and is used interchangeably herein.

[0023] By "low pressure mixer" herein is meant any mixer capable of mixing component A and component B at a pressure of 50 psi up to about 500 psi (0.34 to 3.4 MPa).

[0024] In one embodiment of the polyurethane froth foam kit provided herein, the amount of blowing agent added to each cylinder is sufficient to equalize the pressure in both cylinders, each cylinder being understood to refer to the cylinder containing component A and the cylinder containing component B.

[0025] The present disclosure further provides polyurethane or polyisocyanurate foams prepared by the methods disclosed herein or using the froth foam kits disclosed herein. In one embodiment, the polyurethane foams provided herein have an R value greater than 6 and a closed cell content greater than 80% or greater than 90%.

[0026] In one embodiment, foams according to the present disclosure have a viscosity of 1.8 to 2.5, preferably 1.9 to 2.1 pounds per cubic foot or pcf (28.8 to 40.0, preferably 30.4 to 33.6 kilograms per cubic meter or kg / m 3 ) range of density.

[0027] In one embodiment, the low pressure when performing the methods for producing foams disclosed herein is from about 100 psi up to about 400 psi (about 0.69 MPa up to about 2.76 MPa), or from about 150 psi to about 300 psi (about 1.03 MPa to about 2.07 MPa). In one embodiment, the low pressure is at least 100 psi (0.69 MPa) up to 500 psi (3.4 MPa), or at least 150 psi (1.03 MPa) up to 500 psi (3.4 MPa), or at least 200 psi (1.38 MPa) up to 500 psi (3.4 MPa).

[0028] In one embodiment of the method or froth foam kit, components A and B are provided in separate pressurized cylinders, and the amount of co-blowing agent added to each cylinder is sufficient to equalize the pressure in both cylinders. For example, in the method, prior to mixing components A and B, both cylinders can be pressurized with a co-blowing agent, such as nitrogen, to a pressure of at least about 50 psi to a maximum of about 500 psi, e.g., (at least about 0.34 MPa to a maximum of about 3.4 MPa). The pressure can be at least 100 psi (0.69 MPa), or at least 150 psi (1.03 MPa), or at least 200 psi (1.38 MPa).

[0029] One embodiment of the present disclosure is a foamable composition. The term "foamable composition" refers to a combination of component A and component B. The foamable composition of the present disclosure includes (a) a blowing agent including E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), (b) one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a), (c) an isocyanate, (d) a polyol, (e) a catalyst, and (f) a surfactant.

[0030] In one embodiment of the method, froth foam kit, or foam prepared by the method or using the froth foam kit disclosed herein, component A includes a blowing agent comprising E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze), and component B includes a blowing agent comprising E-HFO-1336mzz. In this embodiment of the method or froth foam kit, components A and B are provided in separate pressurized cylinders, and the amount of blowing agent added to each cylinder is sufficient to equalize the pressure in both cylinders. In one embodiment of the method or froth foam kit, components A and B are provided in separate pressurized cylinders, and one or both cylinders are pressurized with a co-blowing agent to achieve a pressure of at least 50 psi (0.34 MPa). The co-blowing agent may be nitrogen.

[0031] In one embodiment of the method or froth foam kit or foam according to the present disclosure, the A component or the B component, or both, comprise Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). In one embodiment according to the embodiments of this paragraph, the A component comprises Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). According to one embodiment of this paragraph, the A component comprises Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). According to one embodiment of this paragraph, the A component and the B component each comprise Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz).

[0032] In some embodiments of the method, the froth foam kit, the foamable composition, or foams produced by the method or using the froth foam kit or using the foamable composition, one or more butane and / or pentane isomers are added to component A or component B, or both. The pentane isomer can be n-pentane, isopentane, cyclopentane, or a mixture of n-pentane and isopentane, or a mixture of n-pentane and isopentane, or a mixture of n-pentane, isopentane, and cyclopentane, or a mixture of isopentane and cyclopentane.

[0033] In some embodiments of the present method, or the present froth foam kit, or the present foamable composition, or foams produced by the present method or using the present froth foam kit or using the present foamable composition, methyl formate or water is added to the A component or the B component or both.

[0034] In one embodiment of any of the foregoing embodiments of the polyurethane froth foam kit, the A component can include a blowing agent comprising E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze) and the B component can include a blowing agent comprising E-HFO-1336mzz.

[0035] In some embodiments, the amount of E-HFO-1336mzz in Component B of the methods or froth foam kits disclosed herein is from about 0% to about 20% by weight of Component B. The amount of E-HFO-1336mzz in Component B can be, for example, from about 5% to about 20%, from about 5% to about 15%, from about 5% to about 10%, or from about 10% to about 15%.

[0036] For clarity, if the amount of E-HFO-1336mzz in Component B of the present method or froth foam kit is 0%, then Component A must contain E-HFO-1336mzz. The amount of E-HFO-1336mzz in Component A is from about 0% to about 15% by weight of Component A. The amount of E-HFO-1336mzz in Component A can be, for example, from about 5% to about 15%, or from about 5% to about 10%.

[0037] In some embodiments, the amount of co-blowing agent selected from one or more of carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a) in Component B of the present method or froth foam kit is from about 0.1 to about 5%.

[0038] In one embodiment, the co-blowing agent is carbon dioxide and the amount of co-blowing agent in Component B of the present method or froth foam kit is from about 0.1 to about 1%.

[0039] In one embodiment, the co-blowing agent is nitrogen and the amount of co-blowing agent in Component B of the method or froth foam kit is from about 0.1% to about 2%.

[0040] In one embodiment, the co-blowing agent is 1,1-difluoroethane and the amount of co-blowing agent in Component B of the method or froth foam kit is from about 0.1% to about 2%.

[0041] In some embodiments, component A of the method or froth foam kit includes a co-blowing agent, wherein the co-blowing agent is carbon dioxide, nitrogen, or a combination thereof.

[0042] In one embodiment, Component A of the present method or froth foam kit includes a co-blowing agent, the co-blowing agent being carbon dioxide, and the amount of co-blowing agent in Component A being from about 0.1 to about 1%.

[0043] In one embodiment, component A of the method or froth foam kit includes a co-blowing agent, the co-blowing agent being nitrogen, and the amount of co-blowing agent in component A is from about 0.1% to about 2%.

[0044] In carrying out the methods disclosed herein or in providing the froth foam kits disclosed herein, the A component or the B component or both may include two or more co-blowing agents.

[0045] In one embodiment, one or more of Z-HFO-1336mzz, butane, pentane, methyl formate, and water are added to the A component of the method or froth foam kit.

[0046] In one embodiment, the B component of the method or froth foam kit comprises one or more of Z-HFO-1336mzz, butane, pentane, methyl formate, and water.

[0047] In one embodiment, the A component of the method or the froth foam kit comprises Z-HFO-1336mzz and one or more butane isomers. In one embodiment, the one or more butane isomers include or are isobutane. In one embodiment, the A component of the method or the froth foam kit comprises Z-HFO-1336mzz and one or more pentane isomers. In one embodiment, the one or more pentane isomers include or are cyclopentane. In one embodiment, the A component of the method or the froth foam kit comprises Z-HFO-1336mzz and methyl formate. In one embodiment, the A component of the method or the froth foam kit comprises Z-HFO-1336mzz and water.

[0048] In one embodiment, the B component of the present method or the present froth foam kit comprises Z-HFO-1336mzz and one or more butane isomers. In one embodiment, the one or more butane isomers include or are isobutane. In one embodiment, the B component of the present method or the present froth foam kit comprises Z-HFO-1336mzz and one or more pentane isomers. In one embodiment, the one or more pentane isomers include or are cyclopentane. In one embodiment, the B component of the present method or the present froth foam kit comprises Z-HFO-1336mzz and methyl formate. In one embodiment, the B component of the present method or the present froth foam kit comprises Z-HFO-1336mzz and water.

[0049] In one embodiment of the method, component A of the method or froth foam kit comprises E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze) and component B comprises HFO-1336mzz-E. In this embodiment, one option is the absence of a catalyst in component A. One option is the absence of water in component A of the method or froth foam kit. Because catalysts and / or water can degrade component A containing E-HFO-1234ze, the absence of catalyst and water in component A improves the stability of component A containing E-HFO-1234ze.

[0050] The amount of E-HFO-1234ze in Component A of the present method or froth foam kit is about 0% to about 15% by weight of Component A. The amount of E-HFO-1234ze in Component A of the present method or froth foam kit can be, for example, about 5% to about 15%, or about 5% to about 10%.

[0051] In one embodiment of the method or the froth foam kit, when Component B comprises E-HFO-1234ze, Component B further comprises CO. In one embodiment of the method or the froth foam kit, when Component B comprises E-HFO-1234ze, no CO is present in Component B.

[0052] In some of the aforementioned methods or froth foam kits, component A or component B includes Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). When component A or component B includes Z-HFO-1336mzz, the amount of Z-HFO-1336mzz is greater than 0% to about 20%, e.g., 1% to about 15%, e.g., 1% to 10%, percents based on the total weight of component A or component B. In one embodiment, the amount of Z-HFO-1336mzz in component B is about 1% to about 5% based on the total weight of component B.

[0053] In any of the aforementioned methods or foam foam kits, one or more butane isomers or pentane isomers are added to component A or component B. In such methods or foam foam kits, the preferred butane isomer is isobutane. In such methods or foam foam kits, the pentane isomer may be selected from one or more of n-pentane, isopentane, and cyclopentane, preferably cyclopentane. When butane or pentane is used, the amount of butane or pentane added is 1% to 10% based on the total weight of component A or component B.

[0054] In one embodiment of the method or froth foam kit, methyl formate or water is added to either the A component or the B component or both.

[0055] When water is added to component A of the present method or the present froth foam kit or component B of the present method or the present froth foam kit, the amount of water added is greater than 0% to about 5%, e.g., 0.1% to about 3%, e.g., 0.2 to 5%, percent based on the total weight of component A or component B. In one embodiment, the amount of water added to component B is about 1% to about 2% based on the total weight of component B.

[0056] When methyl formate is added to component A of the present method or the present froth foam kit, or component B of the present method or the present froth foam kit, the amount of methyl formate added is greater than 0% up to 4.5%, for example, 0.5% to 3%, the percentage being based on the total weight of component A or component B.

[0057] The combination of Components A and B is referred to herein as the "foamable composition." The foamable composition includes (a) a blowing agent including E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), (b) one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a), (c) an isocyanate, (d) a polyol, (e) a catalyst, and (f) a surfactant.

[0058] One embodiment of the present disclosure is a foamable composition comprising the A and B components disclosed above for the method and froth foam kit. In one embodiment, the foamable composition comprises E-HFO-1234ze.

[0059] In some embodiments of the foamable composition of the present disclosure, the total amount of blowing agent comprising E-HFO-1336mzz and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane comprises from about 5% to about 15% by weight of the foamable composition, for example, from about 10% to about 15% by weight of the foamable composition.

[0060] In one embodiment, the foamable composition comprises Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). The total amount of blowing agents comprising E-HFO-1336mzz, Z-HFO-1336mzz, and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane comprises about 5% to about 15% by weight of the foamable composition, for example, about 10% to about 15% by weight of the foamable composition.

[0061] In some embodiments, the foamable composition comprises one or more butane and / or pentane isomers. The butane isomer is preferably isobutane. Pentane isomers include n-pentane, isopentane, and cyclopentane. The pentane isomer can be n-pentane, isopentane, cyclopentane, or a mixture of n-pentane and isopentane, or a mixture of n-pentane and isopentane, or a mixture of n-pentane, isopentane, and cyclopentane, or a mixture of isopentane and cyclopentane.

[0062] In some embodiments, the foamable composition includes methyl formate or water. The foamable composition may include Z-HFO-1336mzz and methyl formate. The foamable composition may include Z-HFO-1336mzz and water.

[0063] In the present method, the isocyanate can be any suitable isocyanate. Suitable isocyanates have at least two isocyanate groups per molecule. Suitable isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetra ... Examples of the isocyanate include methylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, isomers thereof, and / or combinations of two or more thereof.

[0064] For example, the isocyanate may have an NCO content of 25% to 35%, a functionality of 2.5 to 3.0, and a viscosity of 150 to 220 cP.

[0065] In certain embodiments, the isocyanate-reactive compound is a polyol.

[0066] In some embodiments, the polyol is a polyester polyol. Suitable polyester polyols include those prepared by reacting a carboxylic acid and / or its derivatives or a polycarboxylic acid anhydride with a polyhydric alcohol. The polycarboxylic acid can be any of the known aliphatic, cycloaliphatic, aromatic, and / or heterocyclic polycarboxylic acids, and can be substituted (e.g., with halogen atoms) and / or unsubstituted. Examples of suitable polycarboxylic acids and anhydrides include oxalic acid, malonic acid, glutaric acid, pimelic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, and dimer and trimer fatty acids such as oleic acid, which may be in a mixture with monomeric fatty acids. Simple polycarboxylic acid esters such as terephthalic acid dimethyl ester, terephthalic acid bisglycol, and their extracts can also be used. Polyhydric alcohols suitable for preparing polyester polyols can be aliphatic, cycloaliphatic, aromatic, and / or heterocyclic. The polyhydric alcohol may optionally contain substituents that are inert during the reaction, such as chlorine and bromine substituents, and / or may be unsaturated. Suitable amino alcohols such as monoethanolamine and diethanolamine may also be used. Examples of suitable polyhydric alcohols include ethylene glycol, propylene glycol, polyoxyalkylene glycol di(such as diethylene glycol, polyethylene glycol, dipropylene glycol, and polypropylene glycol), glycerol, and trimethylolpropane.

[0067] Other suitable polyester polyols include, but are not limited to, aromatic polyester polyols, such as those made by transesterifying polyethylene terephthalate (PET) scrap with glycols such as diethylene glycol, or those made by reacting phthalic anhydride with glycols. The resulting polyester polyols can be further reacted with ethylene oxide and / or propylene oxide to form extended polyester polyols containing additional internal alkyleneoxy groups.

[0068] 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 200 mg KOH / g to about 300 mg KOH / g, or about 235 to about 265, or about 230 to about 250, or about 295 to about 315 mg KOH / g.

[0069] Exemplary commercially available polyester polyols include polyester polyols Stepanpol® PS-2352 (Stepan Company, Chicago, IL), Stepanpol® PS-2502A (Stepan Company, Chicago, IL), Stepanpol® PS-2412 (Stepan Company, Chicago, IL), Stepanpol® PS-2520 (Stepan Company, Chicago, IL), Stepanpol® PS-3021 (Stepan Company, Chicago, IL), Stepanpol® PS-3024 (Stepan Company, Chicago, IL), Terol® 256 (Huntsman, The Woodlands, TX), and Terol® 925 (Huntsman, The Woodlands, TX). Woodlands, TX), Terol® 563 (Huntsman, The Woodlands, TX), Terol® 649 (Huntsman, The Woodlands, TX), Terol® 1465 (Huntsman, The Woodlands, TX), Isoexter® TB-305 (COIM, West Deptford, NJ), Isoexter® TB-306 (COIM, West Deptford, NJ), Terate® HT5510 (Invista), Terate® 5232 (Invista), Terate® 5100 (Invista), Terate® 5150 (Invista), Terate® 5170 (Invista), Carpol® PES-240 (Carpenter Co., Richmond, VA), Carpol® PES-265 (Carpenter Co., Richmond, VA), Co., Richmond, VA), Carpol® PES-305 (Carpenter Co.and Carpol® PES-295 (Carpenter Co., Richmond, VA).

[0070] In some embodiments, the polyol comprises one or more polyether polyols. Examples of suitable polyether polyols include, but are not limited to, polyethylene oxide, polypropylene oxide, and mixed polyethylene-propylene oxides with terminal hydroxyl groups, among others. Other suitable polyols can be prepared by reacting ethylene oxide and / or propylene oxide with initiators having 2 to 16 or 3 to 8 hydroxyl groups present in polyhydroxy compounds, such as, for example, glycerol, pentaerythritol, and carbohydrates, such as sorbitol, glucose, and sucrose. Suitable polyether polyols can also include aliphatic or aromatic amine-based polyols. Exemplary commercially available polyether polyols include polyether polyols JEFFOL® PPG-400 (Huntsman, The Woodlands, TX), JEFFOL® PPG-1000 (Huntsman, The Woodlands, TX), JEFFOL® FX31-240 (Huntsman, The Woodlands, TX), JEFFOL® G31-28 (Huntsman, The Woodlands, TX), JEFFOL® R-425X (Huntsman, The Woodlands, TX), JEFFOL® R-470X (Huntsman, The Woodlands, TX), JEFFOL® S-490 (Huntsman, The Woodlands, TX), JEFFOL® SG-360 (Huntsman, The Woodlands, TX), JEFFOL® SG-522 (Huntsman, The Woodlands, TX), and others. Woodlands, TX), Carpol(R) PGP-400 (Carpenter Co., Richmond, VA), Carpol(R) PGP-1000 (Carpenter Co., Richmond, VA), Carpol(R) GP-700 (Carpenter Co., Richmond, VA), Carpol(R) GP-6015 (Carpenter Co., Richmond, VA)VA), Carpol® MX-425 (Carpenter Co., Richmond, VA), Carpol® MX-470 (Carpenter Co., Richmond, VA), Carpol® GSP-355 (Carpenter Co., Richmond, VA), Carpol® GSP-520 (Carpenter Co., Richmond, VA), Carpol® SP-477 (Carpenter Co., Richmond, VA), VORANOL® 220-260 (Dow Chemical, Midland, MI), VORANOL® 220-110 (Dow Chemical, Midland, MI), VORANOL® 230-238 (Dow Chemical, Midland, MI), VORANOL® 232-027 (Dow Chemical, Midland, MI), VORANOL® 470 (Dow Chemical, Midland, MI), VORANOL® 360 (Dow Chemical, Midland, MI), VORANOL® 520 (Dow Chemical, Midland, MI), VORANOL® 391 (Dow Chemical, Midland, MI), Pluracol® P410R (BASF, Lemforde, Germany), Pluracol® P1010 (BASF, Lemforde, Germany), Pluracol® GP730 (BASF, Lemforde, Germany), Pluracol® 220 (BASF, Lemforde, Germany), Lupranol® 3422 (BASF, Lemforde, Germany), Pluracol® SG-360 (BASF, Lemforde, Germany), Pluracol® 824 (BASF, Lemforde, Germany), Pluracol® 735 (BASF, Lemforde, Germany), ARCOL® PPG-425 (Covestro, Leverkusen, Germany)Germany), ARCOL® 1000 (Covestro, Leverkusen, Germany), ARCOL® LHT-240 (Covestro, Leverkusen, Germany), MULTRANOL® 9139 (Covestro, Leverkusen, Germany), MULTRANOL® 3901 (Covestro, Leverkusen, Germany), MULTRANOL® 4034 (Covestro, Leverkusen, Germany), Poly-G® 20-265 (Monument Chemical, Indianapolis, IN), Poly-G® 20-112 (Monument Chemical, Indianapolis, IN), Poly-G® 30-240 (Monument Chemical, Indianapolis, IN), Poly-G® 85-29 (Monument Chemical, Indianapolis, IN). Poly-G® 73-490 (Monument Chemical, Indianapolis, IN), Poly-G® 74-376 (Monument Chemical, Indianapolis, IN), and Poly-G® 74-532.

[0071] In some embodiments, the polyether polyol is a medium-functionality polyether polyol. For example, the polyether polyol has a functionality of about 4. In some embodiments, the polyether polyol is sucrose / glycerin initiated. In some embodiments, the polyether polyol is a Mannich polyether polyol. As used herein, the term "Mannich polyether polyol" refers to an aromatic polyol obtained by alkoxylation with propylene oxide and / or ethylene oxide of a Mannich base obtained by the classical Mannich reaction between a phenol (e.g., phenol, p-nonylphenol), formaldehyde, and an alkanolamine (diethanolamine, diisopropanolamine, monoethanolamine, monoisopropanolamine, etc.). Exemplary 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).

[0072] In some embodiments, the polyol comprises a combination of a polyester polyol and a polyether polyol.

[0073] In some embodiments, one or more additives can be included in the B component described herein. For example, the B component can further include one or more additives including, but not limited to, catalysts, surfactants, flame retardants, stabilizers, preservatives, chain extenders, crosslinkers, water, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, nucleating agents, smoke suppressants, and pigments.

[0074] In some embodiments, the B component comprises at least one catalyst, at least one surfactant, water, at least one flame retardant, and at least one nucleating agent.

[0075] Suitable urethane catalysts 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 amounts that increase the reaction rate of the polyisocyanate. For 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.

[0076] Exemplary catalysts are disclosed, for example, in U.S. Patent No. 5,164,419, the disclosure of which is incorporated herein by reference. Catalysts for the trimerization of polyisocyanates, such as alkali metal alkoxides, alkali metal carboxylates, or quaternary amine salts, may also be optionally used herein. Such catalysts are used in amounts that measurably increase the reaction rate of the polyisocyanates. Typical amounts of catalyst are about 0.1% to about 5% by weight, based on the total weight of all foaming ingredients. Non-limiting examples of catalysts include POLYCAT® 8, N, manufactured by Evonik Industries.N-dimethylcyclohexylamine, POLYCAT® 5 from Evonik Industries, pentamethyldiethylenetriamine, and CURITHANE® 52 from Evonik Industries, 2-methyl(n-methylamino b-acetate sodium nonylphenol), POLYCAT® 30 (Evonik Industries), POLYCAT® 36 (Evonik Industries), POLYCAT® 46 (Evonik Industries), POLYCAT® 77 (Evonik Industries), POLYCAT® 9 (Evonik Industries), Dabco® 2039 (Evonik Industries), Dabco® K15 (Evonik Industries), Dabco® 204 (Evonik Industries), Dabco® 2040 (Evonik Industries), Dabco® BL-19 (Evonik Industries), Dabco® BL-17 (Evonik Industries) Industries), Dabco® T (Evonik Industries), Dabco® T-125 (Evonik Industries), Dabco® K-15 (Evonik Industries), Dabco® TMR (Evonik Industries), Dabco® TMR-2 (Evonik Industries), Dabco® TMR-3 (Evonik Industries), Dabco® TMR-30 (Evonik Industries), Bicat® 8210 (The Shepard Chemical Company, Cincinnati, OH), Bicat® 8840 (The Shepard Chemical Company, Cincinnati, OH), Bicat® 8842 (The Shepard Chemical Company, Cincinnati, OH), K-Kat® XK 651 (King Industries, Norwalk,CT), K-Kat® 614 (King Industries, Norwalk, CT), K-Kat® 672 (King Industries, Norwalk, CT), K-Kat® 604 (King Industries, Norwalk, CT), Niax® UL1 (Momentive Performance Materials Inc., Waterford, NY), Niax® UL22, Niax® UL1 (Momentive Performance Materials Inc., Waterford, NY), Jeffamine® D-230 (Huntsman, The Woodlands, TX), Jeffamine® T403 (Huntsman, The Woodlands, TX), Jeffamine® D2000 (Huntsman, The Woodlands, TX), Jeffamine® T5000 (Huntsman, The Woodlands, TX), Jeffamine® PMDETA (Huntsman, The Examples of suitable amines include Jeffamine® ZF20 (Huntsman, The Woodlands, TX), Jeffcat® DMCHA (Huntsman, The Woodlands, TX), Jeffamine® ZF54 (Huntsman, The Woodlands, TX), tin, dibutyltin mercaptide, potassium octanoate, potassium acetate, bismuth, and bismuth carboxylate mixtures.

[0077] In some embodiments, the foamable composition includes a surfactant. Suitable surfactants can include liquid or solid organosilicone compounds. Other surfactants include polyethylene glycol ethers of long-chain alcohols, long-chain alkyl acid sulfates, alkyl sulfonates, and tertiary amine or alkanolamine salts of alkylaryl sulfonic acids. In some embodiments, the surfactant is a silicone surfactant. In some embodiments, the surfactant is a silicone polyether surfactant. In some embodiments, the surfactant is Dabco® DC5585.

[0078] In some embodiments, the B component comprises a flame retardant. Useful flame retardants include, but are not limited to, tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(1-chloro-2-propyl)phosphate (TCPP), tris(2,3-dibromopropyl)phosphate, tris(1,3-dichloropropyl)phosphate, diammonium phosphate, halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and bromine-containing diester / ether diols of tetrabromophthalic anhydride, such as mixed esters of tetrabromophthalic anhydride with diethylene glycol and propylene glycol. An exemplary commercially available flame retardant is Saytex® RB-79 (Albemarle Corporation, Baton Rouge, LA), a reactive bromine-containing diester / ether diol of tetrabromophthalic anhydride. In some embodiments, the flame retardant is tris(1-chloro-2-propyl)phosphate (TCPP).

[0079] In some embodiments, Component B includes a nucleating agent. The nucleating agent primarily functions to increase the cell count and reduce the cell size in the foam and can be used in an amount of about 0.1 to about 10 parts by weight per 100 parts by weight of resin. Typical nucleating agents include, among others, at least one member selected from the group consisting of talc, sodium bicarbonate-citric acid mixtures, calcium silicate, and carbon dioxide. In some embodiments, the foamable composition does not contain 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 mixtures, calcium silicate, carbon dioxide, and the like.

[0080] In some embodiments, the B component comprises E-HFO-1336mzz, at least one polyhydric alcohol, at least one catalyst, at least one surfactant, at least one flame retardant, and at least one nucleating agent, as described herein. [Example]

[0081] material Opteon™ 1100 (Z-1,1,1,4,4,4-hexafluoro-2-butene, Z-HFO-1336mzz) and Opteon™ 1150 (E-1,1,1,4,4,4-hexafluoro-2-butene, E-HFO-1336mzz) foam blowing agents are available from The Chemours Company FC, LLC (Wilmington, DE). (Note that for convenience, Opteon™ 1100 may be referred to herein as "1100," and Opteon™ 1150 may be referred to herein as "1150.") PS 2352 is Stepanpol PS2352 polyester polyol available from Stepan Company (Northfield, IL). Pluracol® SG-360 polyol is available from BASF Corporation (Wyandotte, MI). Carpol® P-700 polyether polyol is available from Carpenter Co. (Richmond, VA). TCPP is tris(1-chloro-2-propyl) phosphate. PHT4-DIOL™ flame retardant is available from LANXESS Solutions US Inc. (Pittsburgh, PA). DC193 silicone surfactant is commercially available. LK-443 surfactant is available from Evonik Industries. Catalysts, including amine and isocyanurate catalysts, are available from Evonik Industries. Polymeric MDI (isocyanate) is available from Dow Chemical Company (Midland, MI). DEG is commercially available diethylene glycol.

[0082] Example 1. LPSPF Test Formulation 1 Hand-mixed foam To mimic the isocyanate cans in the LPSPF kit, Opteon™ blowing agent was premixed into the isocyanate side by hand mixing. The blowing agents used in the isocyanate were Opteon™ 1100 and Opteon™ 1150 in the same ratios, but at half the loading percentage of the resin loading percentage. These two components were mixed at 4000 rpm using an arrow overhead mixer. Table 1 provides the resin formulation, and Table 2 provides the physical properties of the hand-mixed foam. The hand mixes overwhelmingly show that the Opteon™ blowing agent exceeds the desired R-value of 6 and meets other desired physical properties such as density and closed cell content.

[0083] [Table 1]

[0084] [Table 2]

[0085] Example 2. LPSPF Test Formulation 2 Shelf Life Test Shelf life was evaluated based on the formation of carbonic acid. The theory is that carbonic acid is formed from the reaction of Opteon™ 1150, carbon dioxide, and water. If formed, carbonic acid will react with the amine catalyst over time and interfere with the reactivity of the LPSPF kit.

[0086] Test cylinders capable of holding pressures suitable for LPSPF kits (15-25 psi) were designed to evaluate shelf life in an accelerated aging test. Four test cylinders were filled with the formulations listed in Table 3 and rotated for one hour to ensure uniform mixing. Three cylinders were placed in a 50°C oven for aging. The first cylinder was then opened, poured into a beaker, and immediately hand-mixed with isocyanate to obtain initial reactivity. A similar procedure was followed for the other cylinders to measure reactivity at one, two, and three weeks of aging. Carbonic acid forms rapidly in a heated environment, which could interfere with the catalyst if it were to form.

[0087] [Table 3]

[0088] [Table 4]

[0089] Shelf life testing showed that no significant carbonation occurred as it had no effect on reactivity as illustrated by cream, gel, rise, and tack times.

[0090] Sprayed foam The formulation set forth in Table 3 (Test Formulation 2) was used to spray the LPSPF kit, and the results are provided in Table 5.

[0091] [Table 5]

[0092] Example 3. LPSPF Test Formulation 3 Degradation Test Note: Only the resin side of the LPSPF kit was aged. All isocyanate sides were prepared on the day of spray testing. The isocyanate side was not aged due to the lack of reactivity that could affect the blowing agent, catalyst, or surfactant. The kit was filled with blowing agent but was not pressurized to 200 psi with nitrogen due to safety concerns. When it was time to test the kit, the resin kit was removed from the oven and allowed to cool to room temperature. The resin can, along with the isocyanate can, was pressurized to 200 psi with nitrogen. Separate cans were prepared for the 0 hour, 2 week, 4 week, and 6 week spray times. Tables 6-9 show formulation properties. (MF is methyl formate, and tDCE is trans-dichloroethylene.)

[0093] [Table 6] * DNS indicates "not sprayed."

[0094] [Table 7] DNF indicates samples that did not result in testable polyurethane foam samples. DNS indicates "not sprayed."

[0095] [Table 8] DNF indicates samples that did not produce testable polyurethane foam samples.

[0096] [Table 9] DNF indicates samples that did not result in testable polyurethane foam samples.

[0097] The samples subjected to accelerated degradation were tested for their free ion content by ion chromatography as provided in Table 10. For each sample, 3 grams of side B was diluted with 30 milliliters of pure water and the mixture was stirred overnight. Then it was subjected to IC (ion chromatography) according to ASTM D4327. To ensure accuracy, the sample may be further diluted so that the results fall within the calibration curve of the machine.

[0098]

Table 10

[0099] The free fluorine and chlorine anions in side B are directly related to the decomposition of the blowing agent and TCPP in each formulation. As seen in the "blank" samples without the blowing agent, there are significant levels of chloride anions generated over the course of accelerated degradation. [[ID=*]]

[0100] Opteon (trademark) - based formulations are stable in the resin and common catalysts have little or no effect on these formulations.

[0101] The E - 1234ze - containing formulations were found to be less stable than the E - HFO - 1336mzz - containing formulations in the presence of catalysts and increased chloride levels.

[0102] )

Table 11

[0103] It should be noted that there seems to be a formatting issue with the repeated use of and in the original text which might need to be clarified in the source. The translation above is done as accurately as possible based on the provided text.As shown in the examples, LPSPF formulations containing E-HFO-1336mzz have long shelf life when used in the presence of traditional polyol, catalyst, surfactant, and water levels in LPSPF kits. Such formulations also provided good properties (comments regarding partition ratio, R-value, density, closed cell, etc.).

Claims

1. 1. A method for generating a form, comprising: (a) preparing an A component containing an isocyanate; (b) preparing a B component comprising an isocyanate-reactive compound; (c) mixing the A component and the B component under low pressure to produce a foam; the A component, the B component, or both further comprise a blowing agent comprising E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a); The method wherein the low pressure is at least about 50 psi and at most about 500 psi (at least about 0.34 and at most about 3.4 MPa).

2. 2. The method of claim 1, wherein the A component comprises E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze) and the B component comprises E-HFO-1336mzz.

3. 2. The method of claim 1, wherein Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) is added to the A component, the B component, or both.

4. The method according to claim 3, wherein Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) is added to the A component.

5. The method according to claim 3, wherein Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) is added to the B component.

6. 4. The method of claim 3, wherein Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) is added to both the A component and the B component.

7. 3. The method of claim 2, wherein the A component and the B component are provided in separate pressurized cylinders and the amount of co-blowing agent added to each cylinder is sufficient to equalize the pressure in both cylinders.

8. 4. The method of claim 3, wherein one or both cylinders are pressurized with a co-blowing agent prior to dispensing to achieve a pressure of at least 50 psi (0.34 MPa).

9. 9. The method according to any one of claims 1 to 8, wherein one or more butane isomers or pentane isomers are added to the A component or the B component.

10. 10. The method according to any one of claims 1 to 9, wherein methyl formate or water is added to the A component, the B component, or both.

11. The method of claim 10 wherein water is added to the A component.

12. The method of claim 10 wherein water is added to the B component.

13. 11. The method of claim 10, wherein water is added to both the A component and the B component.

14. The method of claim 10, wherein methyl formate is added to the A component.

15. The method of claim 10, wherein methyl formate is added to the B component.

16. 11. The method of claim 10, wherein methyl formate is added to both the A component and the B component.

17. 10. The method of claim 1, wherein the low pressure is from about 100 psi up to about 400 psi (about 0.69 MPa up to about 2.76 MPa).

18. 10. The method of claim 1, wherein the low pressure is from about 150 psi to about 300 psi (from about 1.03 MPa to about 2.07 MPa).

19. 10. The method of claim 1, wherein the amount of E-HFO-1336mzz in the B part is from about 5% to about 20%, or from about 5% to about 15%, or from about 5% to about 10%, or from about 10% to about 15% by weight of the B part.

20. 10. The method of claim 1, wherein the amount of E-HFO-1336mzz in the A component is from about 0% to about 15% by weight of the A component, or from about 5% to about 20% by weight of the A component, or from about 5% to about 15% by weight, or from about 5% to about 10% by weight, or from about 10% to about 15% by weight.

21. The method of claim 1, wherein the amount of the co-blowing agent in the B component is from about 0.1% to about 2%.

22. 22. The method of claim 21, wherein the co-blowing agent is carbon dioxide and the amount of the co-blowing agent in the B component of the method or froth foam kit is from about 0.1 to about 1%.

23. 22. The method of claim 21, wherein the co-blowing agent is nitrogen and the amount of the co-blowing agent in the B component of the method or froth foam kit is from about 0.1 to about 2%.

24. 22. The method of claim 21, wherein the co-blowing agent is 1,1-difluoroethane and the amount of the co-blowing agent in the B component of the method or froth foam kit is from about 0.1 to about 2%.

25. 10. The method of claim 1, wherein the A part of the method includes a co-blowing agent, and the amount of the co-blowing agent in the A part is from about 0.1% to about 2%.

26. 26. The method of claim 25, wherein the co-blowing agent is carbon dioxide and the amount of the co-blowing agent in the A component of the method or froth foam kit is from about 0.1 to about 1%.

27. 26. The method of claim 25, wherein the co-blowing agent is nitrogen and the amount of the co-blowing agent in the A component of the method or froth foam kit is from about 0.1 to about 2%.

28. 6. The method of claim 5, wherein the butane comprises isobutane and the pentane is selected from one or more of n-pentane, isopentane, and cyclopentane.

29. The method of any one of claims 1 to 28, wherein methyl formate or water is added to the A component, the B component, or both.

30. 30. The method of claim 29, wherein water is added to the A component or the B component, and the amount of water added is up to 2% by weight.

31. 30. The method of claim 29, wherein water is added to the A component or the B component, and the amount of methyl formate added is up to 4.5%.

32. The method of any one of claims 1 to 31, wherein the isocyanate-reactive compound is a polyol.

33. 33. The method of claim 32, wherein the polyol is a polyester polyol.

34. 1. A polyurethane froth foam kit comprising: (a) a cylinder containing an A component containing an isocyanate; (b) a cylinder containing a B component comprising an isocyanate-reactive compound; (c) a low-pressure mixer having a mixing chamber and a spray nozzle; E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a) are added to the A component, the B component, or both; A polyurethane froth foam kit, wherein the A component and the B component are provided in separate pressurized cylinders.

35. 35. The polyurethane froth foam kit of claim 34, wherein the amount of blowing agent added to each cylinder is sufficient to equalize the pressure in both cylinders.

36. A polyurethane foam prepared by the method of any one of claims 1 to 33.

37. A polyisocyanurate foam prepared by the method of any one of claims 1 to 33.

38. 37. The foam of claim 36 having an R value greater than 6 and a closed cell content greater than 90%.

39. 37. The foam of claim 36 having a density in the range of 1.8 to 2.5 pounds per cubic foot (28.8 to 40.0 kilograms per cubic meter).

40. 1. A foamable composition comprising: (a) a blowing agent comprising E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz); (b) one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a); (c) an isocyanate; (d) a polyol; (e) a catalyst; and (f) a surfactant.

41. 41. The foamable composition of claim 40, wherein the composition comprises E-HFO-1234ze.

42. 41. The foamable composition of claim 40, wherein the total amount of the blowing agent comprising E-HFO-1336mzz and the one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane comprises from about 5% to about 15% by weight of the foamable composition.

43. 41. The foamable composition of claim 40, wherein the total amount of the blowing agent comprising E-HFO-1336mzz and the one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane comprises from about 10% to about 15% by weight of the foamable composition.

44. 41. The foamable composition of claim 40, further comprising Z-HFO-1336mzz.

45. 45. The foamable composition of claim 44, wherein the total amount of the blowing agent comprising E-HFO-1336mzz and the one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane comprises from about 5% to about 15% by weight of the foamable composition.

46. 45. The foamable composition of claim 44, wherein the total amount of the blowing agent comprising E-HFO-1336mzz and the one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane comprises from about 10% to about 15% by weight of the foamable composition.

47. 45. The foamable composition of claim 44, further comprising methyl formate.

48. 45. The foamable composition of claim 44, further comprising water.

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