Method for producing foamed foams

Abstract

The present disclosure provides a process for producing foamed polyurethane foams using storage stable components. The method comprises the following steps: preparing a component A containing isocyanate; preparing a component B comprising an isocyanate reactive compound, and generating a foam by mixing the component A and the component B at low pressure; wherein the component A or the component B, or both, further comprises 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 the group consisting of carbon dioxide, nitrogen or 1, 1-difluoroethane (HFC-152a).

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 411,878, filed on September 30, 2022, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] 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), while in another aspect, the invention is directed to a foaming foam kit using a low GWP blowing agent. Background Art

[0004] For polyurethane or polyisocyanurate foam applications, the foamable composition is provided as a two-component formulation, an A component (which contains the isocyanate) and a B component (which contains the isocyanate-reactive compound such as a polyol).

[0005] Certain applications such as foam kit foam require the use of a gaseous blowing agent incorporated into both the A component and the B component to enhance the foamability of the mixture of the A component and the B component and to enhance the mixing of the components in low pressure mixing equipment. The reactive components are each stored under pressure in a separate container, with additional ingredients in each container to support the production of foam, such as catalysts, water, inert gases, etc. The two components are then mixed to produce a foaming foam, which is discharged through an applicator nozzle. After discharge, the foaming foam can be sprayed onto a target as a stream of polyurethane to provide sealing and insulation.

[0006] Historically, blowing agents include 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 high global warming potentials (GWP).

[0007] 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 suggested for use as blowing agents in polyurethane foams having suitable boiling points and properties. However, certain low GWP blowing agents have been found to degrade over time in foamable compositions. For example, it is known that when used in the presence of an amine catalyst for producing foam, E-HFO-1234ze decomposes to produce HF, and E-HFO-1233zd is susceptible to decomposition into corrosive chlorine compounds, including HCl. Despite safety concerns, the presence of HF or HCl in the blowing agent significantly reduces foam reactivity and quality, while prolonging curing time.

[0008]

[0006] Therefore, there is a need for new blowing agent formulations and compositions for foaming foam kits and methods for producing foaming foams. Summary of the invention

[0009] The present invention provides a method for meeting the need for low global warming potential (GWP) and zero ozone depletion potential (ODP) sustainable blowing agents, particularly for low pressure spray polyurethane or polyisocyanurate foams.

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

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

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

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

[0014] The present invention provides a polyurethane foaming kit, which includes: (a) a cylinder including an A component, wherein the A component contains an isocyanate; (b) a cylinder including a B component, wherein the B component contains 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 a polyurethane or polyisocyanurate foam prepared by the method disclosed herein. The present disclosure also provides a polyurethane or polyisocyanurate foam prepared using the polyurethane foaming foam kit as disclosed herein.

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

[0017] Unless indicated to the contrary, all parts and percentages are by weight.

[0018] The present disclosure provides a method for generating foam, the method comprising: (a) preparing an A component containing an isocyanate; (b) preparing a B component containing an isocyanate-reactive compound, and (c) generating foam by mixing the A component and the B component under low pressure; wherein the A component or the B component or both further comprises a blowing agent containing E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), and one or more co-blowing agents selected from the group consisting of carbon dioxide, nitrogen or 1,1-difluoroethane (HFC-152a); and wherein the low pressure is at least about 50 psi and up to about 500 psi (at least about 0.34 MPa 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 the B component is between about 0% and about 20% by weight of the B component. The amount of E-HFO-1336mzz added to the B component 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 the B component is 0%, then the A component must contain E-HFO-1336mzz. The amount of E-HFO-1336mzz added to the A component is between about 0% and about 15% by weight of the A component. The amount of E-HFO-1336mzz added to the A component 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 foam kit comprising: (a) a cylinder comprising an A component, the A component comprising an isocyanate; (b) a cylinder comprising a B component, the 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 wherein the A component and the B component are provided in separate pressurized cylinders.

[0022] Note that "foaming foam kit" and "polyurethane foaming foam kit" are synonymous and used interchangeably herein.

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

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

[0025] The present disclosure also provides a polyurethane or polyisocyanurate foam prepared by the method disclosed herein or using the foaming foam kit as disclosed herein. In one embodiment, the polyurethane foam provided herein has an R value greater than 6 and a closed cell content greater than 80% or greater than 90%.

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

[0027] In one embodiment, in performing the methods disclosed herein for generating foam, the low pressure is about 100 psi and up to about 400 psi (about 0.69 MPa and up to about 2.76 MPa) or 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 present method or foaming foam kit, the A component and the B component are provided in separate pressurized cylinders, and the amount of the co-foaming agent added to each cylinder is sufficient to equalize the pressure in the two cylinders. For example, in the present method, before mixing the A component and the B component, the two cylinders can be pressurized with a co-foaming agent (such as nitrogen) to a pressure of at least about 50 psi and up to about 500 psi (such as at least about 0.34 MPa up to 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 so-called "foamable composition" means a combination of component A and component B. The foamable composition of the present disclosure includes: (a) a blowing agent comprising E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), (b) one or more auxiliary blowing agents selected from the group consisting of carbon dioxide, nitrogen or 1,1-difluoroethane (HFC-152a); (c) isocyanate; (d) polyol; (e) catalyst; and (f) surfactant.

[0030] In one embodiment of the method or foaming foam kit or the foam prepared by the method or using the foaming foam kit disclosed herein, the A component comprises a blowing agent containing E-1,3,3,3-tetrafluoropropylene (E-HFO-1234ze), and the B component comprises a blowing agent containing E-HFO-1336mzz. In the method or foaming foam kit of this embodiment, the A component and the B component are provided in separate pressurized cylinders, and the amount of blowing agent added to each cylinder is sufficient to equalize the pressure in the two cylinders. In a method or foaming foam kit of this embodiment, the A component and the B component 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 50psi (0.34MPa). The co-blowing agent can be nitrogen.

[0031] In one embodiment of the method or foaming 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 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 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 or foaming foam kit or foamable composition or foam produced by the method or using the foaming foam kit or using the foamable composition, one or more isomers of butane and / or pentane are added to component A or component B or both. The pentane isomers 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 method or foaming foam kit or foamable composition or foam produced by the method or using the foaming foam kit or using the 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 foam kit, the A component comprises a blowing agent comprising E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze), and the B component may comprise a blowing agent comprising E-HFO-1336mzz.

[0035] In some embodiments, the amount of E-HFO-1336mzz in the B component of the method or foaming foam kit as disclosed herein is between about 0% and about 20% by weight of the B component. The amount of E-HFO-1336mzz in the B component 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 the B component of the method or foaming foam kit is 0%, then the A component must contain E-HFO-1336mzz. The amount of E-HFO-1336mzz in the A component is between about 0% and about 15% by weight of the A component. The amount of E-HFO-1336mzz in the A component can be, for example, from about 5% to about 15%, or from about 5% to about 10%.

[0037] In some embodiments, the amount of auxiliary blowing agent selected from one or more of carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a) in the B component of the method or foaming 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 the B component of the method or foaming 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 the B component of the method or foaming 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 the B component of the method or foaming foam kit is from about 0.1% to about 2%.

[0041] In some embodiments, the A component of the method or foaming foam kit comprises a co-foaming agent, and the co-foaming agent is carbon dioxide, nitrogen, or a combination thereof.

[0042] In one embodiment, the A component of the method or foaming foam kit comprises a co-blowing agent, and the co-blowing agent is carbon dioxide, and the amount of the co-blowing agent in the A component is from about 0.1% to about 1%.

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

[0044] When performing the method or when providing a foaming foam kit as disclosed herein, the A component or the B component or both may contain more than one co-blowing agent.

[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 process or foaming foam kit.

[0046] In one embodiment, the B component of the method or foaming 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 foaming foam kit comprises Z-HFO-1336mzz and one or more isomers of butane. In one embodiment, the one or more isomers of butane include or are isobutane. In one embodiment, the A component of the method or foaming foam kit comprises Z-HFO-1336mzz and one or more isomers of pentane. In one embodiment, the one or more isomers of pentane include or are cyclopentane. In one embodiment, the A component of the method or foaming foam kit comprises Z-HFO-1336mzz and methyl formate. In one embodiment, the A component of the method or foaming foam kit comprises Z-HFO-1336mzz and water.

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

[0049] In one embodiment of the method of the present invention, the A component of the method or foaming foam kit comprises E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze), and the B component comprises HFO-1336mzz-E. In this embodiment, one option is that the catalyst is not present in the A component. One option is that water is not present in the A component of the method or foaming foam kit. When the catalyst and water are not present in the A component, the stability of the A component comprising E-HFO-1234ze is improved, because the catalyst and / or water can cause the A component comprising E-HFO-1234ze to degrade.

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

[0051] In one embodiment of the method of the present invention or the foamable foam kit of the present invention, when the B component comprises E-HFO-1234ze, the B component further comprises CO 2 In one embodiment of the method or foaming foam kit of the present invention, when the B component comprises E-HFO-1234ze, CO is not present in the B component. 2 .

[0052] In some of the foregoing methods or foaming foam kits, the A component or the B component contains Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). When the A component or the B component contains Z-HFO-1336mzz, the amount of Z-HFO-1336mzz is greater than 0% to about 20%, such as 1% to about 15%, for example 1% to 10%, wherein the percentage is based on the total weight of the A component or the B component. In one embodiment, the amount of Z-HFO-1336mzz in the B component is about 1% to about 5%, based on the total weight of the B component.

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

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

[0055] When water is added to the A component of the method or foaming foam kit or the B component of the method or foaming foam kit, the amount of water added is greater than 0% to about 5%, such as 0.1% to about 3%, for example 0.2% to 5%, wherein the percentage is based on the total weight of the A component or the B component. In one embodiment, the amount of water added to the B component is about 1% to about 2%, based on the total weight of the B component.

[0056] When methyl formate is added to the A component of the method or foaming foam kit or the B component of the method or foaming foam kit, the amount of methyl formate added is greater than 0% up to 4.5%, such as 0.5% to 3%, wherein the percentage is based on the total weight of the A component or the B component.

[0057] The combination of component A and component B is referred to herein as a "foamable composition". The foamable composition comprises: (a) a blowing agent comprising E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz); (b) one or more auxiliary blowing agents selected from the group consisting of 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 component and the B component for use in the method and foaming foam kit as disclosed above. 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 the blowing agent comprising E-HFO-1336mzz and one or more co-blowing agents selected from carbon dioxide, nitrogen, or 1,1-difluoroethane is between about 5% and about 15% by weight of the foamable composition, such as between about 10% and 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 the blowing agent comprising E-HFO-1336mzz, Z-HFO-1336mzz and one or more co-blowing agents selected from carbon dioxide, nitrogen or 1,1-difluoroethane is between about 5% and about 15% by weight of the foamable composition, such as between about 10% and about 15% by weight of the foamable composition.

[0061] In some embodiments, the foamable composition comprises one or more isomers of butane and / or pentane. The butane isomer is preferably isobutane. The isomers of pentane 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 comprises methyl formate or water.The foamable composition may comprise Z-HFO-1336mzz and methyl formate.The foamable composition may comprise 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-toluene diisocyanate, 2,6-toluene 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 ... 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 a combination of two or more of these.

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

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

[0066] In some embodiments, polyol is polyester polyol. Suitable polyester polyol includes those prepared by reacting carboxylic acid and / or its derivative or polycarboxylic acid anhydride with polyol. Polycarboxylic acid can be any one of known aliphatic polycarboxylic acid, alicyclic polycarboxylic acid, aromatic polycarboxylic acid and / or heterocyclic polycarboxylic acid, and can be substituted (for example, substituted by halogen atom) and / or be unsaturated. The example of suitable polycarboxylic acid and acid anhydride comprises oxalic acid, malonic acid, glutaric acid, pimelic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride acid, maleic acid, maleic anhydride, fumaric acid and dimerization and trimerization fatty acid, such as those oleic acids that can be mixed with monomeric fatty acids. Also can use the simple ester of polycarboxylic acid, such as dimethyl terephthalate, glycol terephthalate and their extract.The polyol that is applicable to the preparation of polyester polyol can be aliphatic, alicyclic, aromatic and / or heterocyclic. The polyols may optionally include substituents that are inert in the reaction, such as chlorine and bromine substituents, and / or may be unsaturated. Suitable amino alcohols such as monoethanolamine, diethanolamine, etc. may also be used. Examples of suitable polyols include ethylene glycol, propylene glycol, polyoxyalkylene glycols (e.g., diethylene glycol, polyethylene glycol, dipropylene glycol, and polypropylene glycol), glycerol, and trimethylolpropane.

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

[0068] In some embodiments, polyester polyol has an average molecular weight of about 400 g / mol to about 500 g / mol, such as about 450 g / mol to about 475 g / mol. In some embodiments, polyester polyol is an aromatic polyester polyol having an average hydroxyl number of about 200 mg KOH / g to about 325 mg KOH / g, such as about 200 mg KOH / g to about 300 mg KOH / g, or about 235 mg KOH / g to about 265 mg KOH / g, or about 230 mg KOH / g to about 250 mg KOH / g, or about 295 mg KOH / g to about 315 mg KOH / g.

[0069] Exemplary commercially available polyester polyols include polyester polyols PS-2352(StepanCompany,Chicago,IL)、 PS-2502A(Stepan Company,Chicago,IL)、 PS-2412(Stepan Company,Chicago,IL)、 PS-2520(StepanCompany,Chicago,IL)、 PS-3021(Stepan Company,Chicago,IL)、 PS-3024(Stepan Company,Chicago,IL)、 256(Huntsman,The Woodlands,TX)、and 925(Huntsman,The Woodlands,TX)、 250(Huntsman,The Woodlands,TX)、 305(Huntsman,The Woodlands,TX)、 563(Huntsman,The Woodlands,TX)、 649(Huntsman,The Woodlands,TX)、 1465(Huntsman,The Woodlands,TX)、 TB-305(COIM,West Deptford,NJ)、 TB-306(COIM,West Deptford,NJ)、 HT5510(Invista)、 5232(Invista)、 5100(Invista)、 5150(Invista)、 5170(Invista)、 PES-240(Carpenter Co.,Richmond,VA)、 PES-265(Carpenter Co.,Richmond,VA)、 PES-305(Carpenter Co.,Richmond,VA)、 PES-295(Carpenter Co.,Richmond,VA),

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

[0071] In some embodiments, the polyether polyol is a medium functionalized polyether polyol. For example, the polyether polyol has a functionality of about four. In some embodiments, the polyether polyol is sucrose / glycerol initiated. In some embodiments, the polyether polyol is a Mannich-based polyether polyol. As used herein, the term "Mannich-based polyol" refers to an aromatic polyol obtained by alkoxylation of propylene oxide and / or ethylene oxide with a Mannich base, which is obtained by the classical Mannich reaction between a phenol (e.g., phenol, p-nonylphenol), formaldehyde, and an alkanolamine (diethanolamine, diisopropanolamine, monoethanolamine, monoisopropanolamine, etc.). Exemplary commercially available polyether polyols include 490(DowChemical,Midland,MI)、 MX-425 (Carpenter Co., Richmond, VA) and 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 may be included in the B component described herein. For example, the B component may 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 carbamate catalysts can be used, including amine-based compounds, such as tertiary amine compounds, for example dimethylethanolamine and bis (2-dimethylaminoethyl) ether, and organometallic compounds. Such catalysts are used in an amount that increases the reaction rate of polyisocyanates. By way of example, the typical amount of the catalyst used per 100 parts by weight of polyol is about 0.1 to about 5 parts of catalyst. In some embodiments, the foamable composition includes a gelling catalyst, such as a non-nucleophilic gelling catalyst. In some embodiments, the foamable composition includes a foaming 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 in, for example, U.S. Pat. No. 5,164,419, the disclosure of which is incorporated herein by reference. For example, catalysts for the trimerization of polyisocyanates, such as alkali metal alkoxides, alkali metal carboxylates, or quaternary ammonium salts, may also be optionally employed herein. Such catalysts are used in an amount that measurably increases the reaction rate of the polyisocyanate. Typical catalyst amounts are from about 0.1% by weight to about 5% by weight based on the total weight of all foaming ingredients. Non-limiting examples of catalysts include 8. N,N-dimethylcyclohexylamine from Evonik Industries, 5. Pentamethyldiethylenetriamine from Evonik Industries, and 52. 2-Methyl (sodium n-methylamino b-acetate nonylphenol) from Evonik Industries, 30(Evonik Industries), 36(Evonik Industries), 46(Evonik Industries), 77(Evonik Industries), 9(Evonik Industries), 2039(Evonik Industries)、 K15(Evonik Industries)、 204(Evonik Industries)、 2040(Evonik Industries)、 BL-19(Evonik Industries)、 BL-17(Evonik Industries)、 T(EvonikIndustries)、 T-125(Evonik Industries)、 K-15(Evonik Industries)、 TMR(Evonik Industries)、 TMR-2(Evonik Industries)、 TMR-3(Evonik Industries)、 TMR-30(Evonik Industries)、 8210(The ShepardChemical Company,Cincinnati,OH)、 8840(The Shepard Chemical Company,Cincinnati,OH)、 8842(The Shepard Chemical Company,Cincinnati,OH)、 XK 651(King Industries,Norwalk,CT)、 614(King Industries,Norwalk,CT)、 672(King Industries,Norwalk,CT)、 604(KingIndustries,Norwalk,CT)、 UL1(Momentive Performance Materials Inc.,Waterford,NY)、 UL22, UL1(Momentive Performance Materials Inc.,Waterford,NY, D-230(Huntsman,The Woodlands,TX)、 T403(Huntsman,The Woodlands,TX)、 D2000(Huntsman,The Woodlands,TX)、 T5000(Huntsman,The Woodlands,TX)、 PMDETA(Huntsman,TheWoodlands,TX)、 DMCHA (Huntsman, The Woodlands, TX), ZF20(Huntsman,The Woodlands,TX)、 ZF54 (Huntsman, The Woodlands, TX), tin, dibutyltin mercaptan, potassium octoate, potassium acetate, bismuth, bismuth carboxylate mixtures, and the like.

[0077] In some embodiments, the foamable composition includes a surfactant. Suitable surfactants may include liquid or solid organosiloxane compounds. Other surfactants include polyethylene glycol ethers of long chain alcohols, tertiary amines or alkanolamine salts of long chain alkyl acid sulfates, alkyl sulfonates, and alkyl aryl sulfonic acids. In some embodiments, the surfactant is an organosilicon surfactant. In some embodiments, the surfactant is an organosilicon polyether surfactant. In some embodiments, the surfactant is 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, bromine-containing diesters / ether diols of tetrabromophthalic anhydride, such as mixed esters of tetrabromophthalic anhydride with diethylene glycol and propylene glycol. Exemplary commercially available flame retardants include RB-79, a reactive bromine-containing diester / ether diol of tetrabromophthalic anhydride (Albemarle Corporation, Baton Rouge, LA). In some embodiments, the flame retardant is tris(1-chloro-2-propyl) phosphate (TCPP).

[0079] In some embodiments, the B component comprises a nucleating agent. Nucleating agents are mainly used to increase the number of cells in the foam and reduce the cell size, and can be used in an amount of about 0.1 to about 10 weight portions per 100 weight portions of resin. Typical nucleating agents include at least one member selected from talcum, sodium bicarbonate-citric acid mixture, calcium silicate and carbon dioxide etc. In some embodiments, the foamable composition does not include a nucleating agent. In some embodiments, the method provided herein is carried out in the absence of a nucleating agent. Exemplary nucleating agents include but are not limited to talcum, sodium bicarbonate-citric acid mixture, calcium silicate, carbon dioxide etc.

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

[0081] Example

[0082] Material

[0083] Opteon TM 1100 (Z-1,1,1,4,4,4-hexafluoro-2-butene, Z-HFO-1336mzz) and Opteon TM 1150 (E-1,1,1,4,4,4-hexafluoro-2-butene, E-HFO-1336mzz) foam blowing agent is available from The Chemours Company FC, LLC (Wilmington, DE). (Note that for convenience, Opteon TM 1100 may be referred to herein as "1100", and Opteon TM 1150 may be referred to herein as "1150." ) PS2352 is Stepanpol PS2352 polyester polyol available from Stepan Company, Northfield, IL. SG-360 polyol is available from BASF Corporation, Wyandotte, MI. P-700 polyether polyol is available from Carpenter Co. (Richmond, VA). TCPP is tris(1-chloro-2-propyl)phosphate. PHT4-DIOL TMFlame retardants are available from LANXESS Solutions US Inc. (Pittsburgh, PA). DC 193 silicone surfactant is commercially available. LK-443 surfactant is commercially available from Evonik Industries. Catalysts (including amine catalysts and isocyanurate catalysts) are available from Evonik Industries. Polymeric MDI (isocyanate) is available from Dow Chemical Company (Midland, MI). DEG is diethylene glycol, commercially available.

[0084] Example 1. LPSPF Test Formula 1

[0085] Manually mixed foam

[0086] Opteon by manual mixing TM The blowing agent is premixed into the isocyanate side to simulate the isocyanate tank of the LPSPF kit. The blowing agent used in the isocyanate is the same as Opteon TM 1100 and 1150 were in the same proportions, but their loading percentage was half that of the resin. The two components were mixed using an Arrow overhead mixer at 4000 rpm. Table 1 provides the resin formulations, and Table 2 provides the physical properties of the hand mixed foams. Hand mixing showed that Opteon TM The blowing agent overwhelmingly exceeds the desired R-value of 6 and meets other desired physical properties such as density and closed cell content.

[0087] Table 1. LPSPF Kit Manual Mixing - Test Formulation 1

[0088]

[0089] Table 2: Properties of Test Formulation 1

[0090]

[0091] Example 2. LPSPF Test Formula 2

[0092] Shelf life test

[0093] The shelf life is estimated based on the formation of carbonic acid. The theory is that the carbonic acid is produced by Opteon TM 1150. Carbon dioxide and water react to form. Carbonic acid, if formed, reacts with the amine catalyst over time and hinders the reactivity of the LPSPF kit.

[0094] A test cylinder capable of maintaining a pressure suitable for the LPSPF kit (15psi to 25psi) is designed to evaluate the shelf life in an accelerated aging test. Four test cylinders are loaded with the formulations listed in Table 3 and rolled for one hour to ensure uniform mixing. Three cylinders are placed in an oven at 50°C for aging. The first cylinder is then opened and poured into a beaker and immediately mixed manually with the isocyanate to obtain initial reactivity. Other cylinders follow a similar process to measure reactivity when aged for one, two, and three weeks. If carbonic acid forms and hinders the catalyst, it will form quickly in a heated environment.

[0095] Table 3: Shelf Life - Test Formulation 2

[0096]

[0097] Table 4: Testing of Carbonation via Reactivity Changes

[0098]

[0099] Shelf life testing indicated no significant carbonation was generated as there was no effect on reactivity as shown by creaming, gelling, swelling, and bonding times.

[0100] Spray Foam

[0101] The formulation listed in Table 3 (Test Formulation 2) was used in the spray of the LPSPF kit. The results are provided in Table 5.

[0102] Table 5: Physical properties of the spray LPSPF kit

[0103]

[0104] Example 3. LPSPF Test Formula 3

[0105] Aging test

[0106] NOTE: Only the resin side of the LPSPF kit was aged. All isocyanate sides were made on the day of spray testing. The isocyanate side was not aged due to 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. Along with the isocyanate tank, the resin tank was pressurized to 200 psi with nitrogen. Separate tanks were prepared for 0 hour, 2 week, 4 week, and 6 week spraying. Tables 6 to 9 show the properties of the formulations. (MF is methyl formate; tDCE is trans-dichloroethylene.)

[0107] Table 6: Distribution and aging of spray LPSPF kits

[0108]

[0109]

[0110] * DNS means "do not spray".

[0111] Table 7: Density and aging of spray-coated LPSPF kits

[0112]

[0113] DNF indicates samples for which no testable polyurethane foam samples were prepared. DNS means "do not spray".

[0114] Table 8: Closed Cell Content vs. Aging of Spray-Applied LPSPF Kits

[0115]

[0116]

[0117] DNF indicates samples for which no testable polyurethane foam samples were prepared

[0118] Table 9: R-value (insulation factor) and aging of LPSPF kits

[0119]

[0120] DNF indicates samples for which no testable polyurethane foam samples were prepared.

[0121] The free ion content of samples subjected to accelerated aging was tested via ion chromatography, as provided in Table 10. For each sample, three grams of the B-side were diluted with thirty milliliters of pure water; the mixture was stirred overnight. Then it was subjected to IC (ion chromatography) according to ASTM D4327. The samples can be further diluted so that the results are within the calibration curve of the machine to ensure accuracy.

[0122] Table 10: Ion Chromatogram (ppm) vs. Aging of LPSPF Kit

[0123]

[0124]

[0125] < The minimum detection of fluoride anions in samples with MDL less than the minimum detection limit was 0.2 ppm (parts per million).

[0126] The minimum detection of chloride anions was 0.3 ppm.

[0127] The free fluoride and chloride anions in the B-side 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, a significant amount of chloride anions were generated during accelerated aging.

[0128] Opteon-based TM The formulations are stable in the resin and common catalysts have little effect on these formulations.

[0129] It was found that in the presence of catalyst and increased chloride content, formulations containing E-1234ze were not as stable as formulations containing E-HFO-1336mzz.

[0130] Table 11: Reactivity (seconds) vs. aging of LPSPF kit

[0131]

[0132] X indicates that no measurement was taken.

[0133] As shown in the examples, LPSPF formulations containing E-HFO-1336mzz have long shelf life when used in the presence of traditional polyols, catalysts, surfactants and water levels in the LPSPF kit. Such formulations are also provided (good properties - comments on partition ratio, R-value, density, closed cells, etc.).

Claims

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

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

6. 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. 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 the two cylinders.

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

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

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

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

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

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

19. The method of claim 1 wherein the amount of E-HFO-1336mzz in the B component 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 component.

20. The method of claim 1, wherein the amount of E-HFO-1336mzz in the A component is between about 0% and 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 of the A component.

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

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

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

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

25. The method of claim 1, wherein the A-component of the method comprises a co-blowing agent, the amount of the co-blowing agent in the A-component being from about 0.1% to about 2%.

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

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

28. The method of claim 5, wherein the butane comprises isobutane, and wherein 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 or the B component or both.

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

34. A polyurethane foam kit, comprising: (a) a cylinder comprising an A component, wherein the A component comprises an isocyanate; (b) a cylinder including a B component comprising an isocyanate-reactive compound; (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; and wherein the A component and the B component are provided in separate pressurized cylinders.

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

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

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

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

39. The foam of claim 36 having a density in the range of 1.8 to 2.5 lbs / ft3 (28.8 to 40.0 kg / m3).

40. 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 the group consisting of carbon dioxide, nitrogen, or 1,1-difluoroethane (HFC-152a); (c) an isocyanate; (d) a polyol; (e) a catalyst; and (f) a surfactant.

41. A foamable composition according to claim 40, wherein the composition comprises E-HFO-1234ze.

42. The foamable composition according to 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 is between about 5% and about 15% by weight of the foamable composition.

43. The foamable composition according to 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 is between about 10% and about 15% by weight of the foamable composition.

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

45. The foamable composition according to 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 is between about 5% and about 15% by weight of the foamable composition.

46. ​​The foamable composition according to 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 is between about 10% and about 15% by weight of the foamable composition.

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

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

Images