Blowing agents comprising HFO-1252ZC and HFO-1336MZZ-z and methods for the manufacture of polyurethane and polyisocyanurate foams

Abstract

Processes, foams, foamable compositions, and blowing agents related to thermoset polymer foam compositions comprising an active hydrogen-containing compound; and a blowing agent comprising HFO-1252zc and HFO-1336mzz-Z.

Description

TS0126-WO01TITLE OF THE INVENTION BLOWING AGENTS COMPRISING HFO-1252zc AND HFO-1336MZZ-Z AND METHODS FOR THE MANUFACTURE OF POLYURETHANE AND POLYISOCYAN URATE FOAMS CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 745,448 filed January 15, 2025, the disclosure of which is incorporated herein by reference in its entirety.BACKGROUND OF THE INVENTION

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

[0003] All of these various types of polyurethane foams require blowing (expansion) agents for their manufacture. Insulating foams depend on the use of halocarbon blowing agents, not only to foam the polymer, but also fortheir low vapor thermal conductivity, a very important characteristic for insulation value. Historically, polyurethane foams used CFCs (chlorofluorocarbons, for example CFC-11, trichlorofluoromethane), HCFCs (hydrochlorofluorocarbons, for example HCFC- 141b, 1, 1 -dichloro-1 -fluoroethane), and HFCs (hydrofluorocarbons, for example, HFC-245fa, HFC-365mfc) as the primary blowing agents.

[0004] In general, CFCs produce foams exhibiting good thermal insulation, low flammability, and excellent dimensional stability. However, despite these advantages, CFCs have fallen into disfavor due to the implication of chlorine- containing molecules in the destruction of stratospheric ozone. Further, the production and use of CFCs has been restricted by the Montreal Protocol. HCFCs have been proposed as CFC substitutes and are currently employed as foamTS0126-WO01blowing agents. However, HCFCs have also been shown to contribute to the depletion of stratospheric ozone, and as a result their use has come under scrutiny. The widespread use of HCFCs is scheduled for eventual phase out under the Montreal Protocol.

[0005] Thus, there is a need for effective blowing agents with both low ODP (ozone depletion potential) and GWP (global warming potential).SUMMARY OF THE INVENTION

[0006] According to certain aspects of the present invention, a blowing agent includes HFO-1252zcand HFO-1336mzz-Z. In some aspects, the blowing agent includes HFO-1252zc in an amount of about 0.1 wt% to about 10 wt%; or about 0.1 wt% to about 7 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc. In some aspects, the blowing agent includes cyclopentane in an amount of about 90 wt% to about 99.9 wt%; or about 93 wt% to about 99.9 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc.

[0007] According to certain aspects of the present invention, a foamable composition includes (a) an active hydrogen-containing compound; and (b) a blowing agent comprising HFO-1252zc and HFO-1336mzz-Z. In some aspects, the foamable composition may further comprise an isocyanate, such as for example, at least one of aliphatic, cycloaliphatic, aromatic, and heterocyclic isocyanates.

[0008] In some aspects, the active hydrogen-containing compound comprises a thermoset polymer. The thermoset polymer may comprise a polyol such as a polyester polyol. In some aspects, a suitable polyester polyol may have a hydroxyl number of from about 180 mg KOH / g to about 380 mg KOH / g; from about 200 mg KOH / g to about 300 mg KOH / g; or from about 220 mg KOH / g to about 250 mg KOH / g.

[0009] The abbreviation “pphp” is used herein to mean parts per hundred parts of polyol, unless specified otherwise herein. In some aspects, the foamable composition includes HFO-1252zc in an amount of about 0.1 pphp to about 10 pphp; about 0.1 pphp to about 5 pphp; about 0.1 pphp to about 2 pphp; about 1 to about 10 pphp; or about 6 to about 10 pphp. In some aspects, the foamable compositionTS0126-WO01includes HFO-1336mzz-Z in an amount of about 4 to about 20 pphp; about 5 pphp to about 15 pphp; about 8 pphp to about 16 pphp; or about 10 pphp to about 15 pphp.

[0010] The foamable composition may include the blowing agent in an amount of about 2 wt% to about 15 wt% of the foamable composition. In some aspects, the foamable composition includes one or more additives selected from at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant agent, and at least one nucleating agent. In some aspects, the surfactant is a silicone surfactant. In certain aspects, the foamable composition includes a metal catalyst and an amine catalyst.

[0011] According to certain aspects of the present invention, a thermoset polymer foam includes: (a) an active hydrogen-containing compound; and (b) a blowing agent comprising HFO-1252zc and HFO-1336mzz-Z as described herein. The foams of the present invention may use foamable compositions, active hydrogen-containing compounds, blowing agents, and components thereof as described in various aspects of this disclosure in any useful combination. In some aspects, the foam is a polyurethane foam or a polyisocyanurate foam. In certain aspects, the foam is a closed cell foam such as a closed cell polyisocyanurate foam or a closed cell polyurethane foam.

[0012] In some aspects, the foam includes HFO-1252zc in an amount of about 0.1 pphp to about 10 pphp; about 0.1 pphp to about 5 pphp; about 0.1 pphp to about 2 pphp; about 1 to about 10 pphp; or about 6 to about 10 pphp. In some aspects, the foam includes HFO-1336mzz-Z in an amount of about 4 to about 20 pphp; about 5 pphp to about 15 pphp; about 8 pphp to about 16 pphp; or about 10 pphp to about 15 PPhp.

[0013] In certain aspects, the blowing agent is present in an amount of about 2 wt% to about 15 wt% of the thermoset polymer foam.

[0014] In some aspects, the foam comprises a pour-in-place panel, a foam for use in an appliance, or a foam for use in spray applications.

[0015] According to certain aspects of the present invention, a process for preparing a thermoset polymer foam includes: (a) providing a foamable composition comprising an and a blowing agent, wherein the blowing agent comprises HFO-TS0126-WO011252zc and HFO-1336mzz-Z; and (b) expanding the foamable composition to produce the thermoset polymer foam. The processes of the present invention may use foamable compositions, active hydrogen-containing compounds, blowing agents, and components thereof as described in various aspects of this disclosure in any useful combination. In certain aspects, the process is performed in the absence of a nucleating agent.BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 shows vapor-liquid equilibrium data for HFO-1252zc with HFO- 1336mzz-Z and HFO-1336mzz-E.DETAILED DESCRIPTION OF THE INVENTION

[0017] The present disclosure relates to compositions containing 1,1- difluoropropene (HFO-1252zc), described in further detail below. The present disclosure also provides compositions, and particularly blowing agents, foamable compositions, foamed articles, and methods and systems for forming foam, which utilize HFO-1252zc and HFO-1336mzz-Z. Such foams may be particularly useful for spray foam applications.

[0018] It has surprisingly been found that blowing agents comprising HFO-1252zc and HFO-1336mzz-Z are effective yet still have acceptable environmental fates. Specifically, such blowing agents generate no more than de minimis yields of persistent products of atmospheric decomposition such as trifluoro-acetic acid (“TFA”) and meet the following conditions: (1) have no more than de minimis ODP; (2) are not recognized as ODS under the Montreal Protocol; (3) have low GWP100; (4) have acceptable health and safety profiles (e.g., low toxicity and low or no flammability); and (5) enable acceptable performance as agents for polyurethane foam expansion (e.g., foam thermal resistance, mechanical strength, density, etc.). Additionally, such blowing agents have been found to allow for an improved, efficient process for producing spray applied foams and enable foams that display relatively high insulation values.TS0126-WO01Blowing Agents

[0019] Fluorocarbon fluids have properties that are desirable for use in a variety of applications, including as blowing agents, and other applications. Unfortunately, the use of certain hydrofluorocarbons in industrial applications is now believed to contribute to global warming, and accordingly, have limited their contemporary use. However, the identification of new, environmentally safe compositions comprising HFCs is complicated, due to the fact that many properties which make them useful in these applications are not readily predictable. For example, it is desirable that blowing agent compositions not only have acceptable environmental properties, but also chemical stability, low or no toxicity, and low or no flammability, among others. It is also desirable that the blowing agent has excellent performance when in use, e.g. excellent thermal insulating properties and other desirable foam characteristics.

[0020] Methods and compositions for making conventional foamed materials, such as for example thermoplastic materials and thermosetting materials, have long been known. These methods and compositions have typically utilized chemical and / or physical blowing agents to form the foamed structure in a polymeric matrix. Such blowing agents have included, for example, azo compounds, various volatile organic compounds (VOCs), and chlorofluorocarbons (CFCs). The chemical blowing agents typically undergo some form of chemical change, including chemical reaction with the material that forms the polymer matrix (usually at a predetermined temperature / pressure) that causes the release of a gas, such as nitrogen, carbon dioxide, or carbon monoxide. One of the most frequently used chemical blowing agents is water. The physical blowing agents typically are dissolved in the polymer or polymer precursor material and then expand volumetrically (again at a predetermined temperature / pressure) to contribute to the formation of the foamed structure. Physical blowing agents are frequently used in connection with thermoplastic foams, although chemical blowing agents can be used in place of or in addition to physical blowing agents in connection with thermoplastic foam. It is common to use chemical blowing and / or physical blowing agents in connection with thermosetting foams. Additionally, it is possible that certain compounds and the compositions that contain them may at once constitute a chemical and a physical blowing agent.TS0126-WO01

[0021] Blowing agents of the present invention may include 1,1 -difluoropropene (HFO-1252zc or R-1252zc). HFO-1252zc may be prepared by hydrogenation of 3,3,3-trifluoropropene (HFO-1243zf) over palladium on carbon catalyst to form 1,1,1- trifluoropropane (HFC-263fb), followed by dehydrofluorination of the HFC-263fb over chrome catalyst or by pyrolysis at high temperatures.

[0022] In some aspects, a blowing agent may comprise HFO-1252zc in an amount of about 1 wt% to about 100 wt%; about 1 wt% to about 99 wt%; about 20 wt% to about 80 wt%; about 30 wt% to about 70 wt%; about 40 wt% to about 60 wt%; about 1 wt% to about 50 wt%; about 1 wt% to about 30 wt%: about 1 wt% to about 20 wt%; about 20 wt% to about 40 wt%; about 50 wt% to about 100 wt%; about 50 wt% to about 99 wt%; about 60 wt% to about 100 wt%; about 60 wt% to about 99 wt%; about 75 wt% to about 100 wt%; about 75 wt% to about 99 wt%; or about 60 wt% to about 80 wt% of the blowing agent.

[0023] In some embodiments, blowing agents may further include one or more additional components selected from the group consisting of saturated hydrocarbons (including partially or fully halogenated saturated hydrocarbons), unsaturated hydrocarbons (including partially or fully halogenated unsaturated hydrocarbons), saturated ethers (including partially or fully halogenated saturated ethers), unsaturated ethers (including partially or fully halogenated unsaturated ethers), saturated aldehydes (including partially or fully halogenated saturated aldehydes), unsaturated aldehydes (including partially or fully halogenated unsaturated aldehydes), saturated ketones (including partially or fully halogenated saturated ketones), unsaturated ketones (including partially or fully halogenated unsaturated ketones), saturated alcohols (including partially or fully halogenated saturated alcohols), unsaturated alcohols (including partially or fully halogenated unsaturated alcohols), saturated organic acids (including partially or fully halogenated saturated organic acids), and unsaturated organic acids (including partially or fully halogenated unsaturated organic acids).

[0024] Such additional components may include hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), hydrochloroolefins (HCOs), chloro-fluoroolefins (CFOs), perfluorinated olefins, saturated hydrofluoroethers (HFEs), unsaturated hydrofluoroethers (HFEOs), saturatedTS0126-WO01hydrocarbons, unsaturated hydrocarbons (e.g., olefins or alkenes), and chlorinated hydrocarbons. In some aspects, additional components include HFC-32, HFC-125, HFC-134, HFC-152a, HFO-1132-E, HFO-1132a, HFO-1123, HFO-1132-Z, HFO- 1243yc, HFO-1234ze(E), HFO-1234ze(Z), HFO-1336mzz(E), HFO-1336mzz(Z), HCFO-1233zd(E), HCFO-1233zd(Z), CFO-1112, ethane, propane, butane, isobutane, normal pentane, iso-pentane, cyclopentane, neo-pentane, n-hexane, isohexane, heptane, ethene, propylene, butene, straight chain and branched pentenes, straight chain and branched hexenes, straight chain and branched heptenes, formaldehyde, acetaldehyde, methylal, propanal, butanal, isobutanal, acetone, methanol, ethanol, dimethyl ether, diethyl ether, methyl formate, ethyl formate, formic acid, trans-1,2-dichloroethylene (DCE), chloropropane, methylethylketone, methylisobutylketone, carbon dioxide (CO2), CF31, and water.

[0025] Amounts of HFO-1252zc may be chosen based on based on vapor-liquid equilibrium curves to achieve the desired properties. Figure 1, for example, shows vapor-liquid equilibrium data for HFO-1252zc with HFO-1336mzz-Z and HFO- 1336mzz-E.

[0026] In some aspects, a blowing agent may include HFO-1252zc in combination with HFO-1336mzz-Z. A blowing agent may include HFO-1336mzz-Z in an amount of about 1 wt% to about 99 wt%; about 20 wt% to about 80 wt%; about 30 wt% to about 70 wt%; about 40 wt% to about 60 wt%; about 1 wt% to about 50 wt%; about 1 wt% to about 30 wt%: about 1 wt% to about 20 wt%; about 20 wt% to about 40 wt%; about 50 wt% to about 99 wt%; about 60 wt% to about 99 wt%; about 75 wt% to about 99 wt%; or about 60 wt% to about 80 wt% of the blowing agent.

[0027] In some aspects, a blowing agent includes HFO-1252zc in an amount of about 1 to 10 wt% of the blowing agent and HFO-1336mzz-Z in an amount of 90 to about 99 wt% of the blowing agent. In some aspects, a blowing agent includes HFO- 1252zc in an amount of about 5 wt% of the blowing agent and HFO-1336mzz-Z in an amount of 95 wt% of the blowing agent.

[0028] In some aspects, a blowing agent may include HFO-1252zc in combination with 1,1 -difluoroethane (HFC-152a). A blowing agent may include HFC-152a in an amount of about 1 wt% to about 99 wt%; about 20 wt% to about 80 wt%; about 30 wt% to about 70 wt%; about 40 wt% to about 60 wt%; about 1 wt% to about 50 wt%;TS0126-WO01about 1 wt% to about 30 wt%: about 1 wt% to about 20 wt%; about 20 wt% to about 40 wt%; about 50 wt% to about 99 wt%; about 60 wt% to about 99 wt%; about 75 wt% to about 99 wt%; or about 60 wt% to about 80 wt% of the blowing agent.

[0029] In some aspects, a blowing agent may include HFO-1252zc in combination with one or more pentane component, such as n-pentane. In some aspects, a blowing agent may include one or more pentane component, such as n-pentane, in an amount of about 1 wt% to about 99 wt%; about 20 wt% to about 80 wt%; about 30 wt% to about 70 wt%; about 40 wt% to about 60 wt%; about 1 wt% to about 50 wt%; about 1 wt% to about 30 wt%: about 1 wt% to about 20 wt%; about 20 wt% to about 40 wt%; about 50 wt% to about 99 wt%; about 60 wt% to about 99 wt%; about 75 wt% to about 99 wt%; or about 60 wt% to about 80 wt% of the blowing agent.

[0030] In some aspects, a blowing agent may include HFO-1252zc in combination with HFC-152a and a pentane such as n-pentane.

[0031] In some aspects, a blowing agent may include HFO-1252zc in combination with HFC-152a and HFO-1336mzz-Z.

[0032] In some aspects, a blowing agent may include water. When water is added, it will typically be present in an amount of less than 5 wt% of the blowing agent, such as 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, or 1 wt% or less. In some aspects, a blowing agent may include water in an amount of about 0.2 to about 2.0 pphp.Azeotrope Compositions

[0033] Some compositions of HFO-1252zc may form azeotropic or azeotrope-like compositions with some blend components.

[0034] As used herein, an azeotropic composition is a constant boiling liquid admixture of two or more substances wherein the admixture distills without substantial composition change and behaves as a constant boiling composition. Constant boiling compositions, which are characterized as azeotropic, exhibit either a maximum or a minimum boiling point, as compared with that of the non-azeotropic mixtures of the same substances. Azeotropic compositions as used herein include homogeneous azeotropes which are liquid admixtures of two or more substances that behave as a single substance, in that the vapor, produced by partial evaporationTS0126-WO01or distillation of the liquid, has the same composition as the liquid. Azeotropic compositions as used herein also include heterogeneous azeotropes where the liquid phase splits into two or more liquid phases. In these embodiments, at the azeotropic point, the vapor phase is in equilibrium with two liquid phases and all three phases have different compositions. If the two equilibrium liquid phases of a heterogeneous azeotrope are combined and the composition of the overall liquid phase calculated, this would be identical to the composition of the vapor phase.

[0035] As used herein, near-azeotropic composition means a composition that behaves like an azeotrope (i.e., has constant boiling characteristics or a tendency not to fractionate upon boiling or evaporation). Thus, the composition of the vapor formed during boiling or evaporation is the same as or substantially the same as the original liquid composition. Hence, during boiling or evaporation, the liquid composition, if it changes at all, changes only to a minimal or negligible extent. This is to be contrasted with non-azeotropic compositions in which during boiling or evaporation, the liquid composition changes to a substantial degree.

[0036] Near-azeotropic compositions exhibit dew point pressure and bubble point pressure with virtually no pressure differential. That is to say that the difference in the dew point pressure and bubble point pressure at a given temperature will be a small value. It may be stated that compositions with a difference in dew point pressure and bubble point pressure of less than or equal to 3 percent (based upon the bubble point pressure) may be considered to be a near-azeotropic.

[0037] It is also recognized that both the boiling point and the weight percentages of each component of the azeotropic or near-azeotropic liquid composition may change when the azeotropic or near-azeotropic liquid composition is subjected to boiling at different pressures. Thus, an azeotropic or a near-azeotropic composition may be defined in terms of the unique relationship that exists among the components or in terms of the compositional ranges of the components or in terms of exact weight percentages of each component of the composition characterized by a fixed boiling point at a specified pressure. It is also recognized in the art that various azeotropic compositions (including their boiling points at particular pressures) may be calculated (see, e.g., W. Schotte Ind. Eng. Chem. Process Des. Dev. (1980) 19, 432-439). Experimental identification of azeotropic compositions involving the sameTS0126-WO01components may be used to confirm the accuracy of such calculations and / or to modify the calculations at the same or other temperatures and pressures.Foamable Compositions

[0038] The present disclosure provides foamable compositions including a blowing agent composition such as those described above, and one or more components capable of forming foam. Specifically, the one or more components capable of forming foam are well suited for polyurethane and polyisocyanurate foam compositions.

[0039] In some aspects, a component capable of forming foam comprises an active hydrogen-containing compound. Examples of active hydrogen-containing compounds include polymers such as thermoset polymers. Suitable active hydrogencontaining compounds may include polyols, such as polyether or polyester polyols. In some aspects, some of the hydroxyl groups can be replaced by amine groups, whereby the active hydrogen-containing compound contains both hydroxyl and amine groups. In some aspects, a suitable polyester polyol has a hydroxyl number of from about 180 mg KOH / g to about 380 mg KOH / g, from about 200 mg KOH / g to about 300 mg KOH / g, or from about 220 mg KOH / g to about 250 mg KOH / g.

[0040] Suitable polyols may include sucrose-containing polyols; phenol, a phenol formaldehyde-containing polyol; a glucose-containing polyol; a sorbitol-containing polyol; a methylglucoside-containing polyol; an aromatic amine-containing polyol, such as an ortho-toluene diamine (o-TDA)-containing polyol; an aromatic polyester polyol; glycerol; ethylene glycol; diethylene glycol; propylene glycol; one or more of (a) condensed with one or more of (b), wherein (a) is selected from glycerine, ethylene glycol, diethylene glycol, trimethylolpropane, ethylene diamine, pentaerythritol, soy oil, lecithin, tall oil, palm oil, and castor oil; and (b) is selected from ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide; and combinations thereof, for example.

[0041] In some aspects, the foamable composition includes a polyol in an amount of about 25 pphp to about 100 pphp, about 25 pphp to about 75 pphp, or about 51 to about 100 pphp. In some aspects, the foamable composition may include a copolyol, such as in an amount of about 0 pphp to about 75 pphp, about 25 pphp toTS0126-WO01about 75 pphp, about 0 to about 49 pphp, about 0.5 to about 49 pphp, or up to about 49 pphp.

[0042] In some aspects, the foamable composition comprises an isocyanate. In some aspects, the isocyanate comprises at least one of aromatic, aliphatic, cycloaliphatic, and heterocyclic polyisocyanurates, among others. In some aspects, isocyanates comprise from about 50 wt% to about 70 wt% of the total foam; or about 50 wt% to about 67 wt% of the total foam.

[0043] Suitable isocyanates may include any organic polyisocyanurate which can be employed in polyurethane or polyisocyanurate foam synthesis inclusive of aliphatic and aromatic polyisocyanurate. Suitable organic polyisocyanurates include aliphatic, cycloaliphatic, aromatic, and heterocyclic isocyanates which are well known in the field of polyurethane chemistry. These are described in, for example, U. S. patents 4,868,224; 3,401,190; 3,454,606; 3,277,138; 3,492,330; 3,001,973; 3,394,164; 3,124.605; and 3,201,372.

[0044] In some aspects, the foamable composition further comprises one or more additives selected from at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant agent, and / or at least one nucleating agent. In some aspects, the foamable composition may include stabilizers, chain extenders, cross-linkers, smoke suppressants, pigments, coloring materials, fillers, etc.

[0045] In some aspects, a foamable composition may include a catalyst in an amount of about 2 to about 10 pphp. Suitable catalysts may include amine catalysts and / or metal catalysts. Amine catalysts may include, but are not limited to, primary amine, secondary amine or tertiary amine. Useful tertiary amine catalysts non- exclusively include N, N- dimethylcyclohexylamine, N, N-dimethylethanolamine, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethyl-ethanolamine, N, N, N'- trimethyl-N'- hydroxyethylbisaminoethylether, tetramethyliminobispropylamine,, 2-[[2- [2- (dimethylamino)ethoxy]ethyl] methylamino] ethanol, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, N, N, N', N", N"-pentamethyl- dipropylenetriamine, 1, 1,4,7, 10, 10-hexamethyltriethylenetetramine, N, N-bis(3- dimethylaminopropyl)-N- isopropanolamine, N'-(3-(dimethylamino)propyl)-N, N- dimethyl-1,3-propanediamine, bis(3-dimethylaminopropyl)-N, N-TS0126-WO01dimethylpropanediamine, bis-(2- dimethylaminoethyl)ether, N, N', N"- dimethylaminopropylhexahydrotriazine, tetramethyliminobispropylamine, trimethyl- N',2-hydroxyethyl-propylenediamine, bis- (3-aminopropyl)-methylamine, N, N- dimethyl-1,3-propanediamine, 1- (dimethylamino)hexadecane, benzyldimethylamine, 3-dimethylaminopropyl urea, dicyclohexylmethylamine; ethyldiisopropylamine; dimethylisopropylamine; methylisopropylbenzylamine; methylcyclopentylbenzylamine; isopropyl-sec-butyl- trifluoroethylamine; diethyl-(a- phenylethyl)amine, tri-n-propylamine, or combinations thereof. Useful secondary amine catalysts non-exclusively include dicyclohexylamine; tert-butylisopropylamine; di-tert-butylamine; cyclohexyl-tert- butylamine; di-sec-butylamine, dicyclopentylamine; di-(a-trifluoromethylethyl)amine; di-(a-phenylethyl)amine; or combinations thereof, for example.

[0046] Metal catalysts may include potassium catalysts, such as potassium octoate (Dabco K15) and potassium acetate (Polycat 46), for example; tin catalysts, such as dibutyltin dilaurylmercaptide (Dabco T120, Fomrez UL-1), dibutyltin diisooctylmaleate (Dabco T125), dimethyltin dilaurylmercaptide (Fomrez UL-22), dioctyltin dilaurylmercaptide Fomrez UL-32), and dibutyltin di-(2- ethylhexylthioglycolate) (Fomrez UL-6), for example; and bismuth carboxylate, such as Bicat 8108, Bicat 8210, and the like, for example.

[0047] In some aspects, a foamable composition may include a surfactant in an amount of about 1 to about 5 pphp. Certain surfactants are added to serve as cell stabilizers. Some representative materials are sold under the names of DC-193, B- 8404, and L-5340 which are, generally, polysiloxane polyoxyalkylene block copolymers such as those disclosed in U. S. Patent Nos. 2,834,748, 2,917,480, and 2,846,458, each of which is incorporated herein by reference. Other optional additives for the polyol pre-blend may include flame retardants such as tri(2- chloroethyl)phosphate, tri(2- chloropropyl)phosphate, tri(2,3-dibromopropyl)- phosphate, tri(1,3-dichloropropyl) phosphate, other halogen-free phosphates such as triethyl phosphate, butyl 3-(6- oxidodibenzo[c,e][1,2]oxaphosphinin-6-yl)propionate; (ammonium polyphosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.TS0126-WO01

[0048] In some aspects, a foamable composition may include a flame retardant in an amount of up to 20 pphp, about 0 to about 20 pphp, or about 0.5 to about 20 pphp. In some aspects, a foamable composition may include an emulsifier / blowing agent enhancer in an amount of up to about 5 pphp, about 0 to about 5 pphp, or about 0.5 to about 20 pphp. In some aspects, a foamable composition may include water in an amount of about 0.2 to about 2 pphp.

[0049] In some aspects, a foamable composition may include HFO-1252zc in an amount of about 0.1 pphp, to about 10 pphp, about 0.1 pphp to about 5 pphp, about 0.1 pphp to about 2 pphp, about 1 to about 10 pphp, about 6 to about 10 pphp, about 12 to about 30 pphp, about 6 to about 24 pphp, about 1 to about 30 pphp; about 6 to about 30 pphp, or about 12 to about 24 pphp.

[0050] In some aspects, a foamable composition may include HFO-1336mzz-Z in an amount of about 4 to about 20 pphp, about 5 pphp to about 15 pphp, about 8 pphp to about 16 pphp, or about 10 pphp to about 15 pphp.

[0051] In some aspects, a foamable composition includes HFO-1252zc and HFO- 1336mzz-Z. In some aspects, a blowing agent includes HFO-1252zc in an amount of about 0.1 to 10 wt% and HFO-1336mzz-Z in an amount of 90 to about 99.9 wt% of the total amount of HFO-1252zc and HFO-1336mzz-Z combined. In some aspects, a blowing agent includes HFO-1252zc in an amount of about 0.1 to 7 wt% and HFO- 1336mzz-Z in an amount of 93 to about 99.9 wt% of the total amount of HFO-1252zc and HFO-1336mzz-Z combined. In some aspects, a blowing agent includes HFO- 1252zc in an amount of about 5 wt% and HFO-1336mzz-Z in an amount of 95 wt% of the total amount of HFO-1252zc and HFO-1336mzz-Z combined.

[0052] In some aspects, a foamable composition may include HFC-152a in an amount of about 6 to about 24 pphp, or about 10 to about 20 pphp.

[0053] In some aspects, a foamable composition may include one or more pentane component, such as n-pentane, in an amount of about 12 to about 24 pphp, or about 15 to about 20 pphp.

[0054] The blowing agent of the present disclosure may be present in the foamable composition in an amount of about 2 wt% of the foamable composition or greater, about 3 wt% or greater, about 4 wt% or greater, about 5 wt% or greater,TS0126-WO01about 6 wt% or greater, about 7 wt% or greater, about 8 wt% or less, about 9 wt% or less, about 10 wt% or less, about 11 wt% or less, about 12 wt% or less, about 13 wt% or less, about 14 wt% or less, about 15 wt% or less, or within any range encompassing these endpoints, as a percentage of the total weight of the foamable composition. In some aspects, the foamable composition includes a blowing agent in an amount of about 2 wt% to about 15 wt% of the foamable composition. The total weight of the foamable composition includes all components of the thermoplastic and thermoset foams.Foam

[0055] The present disclosure also relates to a closed cell foam comprising the blowing agent composition of the disclosure. The foam may be a rigid foam, a flexible foam, or an integral skin foam. In some aspects, the disclosure relates to a closed cell rigid foam comprising the blowing agent composition comprising HFO- 1252zc described herein. In some aspects, the disclosure relates to a closed cell rigid foam comprising a blowing agent composition comprising HFO-1252zc and HFO-1336mzz-Z described herein.

[0056] In some aspects, a foam includes a blowing agent in an amount of about 2 wt% to about 15 wt% of the foam. In some aspects, the blowing agent may be present in the foam in an amount of about 2 wt% of the foam or greater, about 3 wt% or greater, about 4 wt% or greater, about 5 wt% or greater, about 6 wt% or greater, about 7 wt% or greater, about 8 wt% or less, about 9 wt% or less, about 10 wt% or less, about 11 wt% or less, about 12 wt% or less, about 13 wt% or less, about 14 wt% or less, about 15 wt% or less, or within any range encompassing these endpoints, as a percentage of the total weight of the foam.

[0057] In some aspects, a foam may include HFO-1252zc in an amount of about 0.1 pphp, to about 10 pphp, about 0.1 pphp to about 5 pphp, about 0.1 pphp to about 2 pphp, about 1 to about 10 pphp, about 6 to about 10 pphp, about 12 to about 30 pphp, about 6 to about 24 pphp, about 1 to about 30 pphp; about 6 to about 30 pphp, or about 12 to about 24 pphp.

[0058] In some aspects, a foam may include HFO-1336mzz-Z in an amount of about 4 to about 20 pphp, about 5 pphp to about 15 pphp, about 8 pphp to about 16 pphp, or about 10 pphp to about 15 pphp.TS0126-WO01

[0059] The foam provided by the present disclosure can be a block, a slab, a laminate, a panel, such as a pour-in-place panel, a spray applied foam, a froth, and the like. The foams described in the present disclosure, particularly thermoset foams disclosed herein, may be used in a wide variety of applications. In certain aspects, the present disclosure comprises appliance foams, such as refrigerator foams, freezer foams, refrigerator / freezer foams, panel foams, and other cold or cryogenic manufacturing applications. Foams of the present disclosure may be particularly useful for spray foam applications.

[0060] The foams of some aspects of the present disclosure may be provided for use in appliance, refrigeration, transportation and building industries (for example as building envelopes). The foams described herein provide one or more exceptional features, characteristics and / or properties, including: thermal insulation efficiency (particularly for thermoset foams), dimensional stability, compressive strength, aging of thermal insulation properties, and flame retardancy, among others, all in addition to the low global warming potential associated with the blowing agents of the present disclosure.

[0061] The foam may be a thermoset foam. The thermoset foam may be a polyisocyanurate (PIR) or polyurethane (PU) foam.Method of Forming Foams

[0062] It is contemplated that all presently known and available methods and systems for forming foam are readily adaptable for use in connection with the compositions of the present disclosure. For example, the methods of the present disclosure generally include combining a blowing agent and an active hydrogencontaining compound such as a polymer to form a foamable composition and then foaming the composition, preferably by a step or series of steps which include causing volumetric expansion of the blowing agent described herein. In general, it is contemplated that the presently used systems and devices for incorporation of a blowing agent and for foaming can readily be used in accordance with the compositions of the present disclosure. In fact, it is believed that one advantage of the present disclosure is the provision of an improved blowing agent which is generally compatible with existing foaming methods and systems.TS0126-WO01

[0063] Thus, the present disclosure relates to the use of the present blowing agents in connection with conventional foaming equipment at conventional processing conditions. The present methods therefore include masterbatch type operations, blending type operations, third stream blowing agent addition, and blowing agent addition at the mixing head.

[0064] In some aspects, the present disclosure relates to methods of forming thermoset foams, such as polyurethane (PU) or polyisocyanurate (PIR). The methods generally comprise providing a blowing agent composition of the present disclosure, adding (directly or indirectly) the blowing agent composition to an active hydrogen-containing compound to form a foamable composition, and reacting the foamable composition under the conditions effective to form a foam or cellular structure, as is well known in the art. Any of the methods well known in the art, such as those described in “Polyurethanes Chemistry and Technology,” Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, which is incorporated herein by reference, may be used in accordance with the present disclosure. In general, such preferred methods comprise preparing thermoset (e.g. polyurethane, or polyisocyanurate foams) by combining an isocyanate, an active hydrogen-containing compound such as a polyol or mixture of polyols, a blowing agent composition of the present disclosure, and optionally other materials such as catalysts, surfactants, flame retardants, colorants, or other additives.

[0065] In some aspects, components for polyurethane or polyisocyanurate foams may be provided in pre-blended formulations. In some aspects, the pre-blended formulation is pre-blended into two components. An isocyanate and optionally certain surfactants comprise the first component, commonly referred to as the “A” component. The active hydrogen-containing compound such as a polyol or polyol mixture; surfactants; catalysts; and / or flame retardants comprise the second component, commonly referred to as the “B” component. Theblowing agent composition may be present in the A component and / or the B component. For example, if the blowing agent composition comprises two blowing agents, the first blowing agent may be present in the A component, and the second blowing agent may be present in the B component.TS0126-WO01

[0066] HFO-1252zc may be present in the B component in an amount of about 10 wt% or greater, about 15 wt% or greater, about 20 wt% or less, about 25 wt% or less, about 30 wt% or less, or any value encompassed by these endpoints, as a percentage of the total B component. In some aspects, a mixture of HFO-1252zc and HFO-1336mzz-Z may be present in the B component in an amount of about 10 wt% or greater, about 15 wt% or greater, about 20 wt% or less, about 25 wt% or less, about 30 wt% or less, or any value encompassed by these endpoints, as a percentage of the total B component. In some aspects, a mixture of HFO-125zc and pentane such as n-pentane may be present in the B component in an amount of about 10 wt% or greater, about 15 wt% or greater, about 20 wt% or less, about 25 wt% or less, about 30 wt% or less, or any value encompassed by these endpoints, as a percentage of the total B component.

[0067] The B component of the present disclosure may include additional components. Such optional additional compounds include, but are not limited to, optionally other blowing agent such as HFO-1336mzz-Z, E-1 -chloro-2, 3,3,3- tetrafluoropropene (HCFO-1224yd(E), Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO- 1336mzz(Z)), E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(E), E-1-chloro- 3,3,3-trifluropropene (HCFO-1233zd(E), 1,1-dichloro-2,3,3,3-tetrafluoropropene (HCFO-1214ya), E-1,3,3,3-tetrafluoropropene (1234ze(E), 2,3,3,3-tetrafluoropropene (HFO-1234yf), and 1, 1 -dichloro-2, 2, -difluoroethylene (CFO-1112); hydrocarbons such as iso-pentane, and n-pentane; hydrofluorocarbons such as 1,1,1,3,3- pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365mfc); organic acids such as formic acid and acetic acid); various polyols; water; catalysts such as amine catalysts or metal catalysts; flame retardants such as organic flame retardants and / or inorganic flame retardants; surfactants (silicon or non-silicone); crossslinkers; de-frothing agents; solubility enhancers; fillers; dispersing agents; antibacterial agents; viscosity reduction modifiers; vapor pressure modifiers; colorants; and dyes.. It should be noted that inclusion of some of the listed components may need to be limited in order to still achieve beneficial environmental properties.

[0068] The polyurethane or polyisocyanurate foams may be readily prepared by bringing together the A and B side components by mixing to form a foam, for example blocks, slabs, laminates, pour-in-place panels and other items, sprayTS0126-WO01applied foams, froths, and the like. The mixing may be performed by hand mix e.g. for small preparations or machine mixing techniques.

[0069] The present methods and systems also include forming a one component thermoset foam, such as polyurethane foam, containing a blowing agent in accordance with aspects of the present disclosure. A portion of the blowing agent may be contained in the foamable composition of the one component foam, such as by being dissolved in the foamable composition which is liquid at the pressure within the container, and a second portion of the blowing agent may be present as a separate gas phase. In such systems, the contained / dissolved blowing agent performs, in large part, to cause the expansion of the foam, and the separate gas phase operates to impart propulsive force to the foamable composition. Such one component systems may be packaged in a container, such as an aerosol type can, and the blowing agent of the present disclosure may provide for expansion of the foam and / or the energy to transport the foam / foamable composition from the package, and in some aspects both. Such systems and methods may comprise charging the package with a fully formulated system (such as isocyanate / polyol system) and incorporating a gaseous blowing agent in accordance with the present disclosure into the package, such as an aerosol type can.Benefits / Properties

[0070] As discussed above, it has surprisingly been found that foams formed using blowing agents comprising HFO-1252zc and HFO-1336mzz-Z display improved thermal conductivity versus foams made with HFO-1252zc without HFO-1336mzz-Z.

[0071] In some aspects, a polyurethane or polyisocyanurate of embodiments of the present invention may have an NCO / OH Index of at least 100, i.e. one CN group- to-one OH group, to an NCO-OH index of no more than about 350 i.e. five CN groups-to-one OH group. In some aspects, a polyurethane or polyisocyanurate of embodiments of the present invention may have an NCO / OH Index of at least 100, i.e. one CN group-to-one OH group, to an NCO-OH index of over 500, i.e. five CN groups-to-one OH group. Such characteristics may result in high Index foams having improved fire resistance, increased rigidity, or compressive strength.

[0072] It has been found that using HFO-1336mzz-Z in combination with HFO-1252zc may enhance the blowing agent solubility in the foamable composition,TS0126-WO01resulting in the capture of more blowing agent during the foam making process, and thereby resulting in lower density foams having improved thermal conductivity. In some aspects, foams made with blowing agents as described herein may have a foam density of less than about 65 kg / m3, less than about 40 kg / m3, less than about 35 kg / m3, or less than about 25 kg / m3. Use of HFO-1336mzz-Z is also expected to reduce the overall cost of the foam, as compared to using HFO-1252zc without HFO- 1336mzz-Z, as it may replace some of the HFO-1252zc without sacrificing performance in certain aspects.

[0073] Regarding the vapor-liquid equilibrium (VLE) of HFO-1336mzz-Z, the addition of small amounts of HFO-1252zc may result in a strong bubble point depression. Surprisingly, foams made with compositions comprising about 93 to about 99.9 wt% HFO-1336mzz-Z and about 0.1 to about 7 wt% HFO-1252zc, based on the total combined weight of HFO-1336mzz-Z and HFO-1252zc, may produce foams having exemplary physical properties including thermal conductivity.

[0074] Further, due to the low boiling point of the HFO-1252zc, spray foams made with blowing agents of the present invention may have the appearance of having a fast reactivity (cream time) due to the frothy nature of the sprayed liquid. This can allow for a reduction in catalyst and thereby reduce cost.

[0075] In some aspects, foams formed using blowing agents comprising HFO- 1252zc and HFO-1336mzz-Z may display improved thermal conductivity versus foams made with HFO-1252zc or HFO-1336mzz-Z alone, demonstrated by a k-factor improvement of greater than about 0.5%; greater than about 1 %; greater than about 2%; greater than about 3%; greater than about 4%; greater than about 5%; greater than about 6%; greater than about 8%; about 0.5% to about 15%; about 0.5% to about 12%; about 0.5% to about 10%; about 1% to about 10%; or about 2% to about 8%.

[0076] In some aspects, foams formed using blowing agents as described herein may display improved thermal resistance. Such foams may have a thermal resistance greater than R-4 per inch, greater than R-5 per inch, or greater than R-5.5 per inch.

[0077] In some aspects, foams formed using blowing agents as described herein may have an absence of structural defects. For example, the thermoset polymerTS0126-WO01foam may have at least 80% closed cells, at least 90% closed cells, at least 95% closed cells, or at least 97% closed cells. Closed cell content can be measured according to ASTM method D6226-05.

[0078] Global warming potential (GWP) is an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide. GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas. The GWP for the 100-year time horizon is commonly the value referenced. For mixtures, a weighted average can be calculated based on the individual GWPs for each component. In some aspects, blowing agents and / or foams formed using blowing agents according to embodiments of the present invention have a GWP100 value within the acceptable value as designated by the Significant New Alternatives Policy (SNAP). In some aspects, blowing agents according to embodiments of the present invention have a GWP100 value of less than about 300; less than about 150; less than about 100; less than about 10; less than about 8; less than about 6; less than about 5; less than about 4; less than about 3; less than about 2; less than about 1; or less than about 0.5. In some aspects, foams formed using blowing agents according to embodiments of the present invention have a GWP100 value of less than about 300; less than about 150; less than about 100; less than about 10; less than about 8; less than about 6; less than about 5; less than about 4; less than about 3; less than about 2; less than about 1; or less than about 0.5.

[0079] Ozone depletion potential (ODP) is a number that refers to the amount of ozone depletion caused by a substance. The ODP is the ratio of the impact on ozone of a chemical compared to the impact of a similar mass of CFC-11 (fluorotrichloromethane). Thus, the ODP of CFC-11 is defined to be 1.0. Other CFCs and HCFCs have ODPs that range from 0.01 to 1.0. HFO-1252zc has zero ozone depletion potential. In some aspects, a blowing agent may have an ODP less than 0.005, less than 0.001, or less than 0.0005.TS0126-WO01EXAMPLESExample 1

[0080] Three foamable compositions with different blowing agents were analyzed for performance. The compositions are listed below.Table 1: CompositionsComposition Composition Composition 32(HFO- (HFO- (HFO- 1336mzz- 1336mzz-Z) 1252zc) Z / HFO-1252zc) pphp pphp pphpNCO / OH 110 110 110 IndexPolyester 50 50 50 polyolCo-polyol 50 50 50 (optional)FR (optional) 10 10 10 Emulsifier / 0 0 0 Blowing AgentEnhancerSurfactant 2 2 2 Catalyst 7 7 7 Water 2.7 2.7 2.7 HFO- 12 9.3 1336mzz-ZHFO-1252ZC 5 0.7TS0126-WO01Table 2: Processing TableIso Component Temperature 130F (54.4C) Polyol Component. 130F (54.4C) TemperatureIso Component Pressure 1500 psi (10.3 MPA) Polyol Component Pressure 1500 psi (10.3 MPA)Substrate Temperature 77F (25C)Table 3: Physical PropertiesComp Comp Comp1 2 3Foam density 2.0 (32 2.0 (32 1.8lb / ft3(kg / m3) kg / m3) kg / m3) (28.8kg / m3) ASTM C518 intial), 0.140 0.150 0.135BTU-in / ft2-hr-F (nW / m- (20.2) (21.6) (19.5)K)ASTM C518 (180 0.170 0.180 0.165days), (24.5) (26.0) (23.8)BTU-in / ft2-hr-F (nW / m-K)

[0081] The modeling predictions show that Composition 1 (which is a control formulation example) has a k-factor of 0.140 / .170and Composition 2 (which is a comparative example) has a k-factor of 0.150 / 0.180. Composition 3 uses HFO- 1252zc with HFO-1336mzz-Z and has a k-factor of 0.135 / 0.165, a significant improvement compared to Compositions 1 and 2.

Claims

TS0126-WO01CLAIMSWhat is claimed is:

1. A process for preparing a thermoset polymer foam, the process comprising:a. providing a foamable composition comprising an active hydrogencontaining compound and a blowing agent, wherein the blowing agent comprises HFO-1252zc and HFO-1336mzz-Z;b. expanding the foamable composition to produce the thermoset polymer foam.

2. The process of claim 1, wherein the foamable composition further comprises an isocyanate.

3. The process of claim 2, wherein the isocyanate comprises at least one of aliphatic, cycloaliphatic, aromatic, and heterocyclic isocyanates.

4. The process of any of the preceding claims, wherein the active hydrogencontaining compound comprises a thermoset polymer.

5. The process of claim 4, wherein the thermoset polymer comprises a polyol.

6. The process of claim 5, wherein the polyol comprises a polyester polyol.

7. The process of claim 5, wherein the polyol comprises a polyester polyol having a hydroxyl number of from about 180 mg KOH / g to about 380 mg KOH / g.

8. The process of claim 5, wherein the polyol comprises a polyester polyol having a hydroxyl number of from about 200 mg KOH / g to about 300 mg KOH / g.

9. The process of claim 5, wherein the polyol is a polyester polyol having a hydroxyl number of from about 220 mg KOH / g to about 250 mg KOH / g.

10. The process of any of the preceding claims, wherein the blowing agent comprises HFO-1252zc in an amount of about 0.1 wt% to about 10 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc.TS0126-WO0111. The process of claims 1-9, wherein the blowing agent comprises HFO-1252zc in an amount of about 0.1 wt% to about 7 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc.

12. The process of claims 1-9, wherein the blowing agent comprises HFO- 1336mzz-Z in an amount of about 90 wt% to about 99.9 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc.

13. The process of claims 1 -9, wherein the blowing agent comprises HFO- 1336mzz-Z in an amount of about 93 wt% to about 99.9 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc.

14. The process of any of the preceding claims, wherein the foamable composition comprises the blowing agent in an amount of about 2 wt% to about 15 wt% of the foamable composition.

15. The process of any of the preceding claims, wherein the foamable composition comprises or more additives selected from at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant agent, and at least one nucleating agent.

16. The process of any of the preceding claims, wherein the foamable composition comprises a metal catalyst and an amine catalyst.

17. The process of claim 15, wherein the surfactant is a silicone surfactant.

18. The process of any of the preceding claims, wherein the process is performed in the absence of a nucleating agent.

19. The process of any of the preceding claims, wherein the foam is a polyurethane foam or a polyisocyanurate foam.

20. The process of any of the preceding claims, wherein the foam is a closed cell foam.

21. A foam formed according to the process of claim 1.

22. A closed cell polyisocyanurate foam prepared according to the process of claim 1.

23. A closed cell polyurethane foam prepared according to the process of claim 1.TS0126-WO0124. A thermoset polymer foam comprising:a. an active hydrogen-containing compound; andb. a blowing agent comprising HFO-1252zc and HFO-1336mzz-Z.

25. The thermoset polymer foam of claim 24, wherein the foam comprises a polyurethane or polyisocyanurate foam.

26. The thermoset polymer foam of claim 24, wherein the foam comprises a closed cell polyisocyanurate foam.

27. The thermoset polymer foam of claim 24, wherein the foam comprises a closed cell polyurethane foam.

28. The thermoset polymer foam of claims 24-27, wherein the active hydrogencontaining compound comprises a thermoset polymer.

29. The thermoset polymer foam of claim 28, wherein the thermoset polymer comprises a polyol.

30. The thermoset polymer foam of claim 29, wherein the polyol comprises a polyester polyol.

31. The thermoset polymer foam of claim 29, wherein the polyol comprises a polyester polyol having a hydroxyl number of from about 180 mg KOH / g to about 380 mg KOH / g.

32. The thermoset polymer foam of claim 29, wherein the polyol comprises a polyester polyol having a hydroxyl number of from about 200 mg KOH / g to about 300 mg KOH / g.

33. The thermoset polymer foam of claim 29, wherein the polyol is a polyester polyol having a hydroxyl number of from about 220 mg KOH / g to about 250 mg KOH / g.

34. The thermoset polymer foam of claims 24-33, wherein the foam comprises HFO-1252zc in an amount of about 0.1 pphp to about 10 pphp.

35. The thermoset polymer foam of claims 24-33, wherein the foam comprises HFO-1252zc in an amount of about 0.1 pphp to about 5 pphp.TS0126-WO0136. The thermoset polymer foam of claims 24-33, wherein the foam comprises HFO-1252zc in an amount of about 0.1 pphp to about 2 pphp.

37. The thermoset polymer foam of claims 24-33, wherein the foam comprises HFO-1252zc in an amount of about 1 to about 10 pphp.

38. The thermoset polymer foam of claims 24-33, wherein the foam comprises HFO-1252zc in an amount of about 6 to about 10 pphp.

39. The thermoset polymer foam of claims 24-33, wherein the foam comprises HFO-1336mzz-Z in an amount of about 4 to about 20 pphp.

40. The thermoset polymer foam of claims 24-33, wherein the foam comprises HFO-1336mzz-Z in an amount of about 5 pphp to about 15 pphp.

41. The thermoset polymer foam of claims 24-33, wherein the foam comprises HFO-1336mzz-Z in an amount of about 8 pphp to about 16 pphp.

42. The thermoset polymer foam of claims 24-33, wherein the foam comprises HFO-1336mzz-Z in an amount of about 10 pphp to about 15 pphp.

43. The thermoset polymer foam of claims 24-42, wherein the blowing agent is present in an amount of about 2 wt% to about 15 wt% of the thermoset polymer foam.

44. The thermoset polymer foam of claims 24-43, wherein the foam comprises a foam for use in spray applications.

45. The thermoset polymer foam of claims 24-43, wherein the foam comprises a pour-in-place panel.

46. The thermoset polymer foam of claims 24-43, wherein the foam comprises a foam for use in an appliance.

47. A foamable composition comprising:a. an active hydrogen-containing compound; andb. a blowing agent comprising HFO-1252zc and HFO-1336mzz-Z.

48. The foamable composition of claim 47, wherein the foamable composition further comprises an isocyanate.TS0126-WO0149. The foamable composition of claim 48, wherein the isocyanate comprises at least one of aliphatic, cycloaliphatic, aromatic, and heterocyclic isocyanates.

50. The foamable composition of claims 47-49, wherein the active hydrogencontaining compound comprises a thermoset polymer.

51. The foamable composition of claim 50, wherein the thermoset polymer comprises a polyol.

52. The foamable composition of claim 51, wherein the polyol comprises a polyester polyol.

53. The foamable composition of claim 51, wherein the polyol comprises a polyester polyol having a hydroxyl number of from about 180 mg KOH / g to about 380 mg KOH / g.

54. The foamable composition of claim 51, wherein the polyol comprises a polyester polyol having a hydroxyl number of from about 200 mg KOH / g to about 300 mg KOH / g.

55. The foamable composition of claim 51, wherein the polyol is a polyester polyol having a hydroxyl number of from about 220 mg KOH / g to about 250 mg KOH / g.

56. The foamable composition of claims 47-56, wherein the foamable composition comprises HFO-1252zc in an amount of about 0.1 pphp to about 10 pphp.

57. The foamable composition of claims 47-56, wherein the foamable composition comprises HFO-1252zc in an amount of about 0.1 pphp to about 5 pphp.

58. The foamable composition of claims 47-56, wherein the foamable composition comprises HFO-1252zc in an amount of about 0.1 pphp to about 2 pphp.

59. The foamable composition of claims 47-56, wherein the foamable composition comprises HFO-1252zc in an amount of about 1 to about 10 pphp.

60. The foamable composition of claims 47-56, wherein the foamable composition comprises HFO-1252zc in an amount of about 6 to about 10 pphp.

61. The foamable composition of claims 47-60, wherein the foamable composition comprises HFO-1336mzz-Z in an amount of about 4 to about 20 pphp.TS0126-WO0162. The foamable composition of claims 47-60, wherein the foamable composition comprises HFO-1336mzz-Z in an amount of about 5 pphp to about 15 pphp.

63. The foamable composition of claims 47-60, wherein the foamable composition comprises HFO-1336mzz-Z in an amount of about 8 pphp to about 16 pphp.

64. The foamable composition of claims 47-60, wherein the foamable composition comprises HFO-1336mzz-Z in an amount of about 10 pphp to about 15 pphp.

65. The foamable composition of claims 47-64, wherein the foamable composition comprises the blowing agent in an amount of about 2 wt% to about 15 wt% of the foamable composition.

66. The foamable composition of claims 47-65, wherein the foamable composition further comprises one or more additives selected from at least one polyol, at least one catalyst, at least one surfactant, water, at least one flame retardant agent, and at least one nucleating agent.

67. The foamable composition of claims 47-66, wherein the foamable composition comprises a metal catalyst and an amine catalyst.

68. The foamable composition of claim 66, wherein the surfactant is a silicone surfactant.

69. A blowing agent comprising HFO-1252zc and HFO-1336mzz-Z.

70. The blowing agent of claim 69, wherein the blowing agent comprises HFO- 1252zc in an amount of about 0.1 wt% to about 10 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc.

71. The blowing agent of claim 69, wherein the blowing agent comprises HFO- 1252zc in an amount of about 0.1 wt% to about 7 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc.

72. The blowing agent of claim 69, wherein the blowing agent comprises HFO- 1336mzz-Z in an amount of about 90 wt% to about 99.9 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc.TS0126-WO0173. The blowing agent of claim 69, wherein the blowing agent comprises HFO- 1336mzz-Z in an amount of about 93 wt% to about 99.9 wt%, based on a total weight of HFO-1336mzz-Z and HFO-1252zc.

Images