Compositions comprising HFO-1252ZC and their use as agents for thermoplastic foam expansion

Abstract

Processes, foams, foamable compositions, and blowing agents related to thermoplastic polymer foam compositions comprising a thermoplastic polymer and a blowing agent comprising HFO-1252zc.

Description

TS0124-W001TITLE OF THE INVENTION COMPOSITIONS COMPRISING HFO-1252ZC AND THEIR USE AS AGENTS FOR THERMOPLASTIC FOAM EXPANSION CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 745,434 filed January 15, 2025, the disclosure of which is incorporated herein by reference in its entirety.FIELD OF THE INVENTION

[0002] This invention relates to the use of 1 ,1 -difluoropropene (HFO-1252zc) and blends thereof as blowing agents for thermoplastic polymers comprising polystyrene.BACKGROUND OF THE INVENTION

[0003] Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been adopted for a wide range of uses including as expansion agents for thermoplastic polymeric foam. For example, CFC-12 was used as the agent for extruded polystyrene foam expansion before 1990. HCFC-142b and HCFC-22 were used as agents for extruded polystyrene foam expansion after 1990. However, many CFCs and HCFCs have been recognized as ozone depleting substances (ODS) under the Montreal Protocol.

[0004] Hydrofluorocarbons (HFCs) have been adopted by many industries as alternatives for CFCs and HCFCs over the past few decades. HFCs do not contribute to the destruction of stratospheric ozone but they contribute to global warming. Some hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) with low global warming potentials have been found suitable as alternatives for CFCs, HCFCs and / or HFCs for many uses.

[0005] The evolving regulatory landscape is now considering, in addition to Ozone Depletion Potential (ODP) and Global Warming Potential (GWP), the environmental fate of products resulting from the atmospheric decomposition of the above versatile compounds (including HFCs and HFOs). Therefore, there is a need for compounds and compositions that meet low ODP and GWP requirements, have favorable environmental and safety profiles, and provide acceptable performance (e.g., meetTS0124-W001energy efficiency standards) in a wide range of uses including as blowing agents for thermoplastic (e.g. polystyrene) foam. More particularly, there is a need for compounds and compositions to replace various incumbent blowing agents for thermoplastic foam (e.g. CFCs, HCFCs, HFCs, HFOs, and HCFOs including R-134a, R-1234yf, and HCFO-1224yd(Z)).SUMMARY OF THE INVENTION

[0006] According to certain aspects of the invention, a blowing agent includes HFO-1252zc. In some aspects, the blowing agent includes HFO-1252zc in an amount of about 1 wt% to about 99 wt%; about 25 wt% to about 75 wt%; about 70 wt% to about 90 wt%; or about 73 wt% to about 87 wt% of the blowing agent. In some aspects, a blowing agent includes one or more of HFC-134, ethanol, dimethylether, methylal, methyl formate, trans-1 ,2-dichloroethylene, chloropropane, normal pentane, cyclopentane, isopentane, neopentane, HFO-1243yc, CFO-1112, HFO- 1234ze(E), HFO-1234ze(Z), HFO-1336mzz(Z), HFO-1336mzz(E), HCFO-1233zd(E), HCFO-1233zd(Z), or combinations thereof.

[0007] In certain aspects, a blowing agent may include one or more of: HFC-134 in an amount of about 10 wt% to about 30 wt%; or about 13 wt% to about 27 wt% of the blowing agent; ethanol in an amount of about 25 wt% to about 75 wt% of the blowing agent; dimethyl-ether in an amount of about 25 wt% to about 75 wt% of the blowing agent; methylal in an amount of about 25 wt% to about 75 wt% of the blowing agent; methyl formate in an amount of about 25 wt% to about 75 wt% of the blowing agent; trans-1 ,2-dichloroethylene in an amount of about 25 wt% to about 75 wt% of the blowing agent; chloropropane in an amount of about 25 wt% to about 75 wt% of the blowing agent; normal pentane in an amount of about 25 wt% to about 75 wt% of the blowing agent; cyclopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent; isopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent; neopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent; HFO-1243yc in an amount of about 25 wt% to about 75 wt% of the blowing agent; CFO-1112 in an amount of about 25 wt% to about 75 wt% of the blowing agent; HFO-1234ze(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent; HFO-1234ze(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent; HFO-1336mzz(Z) in an amount of about 25 wt% to about 75 wt% ofTS0124-W001the blowing agent; HCFO-1233zd(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent; and / or HCFO-1233zd(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent In some aspects, a blowing agent comprises an azeotropic or near-azeotropic composition of HFO-1252zc and one or more blend components.

[0008] According to certain aspects of the present invention, a foamable composition may include a thermoplastic polymer; and a blowing agent comprising HFO-1252zc. Foamable compositions of the present invention may use blowing agents and thermoplastic polymers as described in various aspects of this disclosure in any useful combination. In some aspects, the thermoplastic polymer is selected from the group consisting of polystyrene, polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, acrylonitrile butadiene styrene, styrene acrylonitrile copolymer, and blends thereof. In some aspects, the thermoplastic polymer is selected from the group consisting of a polystyrene homopolymer, a polystyrene copolymer, styrene-acrylonitnie copolymer, and blends thereof.

[0009] In certain aspects, a foamable composition includes from about 5 parts to about 25 parts per hundred parts of thermoplastic polymer by mass. In some aspects, a foamable composition may include a blowing agent in an amount of about 0.01 to about 0.2 moles of blowing agent per 100 grams of the thermoplastic polymer resin (mhr). In some aspects, a foamable composition may include a blowing agent in an amount of about 5 to about 20 wt% of the foamable composition.

[0010] According to certain aspects of the present invention a thermoplastic polymer foam includes a thermoplastic polymer; and, a blowing agent comprising HFO-1252zc. Foams of the present invention may use blowing agents and thermoplastic polymers as described in various aspects of this disclosure in any useful combination.

[0011] In certain aspects, a foam includes from about 5 parts to about 25 parts per hundred parts of thermoplastic polymer by mass. In some aspects, a foam may include a blowing agent in an amount of about 5 to about 20 wt% of the foamable composition. In certain aspects, the foam comprises the blowing agent in an amount of about 4.65 to about 17.15 phr.TS0124-W001

[0012] In some aspects, a foam has beneficial properties including one or more of: a thermal resistance meeting or exceeding the industry standard of R-5; a GWP100 value of less than about 300; a GWP100 value of less than about 50; comprises no more than de minimis ODP; at least 80% closed cells as measured according to ASTM method D6226-05; at least 90% closed cells as measured according to ASTM method D6226-05; and / or is essentially free of structural defects

[0013] According to certain aspects of the present invention, a process for preparing a thermoplastic polymer foam includes providing a foamable composition comprising a thermoplastic polymer and a blowing agent, wherein the blowing agent comprises HFO-1252zc; and expanding the foamable composition to produce the thermoplastic polymer foam. Processes of the present invention may use foamable compositions, blowing agents, and thermoplastic polymers as described in various aspects of this disclosure in any useful combination.DETAILED DESCRIPTION OF THE INVENTION

[0014] 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.

[0015] The present invention solves certain problems associated with many incumbent compounds used as expansion agents for thermoplastic polymeric foams (e.g., extruded polystyrene foam). It has surprisingly been found that blowing agents comprising HFO-1252zc 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, absence of structural defects, etc.).TS0124-W001Blowing Agents

[0016] 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.

[0017] 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.TS0124-W001

[0018] 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.

[0019] In some aspects, a blowing agent may comprise HFO-1252zc in an amount of about 1 wt% to about 99 wt%; about 25 wt% to about 75 wt%; about 70 wt% to about 90 wt%; or about 73 wt% to about 87 wt% of the blowing agent. 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.

[0020] 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).TS0124-W001

[0021] Such additional components may include hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), hydrochloroolefins (HCOs), chloro-fluoroolefins (CFOs), perfluorinated olefins, saturated hydrofluoroethers (HFEs), unsaturated hydrofluoroethers (HFEOs), saturated hydrocarbons, 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.

[0022] In some aspects, a blowing agent is essentially free of 1 ,1 -difluoroethane (HFC-152a). 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 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and HFC-152a in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, the HFC-152a, when present, may be present in the thermoplastic polymer in an amount of up to about 4.0 phr, or in the range of about 1.0 phr to about 3.0 phr.

[0023] In some aspects, a blowing agent may include HFO-1252zc in combination with HFC-134. A blowing agent may include HFC-134 in an amount of about 10 wt% to about 30 wt% of the blowing agent, or about 13 wt% to about 27 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 70 wt% to about 90 wt% and HFC-134 in an amount of about 10 wt% to about 30 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 73 wt% to about 87 wt% and HFC-134 in an amount of about 13 wt% to about 27 wt% of the blowing agent.TS0124-W001

[0024] In some aspects, a blowing agent may include HFO-1252zc in combination with ethanol. A blowing agent may include ethanol in an amount of about 25 wt% to about 75 wt% of the blowing agent In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and ethanol in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0025] In some aspects, a blowing agent may include HFO-1252zc in combination with dimethyl-ether. A blowing agent may include dimethyl-ether in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and dimethyl-ether in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0026] In some aspects, a blowing agent may include HFO-1252zc in combination with methylal. A blowing agent may include methylal in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and methylal in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0027] In some aspects, a blowing agent may include HFO-1252zc in combination with methyl formate. A blowing agent may include methyl formate in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and methyl formate in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0028] In some aspects, a blowing agent may include HFO-1252zc in combination with trans-1 ,2-dichloroethylene. A blowing agent may include trans-1 ,2- dichloroethylene in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and trans-1 ,2-dichloroethylene in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0029] In some aspects, a blowing agent may include HFO-1252zc in combination with chloropropane. A blowing agent may include chloropropane in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and chloropropane in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W001

[0030] In some aspects, a blowing agent may include HFO-1252zc in combination with normal pentane. A blowing agent may include normal pentane in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and normal pentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0031] In some aspects, a blowing agent may include HFO-1252zc in combination with cyclopentane. A blowing agent may include cyclopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and cyclopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0032] In some aspects, a blowing agent may include HFO-1252zc in combination with isopentane. A blowing agent may include isopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and isopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0033] In some aspects, a blowing agent may include HFO-1252zc in combination with neopentane. A blowing agent may include neopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and neopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0034] In some aspects, a blowing agent may include HFO-1252zc in combination with HFO-1243yc. A blowing agent may include HFO-1243yc in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and HFO- 1243yc in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0035] In some aspects, a blowing agent may include HFO-1252zc in combination with CFO-1112. A blowing agent may include CFO-1112 in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and CFO-1112 in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W001

[0036] In some aspects, a blowing agent may include HFO-1252zc in combination with HFO-1234ze(E). A blowing agent may include HFO-1234ze(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and HFO-1234ze(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0037] In some aspects, a blowing agent may include HFO-1252zc in combination with HFO-1234ze(Z). A blowing agent may include HFO-1234ze(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and HFO-1234ze(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0038] 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 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and HFO-1336mzz(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0039] In some aspects, a blowing agent may include HFO-1252zc in combination with HFO-1336mzz(E). A blowing agent may include HFO-1336mzz(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and HFO-1336mzz(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0040] In some aspects, a blowing agent may include HFO-1252zc in combination with HCFO-1233zd(E). A blowing agent may include HCFO-1233zd(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% and HCFO-1233zd(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0041] In some aspects, a blowing agent may include HFO-1252zc in combination with HCFO-1233zd(Z). A blowing agent may include HCFO-1233zd(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent. In some aspects, a blowing agent may include HFO-1252zc in an amount of about 25 wt% to about 75 wt% andTS0124-W001HCFO-1233zd(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

[0042] In some aspects, a blowing agent may include HFO-1252zc in combination with HFC-152a and a pentane such as n-pentane.

[0043] In some aspects, a blowing agent may include carbon dioxide and / or nitrogen. For example, a blowing agent may include carbon dioxide and / or nitrogen in an amount of about 0.5 wt% to about 7 wt% of the blowing agent.

[0044] In some aspects, a blowing agent may include water. When water is added, it will typically be present in an amount of less than 30 wt% of the blowing agent, such as 15 wt% or less, or 5 wt% or less. In some aspects, a blowing agent may include water in an amount of about 0.2 to about 2.0 pphp. The abbreviation “pphp” is used herein to mean parts per hundred parts of polyol, unless specified otherwise herein.

[0045] In some embodiments, the blowing agent provided herein is substantially free of additives. In some embodiments, the blowing agent provided herein comprises one or more additives (e.g., one, two, three, four, or five additives).Azeotrope Compositions

[0046] Some compositions of HFO-1252zc may form azeotropic or near-azeotrope compositions with some blend components.

[0047] 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 evaporation or 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 allTS0124-W001three 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.

[0048] 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.

[0049] 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.

[0050] 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 same components may be used to confirm the accuracy of such calculations and / or to modify the calculations at the same or other temperatures and pressures.TS0124-W001Foamable Compositions

[0051] 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 polystyrene foam compositions.

[0052] In some aspects, components capable of forming foam include a thermoplastic polymer. A suitable thermoplastic polymer may include an alkenyl aromatic polymer. As used herein, the term “alkenyl aromatic polymer” refers to a polymer formed from alkenyl-aromatic monomer units. In some aspects, the alkenylaromatic monomer unit is a C2-6 alkenyl-C6-10 aryl monomer unit. In some aspects, the alkenyl-aromatic monomer unit is a C2-6 alkenyl-phenyl monomer unit, wherein the phenyl is optionally substituted. In some aspects, the alkenyl aromatic polymer is polystyrene.

[0053] The polystyrene can be styrene homopolymer or can contain copolymerized monomer other than styrene (i.e., polystyrene copolymer). In some aspects, the thermoplastic polymer comprises a blend of polystyrene and an additional thermoplastic polymer. In some aspects, the additional thermoplastic polymer is a copolymer of styrene with a monomer other than styrene (e.g., acrylonitrile).

[0054] In some aspects, the thermoplastic polymer is selected from polystyrene, polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, acrylonitrile butadiene styrene, styrene acrylonitrile copolymer, and blends thereof. In certain aspects, the thermoplastic polymer is selected from polystyrene, polyethylene, and polypropylene. In some aspects, the thermoplastic polymer is a polyethylene-polypropylene copolymer. The polyethylene can be ethylene homopolymer or can contain copolymerized monomer other than ethylene, i.e. polyethylene copolymer. The polypropylene can be propylene homopolymer or can contain copolymerized monomer other than propylene, i.e. polypropylene copolymer.

[0055] In some aspects, the thermoplastic polymer is polystyrene.

[0056] Whether the thermoplastic polymer being foamed is polystyrene or blends of polystyrene with other thermoplastic polymer, in some aspects styrene may be theTS0124-W001dominant polymerized monomer (unit) in the thermoplastic polymer being foamed. In some aspects, the polymerized units of styrene constitute at least 70 mol%, at least 80 mol%, at least 90 mol%, or 100 mol% of the polymerized monomer units of the thermoplastic polymer.

[0057] When the thermoplastic polymer contains styrene copolymer, the amount of the additional monomer copolymerized with the styrene may be such that the styrene content of the copolymer is at least 60 mol% of the copolymer, at least 70 mol%, at least 80 mol%, or at least 90 mol% of the copolymer, based on the total number of moles (i.e., 100%) of the copolymer. It is understood that these ratios apply whether the styrene copolymer is the only styrene-containing polymer in the thermoplastic polymer or is a blend with other thermoplastic polymer, such as styrene homopolymer or other styrene copolymer.

[0058] In some aspects, the thermoplastic polymer comprises styrene homopolymer (i.e., polystyrene homopolymer). When the thermoplastic polymer is a blend of polystyrene and other thermoplastic polymer as described above, the polystyrene component of this blend may be styrene homopolymer comprising at least 80 wt% of the combined weight of polystyrene and other thermoplastic polymer.

[0059] The molecular weight of the thermoplastic polymer being foamed may be sufficiently high to provide the strength necessary for the requirements of the foam application. The strength requirement may determine the minimum density of the foamed product. The high molecular weight of the thermoplastic polymer may also contribute to the strength of the foamed product. An indicator of molecular weight is the rate at which the molten polymer flows through a defined orifice under a defined load. The lower the flow, the higher the molecular weight. Measurement of the melt flow rate is determined in accordance with ASTM D 1238 at 200°C and using a 5 kg weight on the molten polymer. The weight of molten polymer flowing through the orifice in a defined amount of time, enables the melt flow rate to be reported in g / 10 min. In some aspects, the melt flow rate of the thermoplastic polymer is no greater than 20 g / 10 min, no greater than 15 g / 10 min, or no greater than 10 g / 10 min.Surprisingly, the higher the molecular weight (lower the melt flow rate), the better the foaming result, especially with respect to the attainability of low density foamed products, while still achieving smooth skin on the foamed product. In some aspects,TS0124-W001the minimum melt flow rate for all the melt flow rates disclosed herein is at least 1 g / 10 min, whereby the melt flow rate ranges disclosed herein include, but are not limited to, 1 to 25, 1 to 20, 1 to 15, and 1 to 10 g / 10 min. In some aspects, the melt flow rate is about 25 g / 10 min or less, as determined in accordance with the procedure of ASTM D 1238 at 200°C using a 5 kg weight on the molten polymer.

[0060] The references to thermoplastic polymer comprising polystyrene also apply to polystyrene by itself. Thus, for example, the disclosure of thermoplastic polymer comprising polystyrene in the preceding paragraph can be replaced by the disclosure polystyrene.

[0061] In some aspects, the foamable composition includes from about 5 parts to about 25 parts per hundred parts of polymer by mass, for example, about 5 to about 20, about 5 to about 15, about 5 to about 10, about 10 to about 25, about 10 to about 20, about 10 to about 15, about 15 to about 25, about 15 to about 20, or about 20 to about 25 parts per hundred parts of polymer by mass. In some embodiments, the foamable composition is from about 7 parts to about 18 parts per hundred parts of polymer by mass.

[0062] In some aspects, the foamable composition can contain additives other than the polymer being foamed and the HFO-1252zc or HFO-1252zc blend blowing agent, such as co-blowing agent, nucleating agent, flame retardant, cell stabilizer agent, surfactant, preservative colorant, antioxidant, reinforcing agent, filler, antistatic agent, infrared (IR) attenuating agent, extrusion aid, plasticizer, viscosity modifier, and other known additives, all in the amount necessary to obtain the effect desired. The present invention is not limited to any particular additive, except as may be specified in any claim appended hereto.

[0063] Examples of suitable nucleating agent include talc, graphite, and magnesium silicate. In some embodiments, the foamable composition further comprises a flame retardant. In some aspects, a suitable flame retardant comprises a polymeric flame retardant or a halogenated flame retardant. In some aspects, the flame retardant is a brominated flame retardant or a chlorinated flame retardant. In some aspects, the flame retardant is a brominated styrene-butadiene block copolymer. Examples of suitable flame retardants include tetrabromo-bis phenol ATS0124-W001and polymeric flame retardants. One example of a brominated styrene-butadiene block copolymer is known commercially as PolyFR.

[0064] The amount of blowing agent in the foamable composition will depend on the amount of additives other than blowing agent and the density desired in the foamed product. In one aspect, the amount of blowing agent may be from about 0.01 to about 0.2 moles of blowing agent per 100 grams of the thermoplastic polymer resin (mhr). In another aspect, the amount of blowing agent may be from about 0.05 to about 0.15 mhr. In another aspect, the amount of blowing agent may be from about 0.08 to about 0.12 mhr. In various aspects, the amount of blowing agent can vary depending on the desired density of the foam, and the composition of the blowing agent. In some aspects, the amount of blowing agent may be in the range of about 0.024 to about 0.344 mhr, or in the range of about 0.046 to about 0.228 mhr. In some aspects, the amount of blowing agent in the foamable composition is from about 5 to about 20 wt% of the foamable composition. In some aspects, the amount of blowing agent in the foamable composition is from about 5 to about 15 wt%, based on the weight of the foamable composition. It is understood that the weight percentage of the blowing agent in the foamable composition can be adjusted based on the desired density of the foam, and the ratio of components in the blowing agent.

[0065] In some aspects, the polymer and blowing agent may be heated in the presence of one or more additives. Exemplary additives include, but are not limited to, nucleating agents, cell stabilizer agents, surfactants, preservative colorants, antioxidants, reinforcing agents, fillers, antistatic agents, IR attenuating agents, extrusion aids, plasticizers, and viscosity modifiers, or any combination thereof, in an amount to obtain the effect desired.Method of Forming Foams

[0066] 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. In some aspects, a foaming process is carried out using an extruder to form the foamable composition and to extrude it to form the foamed product. The thermoplastic polymer may form the feed to the extruder. The blowing agent(s) is (are) may be fed into the extruder at a location intermediate to the feed and extrusion ends of the extruder, typically into the moltenTS0124-W001foamable composition that is created as the extrusion screw advances the feeds to the extruder along its length. Other additives to the foamable composition may be added where convenient and as may be dictated by the state of the additive. For example, solid additives can be conveniently added to the feed end of the extruder, possibly as a mixture with the polymer feed in particulate form to the extruder. The molten foamable composition within the extruder may be extruded through a die, thereby allowing the foamable composition to expand into a foamed product. The foamed product, which can be in such forms as sheet, plank, rod, or tube, is then cooled.

[0067] In the region within the extruder where the composition is melted to form the molten foamable composition, this melting may occur by the input of heat and the heat developed in the mixing process forming the melt. This is considered the melt mixing region of the extruder. In some aspects, the temperature is at least about 185°C, at least about 190°C, at least about 200°C, or at least about 210°C in this melt mixing region. In another aspect, the maximum temperature for all the melt mixing temperatures disclosed herein may be about 250°C. The melt mixing temperatures disclosed herein are the temperatures of the melt in the mixing zone at the time of mixing. In one aspect, the pressure under which the melt mixing is carried out is at least about 2000 psi (138 Bar), at least about 3000 psi (207 Bar), or at least about 4000 psi (276 Bar). In some aspects, the maximum value for all the minimum pressures disclosed under which the melt mixing is carried out is no greater than about 5000 psi (345 Bar). The pressures disclosed herein are gauge pressures.

[0068] In the region within the extruder where the molten composition is extruded, the molten composition may be cooled so that the temperature at which the extrusion is carried out is at least 100°C, at least 110° C, at least 120° C, or at least 125°C. In some aspects, the maximum value for all the minimum extrusion temperatures disclosed herein is no greater than 140°C. The extrusion temperatures disclosed herein are the temperature of the melt at the time of extrusion.

[0069] In some aspects, the extrusion is carried out at a pressure of at least 700 psi (48 Bar), at least 1000 psi (69 Bar), or at least 1300 psi (90 Bar). In some aspects, the maximum value for the minimum extrusion pressures disclosed hereinTS0124-W001is no greater than 2000 psi (138 Bar). The extrusion pressure is the pressure inside the extrusion die.

[0070] In some embodiments, the process is performed at a pressure just before foaming of from about 100 psi to about 5000 psi, for example, about 100 psi to about 4000 psi, about 100 psi to about 3000 psi, about 100 psi to about 2000 psi, about 100 psi to about 1000 psi, about 1000 psi to about 5000 psi, about 1000 psi to about 4000 psi, about 1000 psi to about 3000 psi, about 1000 psi to about 2000 psi, about 2000 psi to about 5000 psi, about 2000 psi to about 4000 psi, about 2000 psi to about 3000 psi, about 3000 psi to about 5000 psi, about 3000 psi to about 4000 psi, or about 4000 psi to about 5000 psi. In some embodiments, the process is performed at a pressure just before foaming of from about 500 psi to about 4000 psi. In some embodiments, the process is performed at a pressure just before foaming of from about 800 psi to about 3000 psi. In some embodiments, the process is performed at a pressure just before foaming of from about 1000 psi to about 2500 psi.

[0071] The disclosures of multiple ranges for melt flow rate, temperature, and pressure above can be used in any combination in the practice of the present invention to obtain the particular foamed structure desired. For example, melt mixing pressures of 2000 to 5000 psi (138 to 345 Bar) may be useful for achieving low foam densities of the foamed product, and this pressure range can be used with any of the melt mixing and extrusion temperature ranges to form any of the smooth-skin, closed cell foam product densities disclosed herein. The same is true for the melt extrusion pressure range of 700 to 2000 psi (48 to 138 Bar) together with the 3000 to 5000 psi (207 to 345 Bar) pressure range for melt mixing. In some aspects, two particular pressure ranges, for melt mixing (138 Bar to 345 Bar) and extrusion (48 to 138 Bar) are used together. The melt flow rates for the polymer being foamed of no greater than 25, 20, 15, and 10, and as little as at least 1, all values being in g / 10 min, can be used with any of these combinations of pressure and temperatures, depending on the foamed product result desired.

[0072] In some aspects a thermoplastic polymer foam is formed by a process comprising extruding a molten composition comprising thermoplastic polymer and blowing agent comprising HFO-1252zc. In some aspects a thermoplastic polymerTS0124-W001foam is formed by a process comprising extruding a molten composition comprising thermoplastic polymer and blowing agent comprising HFO-1252zc and HFC-152a. In some aspects a thermoplastic polymer foam is formed by a process comprising extruding a molten composition comprising thermoplastic polymer andblowing agent comprising HFO-1252zc and HFC-134. The extrusion may be carried out at a temperature of at least 100°C, at least 120°C, or at least 125°C, and under a pressure of at least 700 psi, at least 1000 psi, or at least 1300 psia, and obtaining as a result thereof a substantially closed cell, defect-free foamed thermoplastic polymer. The extrusion temperatures disclosed herein are the temperatures of the melt at the time of extrusion. The extrusion pressures are the pressures inside the extrusion die.Foam

[0073] 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. Preferably, the disclosure relates to a closed cell rigid foam comprising the blowing agent composition comprising HFO-1252zc described herein.

[0074] 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, about 2 wt% to about 15 wt%, or within any range encompassing these endpoints, as a percentage of the total weight of the foam.

[0075] In some aspects, the total amount of blowing agent in the thermoplastic polymer is at least about 2.73 phr, in the range of about 2.73 phr to about 25.37 phr, or in the range of about 4.65 to about 17.15 phr.

[0076] 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,TS0124-W001freezer foams, refrigerator / freezer foams, panel foams, and other cold or cryogenic manufacturing applications.

[0077] 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.

[0078] The foam may be a thermoplastic foam. In certain aspects, the thermoplastic may be polystyrene, polyethylene, or polypropylene.Benefits / Properties

[0079] As discussed above, it has surprisingly been found that foams formed using blowing agents comprising HFO-1252zc, either alone or in combination with HFC- 152a, HFC-134, and / or other components, display desirable foam quality characteristics while also having favorable environmental fate. In particular, thermoplastic polymeric foams formed using blowing agents as described herein may:- generate no more than de minimis yields of persistent products of atmospheric decomposition such as trifluoro-acetic acid (TFA); have no more than de minimis ODP;- are not recognized as ODS under the Montreal Protocol;- have low GWP 100;- have acceptable health and safety profiles (e.g., low toxicity and low or no flammability); and / or- enable acceptable performance as agents for thermoplastic foam expansion (e.g., foam thermal resistance, mechanical strength, etc.) such as thermal resistance meeting or exceeding the industry standard of R-5TS0124-W001

[0080] 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 50; 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 50; 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.

[0081] 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.

[0082] In some aspects, thermoplastic polymeric foams formed using blowing agents as described herein may have low or now flammability; i.e. ASHRAE flammability class 2, 2L or 1.

[0083] In some aspects, the extruded thermoplastic polymer foam and blowing agent exhibits at least one, more than one, or all of the following foamed product attributes:TS0124-W001- The thermoplastic polymer foam has a good foam quality in that it is essentially free of structural defects, including, but not limited to, foam collapse and blowholes of a size exceeding multiple cell diameters.- The thermoplastic polymer foam has an average foam cell diameter greater than 0.10 mm, greater than 0.15 mm, from about 0.005 mm to about 5 mm (i.e. , 5 pm to about 5000 pm), for example, about 0.01 mm to about 5 mm, about 0.05 mm to about 5 mm, about 0.05 mm to about 0.5 mm. In some aspects, the average cell diameter is from about 0.01 mm to about 1 mm. In some aspects, the average cell size is from about 0.02 mm to about 0.5 mm. In some aspects, the average cell size is from about 0.1 mm to about 0.3 mm.- The thermoplastic polymer foam has 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.- The thermoplastic polymer foam has thermal resistance meeting or exceeding the industry standard of R-5 per inch, or greater than R-4 per inch.

[0084] In some embodiments, the extruded thermoplastic polymer foam and blowing agent has a density no greater than about 65 kg / m3, no greater than about 40 kg / m3, no greater than about 35 kg / m3, or no greater than about 25 kg / m3.Density can be measured according to ISO method 845-85. In some embodiments, the minimum required strength (compressive) of the foamed product will dictate that the density be at least 16 kg / m3.EXAMPLESExample 1

[0085] Three foamable compositions with different blowing agents were extruded and analyzed for various properties. The compositions are described in Table 1 below.

[0086] For this example, a 50 mm twin screw laboratory extruder was used with 9 individually controlled, electrically heated zones. The first four zones of the extruder were used to heat and soften the polymer. The remaining zones, from the blowing agent injection location to the end of the extruder, were set at selected lowerTS0124-W001temperatures. A rod die with a 3 mm opening was used to extrude rod-shaped foam specimens. The polystyrene used in this example was styrene homopolymer having a melt flow index (MFI) of 4.0 g / 10 min. A nucleating agent (nucleator), namely talc, was mixed with the polystyrene in the molten composition formed within the extruder. Table 1 summarizes the extrusion conditions and key characteristics of the produced foam specimens. The blowing agents in Table 1 generate no persistent products (e.g., TFA) upon atmospheric decomposition.Table 1. Extrusion of polystyrene foam with blowing agents comprising HFO-1252zc: Operating conditions and foam quality characteristics (Total Blowing Agent: about 0.1 moles per 100 gr of polystyrene)> > >> > >(2)mhr: moles of blowing agent per 100 grams of polystyreneTS0124-W001

[0087] The foams prepared according to Table 1 meet key desirable attributes including: (1) no structural defects; (2) cell diameter from about 0.15 to 0.20 mm; (3) fraction of closed cells exceeding 90%; and (4) thermal resistance meeting or exceeding the industry standard of R-5. This example demonstrates that blowing agents with favorable environmental fate comprising HFO-1252zc, surprisingly, enable the production of thermoplastic foam meeting application requirements.

Claims

TS0124-W001CLAIMSWhat is claimed is:

1. A process for preparing a thermoplastic polymer foam, the process comprising:a. providing a foamable composition comprising a thermoplastic polymer and a blowing agent, wherein the blowing agent comprises HFO- 1252zc; andb. expanding the foamable composition to produce the thermoplastic polymer foam.

2. The process of claim 1 , wherein the thermoplastic polymer is selected from the group consisting of polystyrene, polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, acrylonitrile butadiene styrene, styrene acrylonitrile copolymer, and blends thereof.

3. The process of any of the preceding claims, wherein the thermoplastic polymer is selected from the group consisting of a polystyrene homopolymer, a polystyrene copolymer, styrene-acrylonitrile copolymer, and blends thereof.

4. The process of any of the preceding claims, wherein the foamable composition comprises from about 5 parts to about 25 parts per hundred parts of thermoplastic polymer by mass.

5. The process of any of the preceding claims, wherein the foamable composition comprises the blowing agent in an amount of about 0.01 to about 0.2 moles of blowing agent per 100 grams of the thermoplastic polymer resin (mhr).

6. The process of any of the preceding claims, wherein the foamable composition comprises the blowing agent in an amount of about 5 to about 20 wt% of the foamable composition.

7. The process of any of the preceding claims, wherein the blowing agent comprises HFO-1252zc in an amount of about 1 wt% to about 99 wt%; about 25 wt% to about 75 wt%; about 70 wt% to about 90 wt%; or about 73 wt% to about 87 wt% of the blowing agent.TS0124-W0018. The process of any of the preceding claims, wherein the blowing agent comprises HFC-134, ethanol, dimethyl-ether, methylal, methyl formate, trans- 1 ,2-dichloroethylene, chloropropane, normal pentane, cyclopentane, isopentane, neopentane, HFO-1243yc, CFO-1112, HFO-1234ze(E), HFO- 1234ze(Z), HFO-1336mzz(Z), HFO-1336mzz(E), HCFO-1233zd(E), HCFO- 1233zd(Z), or combinations thereof.

9. The process of any of the preceding claims, wherein the blowing agent comprises HFC-134 in an amount of about 10 wt% to about 30 wt%; or about 13 wt% to about 27 wt% of the blowing agent.

10. The process of any of the preceding claims, wherein the blowing agent comprises ethanol in an amount of about 25 wt% to about 75 wt% of the blowing agent.

11. The process of any of the preceding claims, wherein the blowing agent comprises dimethyl-ether in an amount of about 25 wt% to about 75 wt% of the blowing agent.

12. The process of any of the preceding claims, wherein the blowing agent comprises methylal in an amount of about 25 wt% to about 75 wt% of the blowing agent.

13. The process of any of the preceding claims, wherein the blowing agent comprises methyl formate in an amount of about 25 wt% to about 75 wt% of the blowing agent.

14. The process of any of the preceding claims, wherein the blowing agent comprises trans-1 ,2-dichloroethylene in an amount of about 25 wt% to about 75 wt% of the blowing agent.

15. The process of any of the preceding claims, wherein the blowing agent comprises chloropropane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

16. The process of any of the preceding claims, wherein the blowing agent comprises normal pentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W00117. The process of any of the preceding claims, wherein the blowing agent comprises cyclopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

18. The process of any of the preceding claims, wherein the blowing agent comprises isopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

19. The process of any of the preceding claims, wherein the blowing agent comprises neopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

20. The process of any of the preceding claims, wherein the blowing agent comprises HFO-1243yc in an amount of about 25 wt% to about 75 wt% of the blowing agent.

21. The process of any of the preceding claims, wherein the blowing agent comprises CFO-1112 in an amount of about 25 wt% to about 75 wt% of the blowing agent.

22. The process of any of the preceding claims, wherein the blowing agent comprises HFO-1234ze(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

23. The process of any of the preceding claims, wherein the blowing agent comprises HFO-1234ze(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

24. The process of any of the preceding claims, wherein the blowing agent comprises HFO-1336mzz(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

25. The process of any of the preceding claims, wherein the blowing agent comprises HCFO-1233zd(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

26. The process of any of the preceding claims, wherein the blowing agent comprises HCFO-1233zd(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W00127. The process of any of the preceding claims, wherein the blowing agent comprises an azeotropic or near-azeotropic composition of HFO-1252zc and one or more blend components.

28. A thermoplastic foam formed according to the process of any of the preceding claims.

29. A thermoplastic polymer foam comprising:a. a thermoplastic polymer; and,b. a blowing agent comprising HFO-1252zc.

30. The thermoplastic polymer foam of claim 29, wherein the thermoplastic polymer is selected from the group consisting of polystyrene, polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, acrylonitrile butadiene styrene, styrene acrylonitrile copolymer, and blends thereof.

31. The thermoplastic polymer foam of claim 29, wherein the thermoplastic polymer is selected from the group consisting of a polystyrene homopolymer, a polystyrene copolymer, styrene-acrylonitrile copolymer, and blends thereof.

32. The thermoplastic polymer foam of claims 29-31 , wherein the foam comprises from about 5 parts to about 25 parts per hundred parts of thermoplastic polymer by mass.

33. The thermoplastic polymer foam of claims 29-32, wherein the foam comprises the blowing agent in an amount of about 2 wt% to about 15 wt% of the total weight of the foam.

34. The thermoplastic polymer foam of claims 29-32, wherein the foam comprises the blowing agent in an amount of about 4.65 to about 17.15 phr.

35. The thermoplastic polymer foam of claims 29-34, wherein the blowing agent comprises HFO-1252zc in an amount of about 1 wt% to about 99 wt%; about 25 wt% to about 75 wt%; about 70 wt% to about 90 wt%; or about 73 wt% to about 87 wt% of the blowing agent.

36. The thermoplastic polymer foam of claims 29-35, wherein the blowing agent comprises HFC-134, ethanol, dimethyl-ether, methylal, methyl formate, trans-TS0124-W0011 ,2-dichloroethylene, chloropropane, normal pentane, cyclopentane, isopentane, neopentane, HFO-1243yc, CFO-1112, HFO-1234ze(E), HFO- 1234ze(Z), HFO-1336mzz(Z), HFO-1336mzz(E), HCFO-1233zd(E), HCFO- 1233zd(Z), or combinations thereof.

37. The thermoplastic polymer foam of claims 29-36, wherein the blowing agent comprises HFC-134 in an amount of about 10 wt% to about 30 wt%; or about 13 wt% to about 27 wt% of the blowing agent.

38. The thermoplastic polymer foam of claims 29-37, wherein the blowing agent comprises ethanol in an amount of about 25 wt% to about 75 wt% of the blowing agent.

39. The thermoplastic polymer foam of claims 29-38, wherein the blowing agent comprises dimethyl-ether in an amount of about 25 wt% to about 75 wt% of the blowing agent.

40. The thermoplastic polymer foam of claims 29-39, wherein the blowing agent comprises methylal in an amount of about 25 wt% to about 75 wt% of the blowing agent.

41. The thermoplastic polymer foam of claims 29-40, wherein the blowing agent comprises methyl formate in an amount of about 25 wt% to about 75 wt% of the blowing agent.

42. The thermoplastic polymer foam of claims 29-41 , wherein the blowing agent comprises trans-1 ,2-dichloroethylene in an amount of about 25 wt% to about 75 wt% of the blowing agent.

43. The thermoplastic polymer foam of claims 29-42, wherein the blowing agent comprises chloropropane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

44. The thermoplastic polymer foam of claims 29-43, wherein the blowing agent comprises normal pentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W00145. The thermoplastic polymer foam of claims 29-44, wherein the blowing agent comprises cyclopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

46. The thermoplastic polymer foam of claims 29-45, wherein the blowing agent comprises isopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

47. The thermoplastic polymer foam of claims 29-46, wherein the blowing agent comprises neopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

48. The thermoplastic polymer foam of claims 29-47, wherein the blowing agent comprises HFO-1243yc in an amount of about 25 wt% to about 75 wt% of the blowing agent.

49. The thermoplastic polymer foam of claims 29-48, wherein the blowing agent comprises CFO-1112 in an amount of about 25 wt% to about 75 wt% of the blowing agent.

50. The thermoplastic polymer foam of claims 29-49, wherein the blowing agent comprises HFO-1234ze(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

51. The thermoplastic polymer foam of claims 29-50, wherein the blowing agent comprises HFO-1234ze(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

52. The thermoplastic polymer foam of claims 29-51 , wherein the blowing agent comprises HFO-1336mzz(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

53. The thermoplastic polymer foam of claims 29-52, wherein the blowing agent comprises HCFO-1233zd(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

54. The thermoplastic polymer foam of claims 29-53, wherein the blowing agent comprises HCFO-1233zd(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W00155. The thermoplastic polymer foam of claims 29-54, wherein the blowing agent comprises an azeotropic or near-azeotropic composition of HFO-1252zc and one or more blend components.

56. The thermoplastic polymer foam of claims 29-55, wherein the foam comprises a thermal resistance meeting or exceeding the industry standard of R-5.

57. The thermoplastic polymer foam of claims 29-56, wherein the foam comprises a GWP100 value of less than about 300.

58. The thermoplastic polymer foam of claims 29-57, wherein the foam comprises a GWP100 value of less than about 50.

59. The thermoplastic polymer foam of claims 29-58, wherein the foam comprises no more than de minimis ODP.

60. The thermoplastic polymer foam of claims 29-59, wherein the foam has at least 80% closed cells as measured according to ASTM method D6226-05.

61. The thermoplastic polymer foam of claims 29-60, wherein the foam has at least 90% closed cells as measured according to ASTM method D6226-05.

62. The thermoplastic polymer foam of claims 29-61 , wherein the foam is essentially free of structural defects63. A foamable composition comprising:a. a thermoplastic polymer; and,b. a blowing agent comprising HFO-1252zc.

64. The foamable composition of claim 63, wherein the thermoplastic polymer is selected from the group consisting of polystyrene, polyethylene, polyethylene copolymer, polypropylene, polypropylene copolymer, acrylonitrile butadiene styrene, styrene acrylonitrile copolymer, and blends thereof.

65. The foamable composition of claim 63, wherein the thermoplastic polymer is selected from the group consisting of a polystyrene homopolymer, a polystyrene copolymer, styrene-acrylonitrile copolymer, and blends thereof.

66. The foamable composition of claims 63-65, comprising from about 5 parts to about 25 parts per hundred parts of thermoplastic polymer by mass.TS0124-W00167. The foamable composition of claims 63-66, comprising the blowing agent in an amount of about 0.01 to about 0.2 moles of blowing agent per 100 grams of the thermoplastic polymer resin (mhr).

68. The foamable composition of claims 63-67, comprising the blowing agent in an amount of about 5 to about 20 wt% of the foamable composition.

69. The foamable composition of claims 63-68, wherein the blowing agent comprises HFO-1252zc in an amount of about 1 wt% to about 99 wt%; about 25 wt% to about 75 wt%; about 70 wt% to about 90 wt%; or about 73 wt% to about 87 wt% of the blowing agent.

70. The foamable composition of claims 63-69, wherein the blowing agent comprises HFC-134, ethanol, dimethyl-ether, methylal, methyl formate, trans- 1 ,2-dichloroethylene, chloropropane, normal pentane, cyclopentane, isopentane, neopentane, HFO-1243yc, CFO-1112, HFO-1234ze(E), HFO- 1234ze(Z), HFO-1336mzz(Z), HFO-1336mzz(E), HCFO-1233zd(E), HCFO- 1233zd(Z), or combinations thereof.

71. The foamable composition of claims 63-70, wherein the blowing agent comprises HFC-134 in an amount of about 10 wt% to about 30 wt%; or about 13 wt% to about 27 wt% of the blowing agent.

72. The foamable composition of claims 63-71 , wherein the blowing agent comprises ethanol in an amount of about 25 wt% to about 75 wt% of the blowing agent.

73. The foamable composition of claims 63-72, wherein the blowing agent comprises dimethyl-ether in an amount of about 25 wt% to about 75 wt% of the blowing agent.

74. The foamable composition of claims 63-73, wherein the blowing agent comprises methylal in an amount of about 25 wt% to about 75 wt% of the blowing agent.

75. The foamable composition of claims 63-74, wherein the blowing agent comprises methyl formate in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W00176. The foamable composition of claims 63-75, wherein the blowing agent comprises trans-1 ,2-dichloroethylene in an amount of about 25 wt% to about 75 wt% of the blowing agent.

77. The foamable composition of claims 63-76, wherein the blowing agent comprises chloropropane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

78. The foamable composition of claims 63-77, wherein the blowing agent comprises normal pentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

79. The foamable composition of claims 63-78, wherein the blowing agent comprises cyclopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

80. The foamable composition of claims 63-79, wherein the blowing agent comprises isopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

81. The foamable composition of claims 63-80, wherein the blowing agent comprises neopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

82. The foamable composition of claims 63-81 , wherein the blowing agent comprises HFO-1243yc in an amount of about 25 wt% to about 75 wt% of the blowing agent.

83. The foamable composition of claims 63-82, wherein the blowing agent comprises CFO-1112 in an amount of about 25 wt% to about 75 wt% of the blowing agent.

84. The foamable composition of claims 63-83, wherein the blowing agent comprises HFO-1234ze(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

85. The foamable composition of claims 63-84, wherein the blowing agent comprises HFO-1234ze(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W00186. The foamable composition of claims 63-85, wherein the blowing agent comprises HFO-1336mzz(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

87. The foamable composition of claims 63-86, wherein the blowing agent comprises HCFO-1233zd(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

88. The foamable composition of claims 63-87, wherein the blowing agent comprises HCFO-1233zd(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

89. The foamable composition of claims 63-88, wherein the blowing agent comprises an azeotropic or near-azeotropic composition of HFO-1252zc and one or more blend components.

90. A blowing agent comprising HFO-1252zc.

91. The blowing agent of claim 90, comprising HFO-1252zc in an amount of about 1 wt% to about 99 wt%; about 25 wt% to about 75 wt%; about 70 wt% to about 90 wt%; or about 73 wt% to about 87 wt% of the blowing agent.

92. The blowing agent of claims 90-91 , comprising HFC-134, ethanol, dimethylether, methylal, methyl formate, trans-1 ,2-dichloroethylene, chloropropane, normal pentane, cyclopentane, isopentane, neopentane, HFO-1243yc, CFO- 1112, HFO-1234ze(E), HFO-1234ze(Z), HFO-1336mzz(Z), HFO-1336mzz(E), HCFO-1233zd(E), HCFO-1233zd(Z), or combinations thereof.

93. The blowing agent of claims 90-92, comprising HFC-134 in an amount of about 10 wt% to about 30 wt%; or about 13 wt% to about 27 wt% of the blowing agent.

94. The blowing agent of claims 90-93, comprising ethanol in an amount of about 25 wt% to about 75 wt% of the blowing agent.

95. The blowing agent of claims 90-94, comprising dimethyl-ether in an amount of about 25 wt% to about 75 wt% of the blowing agent.

96. The blowing agent of claims 90-95, comprising methylal in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W00197. The blowing agent of claims 90-96, comprising methyl formate in an amount of about 25 wt% to about 75 wt% of the blowing agent.

98. The blowing agent of claims 90-97, comprising trans-1 ,2-dichloroethylene in an amount of about 25 wt% to about 75 wt% of the blowing agent.

99. The blowing agent of claims 90-98, comprising chloropropane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

100. The blowing agent of claims 90-99, comprising normal pentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

101. The blowing agent of claims 90-100, comprising cyclopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

102. The blowing agent of claims 90-101, comprising isopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

103. The blowing agent of claims 90-102, comprising neopentane in an amount of about 25 wt% to about 75 wt% of the blowing agent.

104. The blowing agent of claims 90-103, comprising HFO-1243yc in an amount of about 25 wt% to about 75 wt% of the blowing agent.

105. The blowing agent of claims 90-104, comprising CFO-1112 in an amount of about 25 wt% to about 75 wt% of the blowing agent.

106. The blowing agent of claims 90-105, comprising HFO-1234ze(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

107. The blowing agent of claims 90-106, comprising HFO-1234ze(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

108. The blowing agent of claims 90-107, comprising HFO-1336mzz(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

109. The blowing agent of claims 90-108, comprising HCFO-1233zd(E) in an amount of about 25 wt% to about 75 wt% of the blowing agent.

110. The blowing agent of claims 90-109, comprising HCFO-1233zd(Z) in an amount of about 25 wt% to about 75 wt% of the blowing agent.TS0124-W001111. The blowing agent of claims 90-110, comprising an azeotropic or near- azeotropic composition of HFO-1252zc and one or more blend components.

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