Blowing agents containing Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z))

Abstract

The present disclosure provides a blowing agent for polyurethane and polyisocyanurate foams comprising Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane in amounts of 65% to 99% by weight and 1% to 35% by weight, respectively. The present disclosure further provides a polyurethane or polyisocyanurate foam and a foam formed from the blowing agent comprising Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane having a low initial lambda value.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 167950, filed March 30, 2021, which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION The present disclosure relates to mixtures comprising Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane. The present disclosure also provides blowing agent mixtures comprising Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane, methods for foaming using these compositions, and blowing agents comprising these compositions. [Background technology]

[0003] Fluorocarbon-based fluids find widespread use in industry in many applications including as refrigerants, aerosol propellants, foam blowing agents, heat transfer media, gaseous dielectrics, and flame suppressants.

[0004] The industry is constantly seeking new fluorocarbon-based mixtures that offer alternatives and are considered to be environmentally safer replacements for the CFCs, HCFCs, and HFCs in use today. Of particular interest are mixtures containing hydrofluorocarbons, fluoroolefins, iodide-containing compounds, and other fluorinated compounds that have low ozone depletion potential and low global warming potential. Such mixtures are the subject of the present disclosure. Summary of the Invention

[0005] The present disclosure provides a foamable composition comprising a foam-forming agent and a blowing agent composition comprising a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane. The blowing agent composition may comprise cyclopentane in an amount of about 1% to about 35% by weight and Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) in an amount of about 65% to about 99% by weight, based on the total weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane. The foamable composition may comprise at least one of polyurethane foam and isocyanurate foam.

[0006] The present disclosure further provides a foam formed using a blowing agent composition comprising a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane in amounts of 1% to 35% by weight of cyclopentane and 65% to 99% by weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)), based on the total weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane. The initial lambda value of the foam may be 20.5 mW / mK or less. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a graph of initial lambda versus mole percentage of cyclopentane in polyurethane foams described in Example 1. [Figure 2] 1 is a graph of initial lambda versus mole percentage of cyclopentane in polyisocyanurate foams described in Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure provides mixtures comprising Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane, which are described in further detail below. The present disclosure also provides compositions, particularly blowing agents, foamable compositions, foam articles, and methods and systems for forming foams, that utilize mixtures of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane.

[0009] Surprisingly, it has been found that foams formed using a blowing agent comprising a combination of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane exhibit low initial lambda values ​​when the cyclopentane is added in an amount of from about 1 wt % to about 35 wt %, based on the total weight of the Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane.

[0010] The amount of cyclopentane can also be expressed as a mole percentage. Specifically, foams formed using a blowing agent comprising a combination of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane exhibit low initial lambda values ​​when the cyclopentane is added in an amount of about 1 mole % to about 50 mole %, based on the number of moles of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane.

[0011] Because the use of hydrocarbons in blowing agent compositions typically adversely affects the initial lambda value in the resulting foam, one skilled in the art would expect that the addition of cyclopentane to a blowing agent composition containing Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) would immediately increase the initial lambda value of the resulting foam in proportion to the amount of cyclopentane added to the blowing agent composition. However, it has surprisingly been found that the initial lambda values ​​of foams formed using Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) as the blowing agent remain substantially unchanged when cyclopentane is added to Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) in an amount of up to about 35 wt %, based on the combined weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane.

[0012] This presents an important commercial advantage in that Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) is relatively expensive compared to cyclopentane, and therefore, foams using a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane as the blowing agent may have desirable initial lambda values, but may be relatively less expensive to produce than foams made using only Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) as the blowing agent.

[0013] I. Blowing agent comprising a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane Fluorocarbon fluids have desirable properties for use in a variety of applications, including as blowing agents and other uses. Unfortunately, the use of certain hydrofluorocarbons (HFCs) in industrial applications is now believed to contribute to global warming, and therefore their use is currently restricted. However, the identification of new, environmentally safe HFC-containing compositions is complicated by the fact that many of the properties that make them useful in these applications are not easily predictable. For example, it is desirable for blowing agent compositions to not only have acceptable environmental properties, but also to be chemically stable, low or non-toxic, and low or non-flammable, among other things. It is also desirable for blowing agents to have excellent performance during use, such as excellent thermal insulation properties and other desirable blowing properties.

[0014] Methods and compositions for producing conventional foam materials, such as thermoplastic and thermosetting materials, have long been known. These methods and compositions typically utilize chemical and / or physical blowing agents to form a foam structure in a polymer matrix. Such blowing agents include, for example, azo compounds, various volatile organic compounds (VOCs), and chlorofluorocarbons (CFCs). Chemical blowing agents typically undergo some form of chemical change, including a chemical reaction with the materials forming the polymer matrix (usually at a given temperature / pressure), which causes the release of gases such as nitrogen, carbon dioxide, or carbon monoxide. One of the most frequently used chemical blowing agents is water. Physical blowing agents are typically dissolved in a polymer or polymer precursor material and then undergo volumetric expansion (again, at a given temperature / pressure) to contribute to the formation of a foam structure. While physical blowing agents are often used in conjunction with thermoplastic foams, chemical blowing agents can be used instead of or in addition to physical blowing agents associated with thermoplastic foams. It is common to use chemical and / or physical blowing agents in conjunction with thermosetting foams. It will be appreciated that certain compounds and compositions containing them may constitute both chemical and physical blowing agents.

[0015] The blowing agent of the present disclosure may comprise a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane. The cyclopentane may be present in the mixture in an amount of about 1% by weight or more, about 5% by weight or more, about 10% by weight or more, about 15% by weight or more, about 20% by weight or less, about 25% by weight or less, about 30% by weight or less, about 35% by weight or less, or any value encompassed by these endpoints, based on the combined weight of the Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane. Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) can be present in the mixture in an amount of about 65% by weight or more, about 70% by weight or more, about 75% by weight or more, about 80% by weight or more, about 85% by weight or less, about 90% by weight or less, about 95% by weight or less, about 99% by weight or less, or any value encompassed by these endpoints, based on the combined weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane.

[0016] When the blowing agent includes only Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane, the above percentages are based on the total weight of the blowing agent composition.

[0017] Alternatively, the blowing agent can consist essentially of a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane. Alternatively, the blowing agent can consist of a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane.

[0018] When used as a blowing agent, a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane is often used in the production of, for example, 1,1-difluoroethane (HFC-152a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2,-tetrafluoroethane (HFC-134b), 1,1,2,2,3-tetrafluoroethane (HFC-134c), 1,1,2,2,3-tetrafluoroethane (HFC-134d ... Fluoroethane (HFC-134), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), propane, butane, pentane, hexane, E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-133 6mzz(E)), Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(Z)), E-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), Z-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(Z)), E-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd( E)), 1,1-dichloro-2,3,3,3-tetrafluoropropene (HFO-1214ya), trans-dichloroethylene (trans-DCE), methyl formate, methylal, formic acid, acetic acid, C1-C4 aldehydes, C3-C4 ketones, C2-C4 ethers, diethers, water, and combinations thereof.

[0019] If water is added, it is typically present in an amount less than 5% by weight, for example, 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, or 1% by weight or less.

[0020] II. Foamable compositions containing a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane The present disclosure provides a foamable composition comprising a blowing agent composition, such as those described above, and one or more components capable of forming a foam. In particular, the mixture is well suited for polyurethane and polyisocyanurate foam compositions. In principle, the mixture is added to a foamable composition, which may contain other components necessary to react under specific reaction conditions to produce a foam.

[0021] As used herein, the term "foam former" is used to refer to a component or combination of components capable of forming a foam structure, preferably a generally cellular foam structure, without additives such as, for example, flame retardants, surfactants, crosslinkers, defoamers, solubility promoters, fillers, dispersants, antimicrobial agents, viscosity reduction modifiers, vapor pressure modifiers, colorants, and dyes.

[0022] The one or more components capable of forming a foam may be a composition capable of forming a thermoset foam. Examples of thermoset foams may include polyurethane and polyisocyanurate foams.

[0023] The present disclosure also relates to closed-cell foams containing the blowing agent compositions of the present disclosure. The foams may be rigid, flexible, or integral-skin foams. Preferably, the present disclosure relates to closed-cell rigid foams containing the blowing agent composition containing the mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane.

[0024] The foams provided by the present disclosure may be blocks, slabs, laminates, panels such as pour-in-place foam panels, spray-applied foams and floss, etc. The foams described in the present disclosure, particularly the thermoset foams disclosed herein, may be used in a wide variety of applications, and in certain preferred embodiments, the present disclosure includes appliance foams according to the present disclosure, including appliance foams such as refrigerator foams, freezer foams, refrigerator / freezer foams, panel foams; and other low-temperature or cryogenic manufacturing applications.

[0025] The foams of the present disclosure are provided for use in the appliance, refrigeration, transportation, and construction industries (e.g., building envelopes), among others. The foams described herein offer one or more exceptional features, characteristics, and / or properties, including, among others, thermal insulation efficiency (especially in the case of thermoset foams), dimensional stability, compressive strength, thermal insulation property aging, and flame retardancy, in addition to the low global warming potential, all of which are associated with the blowing agents of the present disclosure.

[0026] The foam may be a thermoset foam or a thermoplastic foam. The thermoplastic foam may be polyethylene (PE), polypropylene (PP), polystyrene (PS), or polyethyleneterepthalate (PET). The thermoset foam may be a polyisocyanurate (PIR) or polyurethane (PU) foam.

[0027] The blowing agents of the present disclosure may be present in the foamable composition in an amount, as a percentage of the total weight of the foamable composition, of about 2% by weight or more, about 3% by weight or more, about 4% by weight or more, about 5% by weight or more, about 6% by weight or more, about 7% by weight or more, about 8% by weight or less, about 9% by weight or less, about 10% by weight or less, about 11% by weight or less, about 12% by weight or less, about 13% by weight or less, about 14% by weight or less, about 15% by weight or less, or any range inclusive of these endpoints. The total weight of the foamable composition includes all components of the thermoplastic foam and the thermoset foam.

[0028] III. Methods for Forming Foams It is contemplated that all currently known and available methods and systems for forming foams can be easily adapted for use in connection with the compositions of the present disclosure. For example, the methods of the present disclosure generally incorporate a blowing agent into a foamable composition, and then foam the composition by a step or series of steps that preferably cause the volume expansion of the blowing agent as described herein. In general, it is contemplated that systems and devices currently used for incorporating and forming a blowing agent can easily be used in accordance with the compositions of the present disclosure. Indeed, it is believed that one advantage of the present disclosure is to provide an improved blowing agent that is generally compatible with existing foaming methods and systems.

[0029] It will therefore be understood that the present disclosure includes methods and systems for forming all types of foams, including thermoset and thermoplastic foams. Accordingly, the present disclosure relates to the use of the blowing agents of the present invention in conjunction with conventional foaming equipment under conventional processing conditions. The present methods therefore include masterbatch-type operations, blend-type operations, third blowing agent addition, and blowing agent addition at the mixhead.

[0030] For thermoplastic foams, the preferred method generally involves introducing a blowing agent into a thermoplastic material, preferably a thermoplastic polymer, and then subjecting the thermoplastic material to conditions effective to cause foaming.

[0031] For example, the step of introducing a blowing agent to the thermoplastic material may include introducing the blowing agent into an extruder (e.g., a screw extruder) containing the thermoplastic material, and the step of foaming may include reducing pressure on the thermoplastic material, thereby causing the blowing agent to expand and contribute to foaming the material.

[0032]

[0013] With particular consideration given to the disclosure contained herein, it will be understood that the order and manner in which the blowing agents of the present disclosure are formed and / or added to the foamable composition generally does not affect the operability of the present invention. For example, in the case of extrudable foams, the various components of the blowing agent, as well as the components of the foamable composition, need not be mixed prior to introduction into the extrusion equipment, or even the components need not be added to the same location in the extrusion equipment. Moreover, the blowing agent can be introduced either directly or as part of a premix, which is then further added to other portions of the foamable composition.

[0033] It may therefore be desirable to introduce one or more components of the blowing agent into the extruder at a first location upstream from the addition point of one or more other components of the blowing agent, in the hope that by this means the components will come together and / or work more efficiently in the extruder. Nevertheless, it may be preferable to pre-combine two or more components of the blowing agent and introduce them together into the foamable composition, either directly or as part of a premix, before further adding them to other portions of the foamable composition.

[0034] The present disclosure also relates to methods for forming thermoset foams, such as polyurethane (PU) or polyisocyanurate (PIR). The methods generally include providing a blowing agent composition of the present disclosure, adding (directly or indirectly) a blowing agent composition to the foamable composition, and reacting the foamable composition under 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, can be used in accordance with the present disclosure, which is incorporated herein by reference. Generally, such preferred methods include preparing a thermoset (e.g., polyurethane or polyisocyanurate foam) by combining an isocyanate, a polyol or mixture of polyols, the blowing agent composition of the present disclosure, and, optionally, other materials such as a catalyst, surfactant, flame retardant, colorant, or other additives.

[0035] It is convenient to provide the components for polyurethane or polyisocyanurate foams in a preblended formulation. Most typically, the preblended formulation is preblended into two components. The isocyanate and, optionally, certain surfactants comprise the first component, commonly referred to as the "A" component. The polyol or polyol mixture, surfactant, catalyst, and flame retardant comprise the second component, commonly referred to as the "B" component. The blowing agent composition can be present in the A component and / or the B component. For example, if the blowing agent composition includes two blowing agents, the first blowing agent can be present in the A component and the second blowing agent can be present in the B component.

[0036] The mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane may be present in the polyol preblend mixture (B component) in an amount, as a percentage of the total polyol preblend resin (B component), of about 10% by weight or more, about 15% by weight or more, about 20% by weight or less, about 25% by weight or less, about 30% by weight or less, or any value encompassed by these endpoints.

[0037] The polyol preblend mixture of the present disclosure may contain additional components. Such optional additional compounds may include any other blowing agent, for example, 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-trifluoropropene (HFO-1233zd(E), 1,1-dichloro-2,3,3,3-tetrafluoropropene (HFO-1214ya), E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,1-dichloro-2,2-difluoroethylene (HFO-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 and / or inorganic flame retardants; surfactants (silicone or non-silicone); crosslinking agents; antifoaming agents; solubility enhancers; fillers; dispersants; antimicrobial agents; viscosity reducing modifiers; vapor pressure modifiers; colorants; and pigments.

[0038] Suitable polyols can include, for example, sucrose-containing polyols; phenol, phenol formaldehyde-containing polyols; glucose-containing polyols; sorbitol-containing polyols; methyl glucoside-containing polyols; aromatic amine-containing polyols, such as ortho-toluene diamine (o-TDA)-containing polyols; aromatic polyester polyols; glycerol; ethylene glycol; diethylene glycol; propylene glycol; one or more of (a) condensed with one or more of (b), where (a) is selected from glycerin, ethylene glycol, diethylene glycol, trimethylolpropane, ethylenediamine, pentaerythritol, soybean oil, lecithin, tall oil, palm oil, and castor oil, and (b) is selected from ethylene oxide, propylene oxide, mixtures of ethylene oxide and propylene oxide, and combinations thereof.

[0039] Suitable catalysts may include amine catalysts and / or metal catalysts. Amine catalysts may include, but are not limited to, primary amines, secondary amines, or tertiary amines. Useful tertiary amine catalysts include, but are not limited to, N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine, dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethylethanolamine, N,N,N'-trimethyl-N'-hydroxyethyl bisaminoethyl ether, 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-dimethylpropanediamine, 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-dimethylaminopropylurea, dicyclohexylmethylamine; ethyldiisopropylamine; dimethylisopropylamine; methylisopropylbenzylamine; methylcyclopentylbenzylamine; isopropyl-sec-butyl-trifluoroethylamine; diethyl-(α-phenylethyl)amine, tri-n-propylamine, or a combination thereof.Useful secondary amine catalysts may non-exclusively include, for example, dicyclohexylamine; tert-butylisopropylamine; di-tert-butylamine; cyclohexyl-tert-butylamine; di-sec-butylamine, dicyclopentylamine; di-(α-trifluoromethylethyl)amine; di-(α-phenylethyl)amine; or combinations thereof.

[0040] Examples of metal catalysts include potassium catalysts such as potassium octanoate (Dabco K15) and potassium acetate (Polycat 46); tin catalysts such as dibutyltin dilauryl mercaptide (Dabco T120, Fomrez UL-1), dibutyltin diisooctyl maleate (Dabco T125), dimethyltin dilauryl mercaptide (Fomrez UL-22), dioctyltin dilauryl mercaptide (Fomrez UL-32), and dibutyltin di-(2-ethylhexylthioglycolate) (Fomrez UL-6); and bismuth carboxylates such as Bicat 8108 and Bicat 8210.

[0041] Suitable isocyanates include any organic polyisocyanurate that can be used in polyurethane or polyisocyanurate foam synthesis, including aliphatic and aromatic polyisocyanurates. Suitable organic polyisocyanurates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates that are well known in the field of polyurethane chemistry. These are described, for example, in U.S. Patent Nos. 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.

[0042] Certain surfactants are added to function as foam stabilizers. Some representative materials are sold under the names DC-193, B-8404, and L-5340. These are generally polysiloxane polyoxyalkylene block copolymers such as those disclosed in U.S. Pat. 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 preblend 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 polyphosphates, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, etc.

[0043] Polyurethane or polyisocyanurate foams are readily prepared by mixing the A and B side components together to form foams such as blocks, slabs, laminates, pour-in-place foam panels and other articles, spray-applied foams and froths, etc. Mixing can be by hand mixing, for example for small scale preparations, or by mechanical mixing techniques.

[0044] The methods and systems of the present invention also include forming one-component thermoset foams, preferably polyurethane foams, containing the blowing agent of the present disclosure. A portion of the blowing agent may be contained in the foam-forming agent of the one-component foam by dissolving it in the foam-forming agent, which is preferably liquid at the pressure within the container, and a second portion of the blowing agent may exist as a separate gas phase. In such systems, the contained / dissolved blowing agent largely causes the expansion of the foam, and the separate gas phase acts to impart a driving force to the foam-forming agent. Such one-component systems are typically packaged in a container, such as an aerosol-type can, and thus the blowing agent of the present disclosure preferably provides the energy for expanding the foam and / or transporting the foam / foamable material from the package, and preferably both. Such systems and methods may include filling the package with a fully formulated system (preferably an isocyanate / polyol system) and introducing the gaseous blowing agent of the present invention into the package, preferably an aerosol-type can.

[0045] IV. Foam As described above, it has been surprisingly discovered that foams formed using a blowing agent comprising Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane exhibit low lambda values. Specifically, when cyclopentane is present in an amount up to 35 wt. % relative to Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)), the initial lambda does not increase significantly, as shown in FIG. 1 . Given the high initial lambda values ​​of hydrocarbons in general, and cyclopentane in particular, one would expect the initial lambda value of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) to increase immediately upon the addition of cyclopentane. However, as disclosed herein, the initial lambda value remains essentially unchanged even with the addition of up to about 33 wt. % cyclopentane.

[0046] When the mixtures of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane disclosed herein are used as blowing agents in polyurethane or polyisocyanurate foams, the initial lambda (at an average temperature of 10° C.) can be 19 mW / mK or greater, 19.2 mW / mK or greater, 19.4 mW / mK or greater, 19.6 mW / mK or greater, 19.8 mW / mK or less, 20.0 mW / mK or less, 20.2 mW / mK or less, 20.4 mW / mK or less, 20.5 mW / mK or less, or any value encompassed by these values.

[0047] The foams of the present disclosure may be in the form of, for example, blocks, slabs, or laminates. The foams of the present disclosure may be used as appliance foams, for example, in refrigerators, freezers, coolers, refrigerated trucks, rail cars, and water heaters. The foams of the present disclosure may be used in foam-core metal panels. These foam-core metal panels can be manufactured by either continuous or discontinuous manufacturing methods, and both such methods are suitable for use within the scope of the present disclosure. In the construction industry, such articles in the form of rigid panels may be used as insulation in the building envelope of commercial structures.

[0048] Any of the methods known in the art can be used or adapted in accordance with the foam-forming embodiments of the present disclosure, 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 are incorporated herein by reference.

[0049] The following non-limiting examples serve to illustrate the present disclosure. [Example]

[0050] All foams (polyisocyanurate (PIR) and polyurethane (PU)) were formulated using the following starting materials: Stepanpol PS 2352 available from Stepan (polyester polyol, hydroxy number: 240 mg KOH / g, functionality: 2); Voranol 490 available from Dow (sucrose / glycerin initiated polyether polyol, hydroxy number: 490 mg KOH / g, functionality: 4.3); Voranol 391 available from Dow (amine (ortho-diaminotoluene) initiated polyol, hydroxy number: 395 mg KOH / g, functionality: 4); Voranol 270 available from Dow (glycerin initiated polyether polyol, hydroxy number: 238 mg KOH / g, functionality: 3); Terate HT5510 ("HT5510") available from Invista (aromatic polyester polyol, hydroxy number: 260 mg KOH / g, functionality: 2); Tegostab B84210 ("B84210") (a silicone surfactant from Evonik); Tegostab B8465 ("B8465") (a silicone surfactant from Evonik); Dabco K15 ("K15") (potassium octanoate in diethylene glycol from Evonik); Polycat 8 (N,N-dimethylcyclohexylamine from Evonik); Polycat 5 (pentamethyldiethylenetriamine from Evonik); Polycat 41 (1,3,5-tris[3-(dimethylamino)propyl]hexahydro-1,3,5-triazine from Evonik); Lupranate M20 (polymeric isocyanate, 31.5% NCO, functionality: 2.7) available from BASF; TCPP (tris(1-chloro-2-propyl)phosphate) phosphorus content: 9.4% by weight; chlorine content: 33% by weight.

[0051] The foams were formulated by hand mixing based on the formulations set forth in the examples below. Lambda values ​​were recorded using a LaserComp FOX50 on a sample size of 12" x 12" x 1".

[0052] Example 1: Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane in polyurethane foam Various mixtures of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane were used as blowing agents in polyurethane foams and tested for their initial lambda values. The compositions of the different foams are shown in Table 1 below, with each component listed as parts per 100 parts polyol (php).

[0053] [Table 1]

[0054] Each of the formed foams was then tested for initial lambda using the method described in ASTM C518. Initial lambda values ​​were approximately 19.5 mW / mK or less when a mixture of 1 wt% to 35 wt% cyclopentane and 65 wt% to 99 wt% Z-1-chloro-2,3,3,3-tetrafluoropene (HCFO-1224yd(Z)) was used as the blowing agent, and began to rise as more cyclopentane was added. These results are shown in graphical form in Figure 1.

[0055] Example 2: Z-1-chloro-2,3,3,3-tetrafluoropene (HCFO-1224yd(Z)) and cyclopentane in polyisocyanurate foam Various mixtures of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane were used as blowing agents in polyisocyanurate foams and tested for their initial lambda values. The compositions of the different foams are shown in Table 2 below. All values ​​are given in parts per hundred parts polyol (php).

[0056] [Table 2]

[0057] The initial lambda of each of the foams formed was then tested. The initial lambda values ​​were approximately 20.5 mW / mK or less when a mixture of 1 wt% to 24 wt% cyclopentane and 76 wt% to 99 wt% Z-1-chloro-2,3,3,3-tetrafluoropene (HCFO-1224yd(Z)) was used as the blowing agent, and began to rise as more cyclopentane was added. These results are shown in graphical form in Figure 2.

[0058] Aspects Aspect 1 is a foamable composition comprising: a foam-forming agent; and a blowing agent composition comprising a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane in amounts of 1% to 35% by weight of cyclopentane and 65% to 99% by weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)), based on the total weight of the Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane.

[0059] Aspect 2 is the foamable composition of aspect 1, wherein the foam-forming agent comprises at least one of a polyurethane foam and a polyisocyanurate foam.

[0060] Aspect 3 is the foamable composition of either Aspect 1 or Aspect 2, further comprising at least one surfactant.

[0061] Aspect 4 is the foamable composition of any one of Aspects 1-3, further comprising at least one catalyst.

[0062] Aspect 5 is the foamable composition of any one of Aspects 1-4, further comprising at least one flammability suppressant.

[0063] Aspect 6 is the foamable composition of any one of Aspects 1-5, further comprising at least one adjuvant selected from the group consisting of polymer modifiers, toughening agents, colorants, pigments, solubility enhancers, rheology modifiers, plasticizers, antimicrobial agents, viscosity reduction modifiers, fillers, vapor pressure modifiers, and combinations of any two or more thereof.

[0064] Aspect 7 is a foam formed from a foam-forming agent and a blowing agent composition comprising a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane in amounts of 1% to 35% by weight cyclopentane and 65% to 99% by weight Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)), based on the combined weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane.

[0065] Example 8 is the foam of Example 7, wherein the foam-forming agent comprises polyurethane foam or polyisocyanurate foam.

[0066] Aspect 9 is the foam of aspect 7 or 8, wherein the foam has an initial lambda value of 20.5 mW / mK or less.

[0067] A tenth embodiment is a block comprising the foam of any one of the seventh to ninth embodiments.

[0068] Embodiment 11 is a slab comprising the foam of any one of embodiments 7-9.

[0069] A twelfth embodiment is a laminate comprising the foam of any one of the seventh to ninth embodiments.

[0070] A thirteenth aspect is the foam of any one of the seventh to ninth aspects, which is in the form of a foam for home appliances.

[0071] As used herein, the phrase "within any range defined between any two of the preceding values" means that any range may be selected from any two of the values ​​listed before such phrase, regardless of whether those values ​​are in the lower portion of the list or the upper portion of the list. For example, a pair of values ​​may be selected from two lower values, two higher values, or a lower value and an upper value.

[0072] As used herein, the singular forms "a," "an," and "the" include the plural unless the context clearly dictates otherwise. Furthermore, when an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed from any pairing of any upper range or upper preferred value with any lower range or lower preferred value, regardless of whether the ranges are separately disclosed. When a range of numerical values ​​is recited herein, unless otherwise specified, the range is intended to include its endpoints, and all integers and fractions within the range. The scope of the present disclosure is not intended to be limited to the specific values ​​recited when defining a range.

[0073] As used herein, the phrase "within any range defined between any two of the preceding values" means that any range may be selected from any two of the values ​​listed before such phrase, regardless of whether those values ​​are in the lower portion of the list or the upper portion of the list. For example, a pair of values ​​may be selected from two lower values, two higher values, or a lower value and an upper value.

[0074] It should be understood that the foregoing description is merely illustrative of the present disclosure. Various alternatives and modifications may be devised by those skilled in the art without departing from the present disclosure. Accordingly, the present disclosure is intended to embrace all such alternatives, modifications, and variations that fall within the scope of the appended claims. The present invention includes the following aspects. [1] 1. A foamable composition comprising: a foam former; and 1. A blowing agent composition comprising: and a blowing agent composition comprising a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane in amounts of 1% by weight to 35% by weight of cyclopentane and 65% by weight to 99% by weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)), based on the total weight of the Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane. [2] 10. The foamable composition of claim 1, wherein the foam former comprises at least one of polyurethane foam and polyisocyanurate foam. [3] 3. The foamable composition of any one of 1 or 2, further comprising at least one surfactant. [4] 4. The foamable composition according to any one of 1 to 3, further comprising at least one catalyst. [5] 5. The foamable composition of any one of claims 1 to 4, further comprising at least one flammability suppressant. [6] 6. The foamable composition of any one of claims 1 to 5, further comprising at least one adjuvant selected from the group consisting of polymer modifiers, toughening agents, colorants, pigments, solubility enhancers, rheology modifiers, plasticizers, antimicrobial agents, viscosity reduction modifiers, fillers, vapor pressure modifiers, and combinations of any two or more thereof. [7] A foam, a foam former, and 1. A blowing agent composition comprising: A foam formed from a blowing agent composition comprising a mixture of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane in amounts of 1% to 35% by weight of cyclopentane and 65% to 99% by weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)), based on the total weight of the Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane. [8] 8. The foam of claim 7, wherein the foam former comprises polyurethane foam or polyisocyanurate foam. [9] 9. The foam of claim 7 or 8, wherein the foam has an initial lambda value of 20.5 mW / mK or less.

[10] A block comprising the foam according to any one of 7 to 9.

[11] A slab comprising the foam according to any one of claims 7 to 9.

[12] A laminate comprising the foam according to any one of 7 to 9.

[13] 10. The foam according to any one of claims 7 to 9, which is in the form of a foam for home appliances.

Claims

1. a foam former comprising at least one of a polyurethane foam and a polyisocyanurate foam; and a blowing agent composition comprising a mixture of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane in amounts of 1 to 35% by weight of cyclopentane and 65 to 99% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), based on the total weight of the Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane; A foam for home appliances formed from

2. The foam described in claim 1, wherein the foam for home appliances is a foam for refrigerators, a foam for freezers, or a foam for refrigerators / freezers.

3. The blowing agent composition may comprise 1,1-difluoroethane (HFC-152a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), propane, butane, pentane, hexane, E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(E)), Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(E)), or Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(E)).

10. The foam of claim 1, further comprising one or more additional blowing agents selected from chloropropene (HFO-1336mzz(Z)), E-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), Z-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(Z)), E-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), 1,1-dichloro-2,3,3,3-tetrafluoropropene (HFO-1214ya), trans-dichloroethylene (trans-DCE), methyl formate, methylal, formic acid, acetic acid, C1-C4 aldehydes, C3-C4 ketones, C2-C4 ethers, diethers, water, and combinations thereof.

4. 10. The foam of claim 1, wherein the blowing agent composition consists essentially of a mixture of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane.

5. 5. The foam of claim 4, wherein the blowing agent composition comprises a mixture of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane.

6. 1. A method of forming an appliance foam, comprising: (a) providing a foamable composition comprising: (i) a thermosetting foam former comprising an isocyanate and a polyol or a mixture of polyols; and (ii) a blowing agent composition comprising a mixture of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane in amounts of 1% to 35% by weight of cyclopentane and 65% to 99% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), based on the combined weight of the Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane; (b) foaming the foamable composition to provide an appliance foam having an initial lambda value of 20.5 mW / mK or less; A method comprising:

7. The blowing agent composition may be selected from the group consisting of 1,1-difluoroethane (HFC-152a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), propane, butane, pentane, hexane, E-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(E)), Z-1,1,1,4,4,4-hexafluoro-2- 7. The method of claim 6, further comprising one or more additional blowing agents selected from butene (HFO-1336mzz(Z)), E-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), Z-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(Z)), E-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), 1,1-dichloro-2,3,3,3-tetrafluoropropene (HFO-1214ya), trans-dichloroethylene (trans-DCE), methyl formate, methylal, formic acid, acetic acid, C1-C4 aldehydes, C3-C4 ketones, C2-C4 ethers, diethers, water, and combinations thereof.

8. 8. The method of claim 7, wherein when the blowing agent composition further comprises water, the blowing agent composition is present in an amount less than 5 wt%.

9. 7. The method of claim 6, wherein the blowing agent composition consists essentially of a mixture of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane.

10. 10. The method of claim 9, wherein the blowing agent composition comprises a mixture of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane.

11. The method of claim 6 further comprising at least one catalyst.

12. The method of claim 11 , wherein the catalyst is an amine catalyst and / or a metal catalyst.

13. 13. The method of claim 12, wherein the amine catalyst is a primary amine, a secondary amine, or a tertiary amine.

14. Examples of the tertiary amine include N,N-dimethylcyclohexylamine, N,N-dimethylethanolamine, dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethylethanolamine, 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-dimethylamino ...

14. The method of claim 13, wherein the compound comprises one or more of the following: N,N-dimethylpropanediamine, 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-dimethylaminopropylurea, dicyclohexylmethylamine, ethyldiisopropylamine, dimethylisopropylamine, methylisopropylbenzylamine, methylcyclopentylbenzylamine, isopropyl-sec-butyl-trifluoroethylamine, diethyl-(α-phenylethyl)amine, tri-n-propylamine.

15. 14. The method of claim 13, wherein the secondary amine comprises one or more of dicyclohexylamine, tert-butylisopropylamine, di-tert-butylamine, cyclohexyl-tert-butylamine, di-sec-butylamine, dicyclopentylamine, di-(α-trifluoromethylethyl)amine, di-(α-phenylethyl)amine.

16. The method of claim 12 , wherein the metal catalyst is a potassium catalyst.

17. 17. The method of claim 16, wherein the potassium catalyst is selected from potassium octoate (Dabco K15) and potassium acetate (Polycat 46).

18. The method of claim 12 wherein the metal catalyst is a tin catalyst.

19. 19. The method of claim 18, wherein the tin catalyst is selected from dibutyltin dilauryl mercaptide (Dabco T120, Fomrez UL-1), dibutyltin diisooctyl maleate (Dabco T125), dimethyltin dilauryl mercaptide (Fomrez UL-22), dioctyltin dilauryl mercaptide (Fomrez UL-32), and dibutyltin di-(2-ethylhexyl thioglycolate) (Fomrez UL-6).

20. 13. The method of claim 12, wherein the metal catalyst is a bismuth carboxylate.

21. 21. The method of claim 20, wherein the bismuth carboxylate is selected from Bicat 8108 and Bicat 8210.

22. 8. The method of claim 6 or 7, wherein the blowing agent composition is present in an amount of from 2 to 15 wt.%, inclusive, as a percentage of the total weight of the foamable composition.

23. 7. The method of claim 6, wherein the foamable composition is provided as a preblend of two components, an isocyanate is provided as a first component and a polyol or polyol mixture is provided as a second component, and the first component and / or the second component comprises the blowing agent composition.

24. 24. The method of claim 23, wherein the first component further comprises a surfactant and the second component further comprises a surfactant, a catalyst, and a flame retardant.

25. 25. The method of claim 24, wherein the mixture of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane is present in the second component.

26. 26. The method of claim 25, wherein the mixture of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane in the second component is present in an amount of 10% by weight or greater, as a percentage of the total polyol preblend resin.

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