Blowing agent comprising z-1-chloro 2333 tetrafluoropentene (HCFO 1224yd (z))

Abstract

To provide a mixture containing a hydrofluorocarbon, a fluoroolefin, an iodide-containing compound and other fluorinated compounds, which has a low ozone depletion potential and a low global warming potential.SOLUTION: Provided are blowing agents for polyurethane and polyisocyanurate foams comprising Z-1-chloro - 2333 - tetrafluoropentene (HCFO - 1224yd (Z)) and cyclopentane in amounts of 65 wt% to 99 wt% and 1 wt% to 35 wt%, respectively. There is further provided a foam formed from a polyurethane or polyisocyanurate foam and a blowing agent comprising Z-l-chloro - 2333 - tetrafluoropentene (HCFO - 1224yd (Z)) and cyclopentane having a low initial lambda value.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application is a continuation of U.S. Provisional Patent Application No. 63 / 167950, filed March 30, 2021. No. 60 / 699,997, filed on Dec. 1, 2003, which is hereby incorporated by reference in its entirety.

[0002] FIELD OF THE INVENTION The present disclosure relates to Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1 224yd(Z)) and cyclopentane. Chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and and cyclopentane, and methods for foaming using these compositions - Patents.com and foaming agents comprising these compositions. [Background technology]

[0003] Fluorocarbon fluids are used as refrigerants, aerosol propellants, foam blowing agents, heat transfer media, gaseous dielectrics, and It has found widespread use in industry in many applications, including as a flame retardant, flame retardant, and flame retardant. There are.

[0004] The industry offers alternatives to the CFCs, HCFCs, and HFCs used today. New fluorocarbon mixtures are constantly being developed that are considered to be environmentally safer alternatives. Hydrofuls, which have low ozone depletion potential and low global warming potential, are being pursued. Fluorocarbons, fluoroolefins, iodide-containing compounds, and other fluorinated compounds. Of particular interest are mixtures containing methyl methyl acrylate and methyl methacrylate. Such mixtures are the subject of the present disclosure. Summary of the Invention

[0005] The present disclosure relates to a foam-forming agent and a Z-1-chloro-2,3,3,3-tetrafluoropentene a blowing agent composition containing a mixture of cyclopentane (HCFO-1224yd(Z)) and cyclopentane; The blowing agent composition comprises Z-1-chloro-2,3,3,3 -Sum of tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane Cyclopentane in an amount of about 1% to about 35% by weight and about 65% to about 99% by weight of Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO The foamable composition may comprise polyurethane foam and isopropyl alcohol. cyanurate foam.

[0006] The present disclosure relates to Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1 A mixture of 224yd(Z)) and cyclopentane was treated with Z-1-chloro-2,3,3,3- Total weight of tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane Based on the amount, 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 The present invention further provides a foam formed using a blowing agent composition comprising an initial amount of The lambda value may be less than or equal to 20.5 mW / mK. [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 relates to Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1 224yd(Z)) and cyclopentane, which are described in more detail below. The present disclosure also provides Z-1-chloro-2,3,3,3-tetrafluoropentene (HC Compositions, particularly foaming compositions, utilizing a mixture of FO-1224yd(Z) and cyclopentane Also provided are agents, foamable compositions, foam articles, and methods and systems for forming foams. do.

[0009] Surprisingly, cyclopentane is Z-1-chloro-2,3,3,3-tetrafluoro Approximately based on the total weight of pentene (HCFO-1224yd(Z)) and cyclopentane When added in an amount of 1% to about 35% by weight, Z-1-chloro-2,3,3,3-tetra ... A combination of tetrafluoropentene (HCFO-1224yd(Z)) and cyclopentane It has been found that foams formed using blowing agents containing It was.

[0010] The amount of cyclopentane can also be expressed as a mole percentage. Tan Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224 The amount of cyclopentane is about 1 mole % to about 50 mole % based on the number of moles of cyclopentane and cyclopentane. When added, Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO -1224yd(Z)) and cyclopentane. The foams exhibit low initial lambda values.

[0011] The use of hydrocarbons in the blowing agent composition typically results in a higher molecular weight in the resulting foam. Since this adversely affects the initial lambda value in the The foaming agent composition containing tetrafluoropentene (HCFO-1224yd(Z)) The addition of cyclopentane to the blowing agent composition was proportional to the amount of cyclopentane added to the blowing agent composition. One would expect this to immediately increase the initial lambda value of the resulting foam. Surprisingly, Z-1-chloro-2,3,3,3-tetrafluoroethylene was used as a blowing agent. The initial lambda value of the foam formed using pentane (HCFO-1224yd(Z)) was , cyclopentane is converted to Z-1-chloro-2,3,3,3-tetrafluoropentene (HC Based on the total weight of FO-1224yd(Z) and cyclopentane, Z-1-chloro -2,3,3,3-Tetrafluoropentene (HCFO-1224yd(Z)) up to approximately It was found to remain substantially unchanged when added in an amount of 35% by weight.

[0012] This is Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-12 24yd(Z)) is relatively expensive compared to cyclopentane, and therefore is not suitable as a blowing agent. Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd Foams using mixtures of (Z)) and cyclopentane have desirable initial lambda values. However, Z-1-chloro-2,3,3,3-tetrafluoropentene (HC Relatively cheaper to produce than foams made using only FO-1224yd(Z) This presents a significant commercial advantage in that it can

[0013] I. Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-122 A blowing agent containing a mixture of 4yd(Z) and cyclopentane Fluorocarbon fluids are desirable for use in a variety of applications, including as blowing agents, and other uses. Unfortunately, the industrial use of certain hydrofluorocarbons (HFCs) The use of ' is now considered to contribute to global warming and therefore However, new, environmentally safer HFC-containing compositions are being developed. Acknowledgment is due to the fact that many properties that will be useful in these applications are not easily predicted. For example, it is difficult to develop a blowing agent composition that not only has acceptable environmental properties, but also Among other things, chemical stability, low or no toxicity, and low or no flammability are also desirable. The blowing agent also provides superior performance in use, for example, superior thermal insulating properties and other desirable properties. It is also desirable to have fast foaming properties.

[0014] Methods for making conventional foam materials, e.g., thermoplastic and thermoset materials These methods and compositions have been known for a long time. Chemical and / or physical blowing agents are used to create a foam structure in the trichomes. Such blowing agents include, for example, azo compounds, various volatile organic compounds, VOCs and CFCs Chemical blowing agents are typically gases such as nitrogen, carbon dioxide, or carbon monoxide. Materials that form a polymer matrix that causes the release (usually at a given temperature / pressure) undergo some form of chemical transformation, including chemical reactions with One of the foaming agents is water. Physical foaming agents are typically polymers or polymer precursors. It is dissolved in the material and then volumetrically expands (again at a given temperature / pressure) to form a foam structure. Physical blowing agents are often used in conjunction with thermoplastic foams, but The use of chemical blowing agents in place of, or in addition to, the physical blowing agents associated with plastic foams. In conjunction with thermoset foams, chemical and / or physical blowing agents may be used. It is understood that specific compounds and compositions containing them are , may constitute chemical and physical blowing agents.

[0015] The blowing agent of the present disclosure is Z-1-chloro-2,3,3,3-tetrafluoropentene (HC It may also contain a mixture of FO-1224yd(Z) and cyclopentane. Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224 about 1% by weight or more, about 5% by weight or more, based on the total weight of yd(Z)) and cyclopentane Above, 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 3 In an amount of 0% by weight or less, about 35% by weight or less, or any value encompassed by these endpoints. , may be present in a mixture. Z-1-chloro-2,3,3,3-tetrafluoropentene ( HCFO-1224yd(Z)) is Z-1-chloro-2,3,3,3-tetrafluoroethylene Based on the total weight of pentene (HCFO-1224yd(Z)) and cyclopentane 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 % by weight or less, about 90% by weight or less, about 95% by weight or less, about 99% by weight or less, or endpoints thereof The amount of hydroxybenzoates may be present in the mixture in any amount encompassed by the formula:

[0016] The blowing agent is Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-12 When only 24yd(Z)) and cyclopentane are included, the above percentages are Based on total weight.

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

[0018] When used as a blowing agent, Z-1-chloro-2,3,3,3-tetrafluoroethylene A mixture of 1,1-hexene (HCFO-1224yd(Z)) and cyclopentane is, for example, -Difluoroethane (HFC-152a), 1,1,1,3,3-pentafluoropropane fluoroethane (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, hexafluorobutane Sun, 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(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-1214 ya), trans-dichloroethylene (trans-DCE), methyl formate, methyl alcohol, formic acid, acetic acid, C1-C4 aldehydes, C3-C4 ketones, C2-C4 ethers, diols one or more additional blowing agents, such as one or more of ether, water, and combinations thereof; may be used in combination with

[0019] If water is added, it is typically less than 5% by weight, for example, 5% by weight or less, 4% by weight or more. In some embodiments, the hydroxybenzoates are present in an amount of 0.1 wt % or less, 0.2 wt % or less, 0.3 wt % or less, 0.5 wt % or less, 0.6 wt % or less, 0.7 wt % or less, 0.8 wt % or less, 0.9 ...

[0020] II. Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-12 A foamable composition containing a mixture of 24yd(Z) and cyclopentane The present disclosure relates to blowing agent compositions such as those described above and one or more additives capable of forming a foam. A foamable composition is provided comprising the above components. In particular, the mixture comprises a polyurethane and a polyisocyanate. cyanurate foam compositions. In principle, the mixture can be is added to a foamable composition which may contain other ingredients necessary to react with the .

[0021] As used herein, the term "foam former" includes, for example, flame retardants, surfactants, and the like. Detergent, crosslinking agent, defoamer, dissolution promoter, filler, dispersant, antibacterial agent, viscosity reducing agent, vapor pressure A foam structure, preferably a general foam, free of additives such as modifiers, colorants, and dyes. Foam is used to refer to a component or combination of components that can form a foam structure. do.

[0022] The one or more foam-forming components may be capable of forming a thermoset foam. Examples of thermoset foams include polyurethanes and polyisocyanates. An annular foam may be included.

[0023] The present disclosure also relates to closed-cell foams comprising the blowing agent compositions of the present disclosure. It may be a foam, a soft foam or an integral skin foam. Preferably, the present disclosure , Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-122 Closed-cell rigid foam containing a blowing agent composition containing a mixture of 4yd(Z) and cyclopentane Regarding the body.

[0024] The foams provided by the present disclosure may be used in the form of blocks, slabs, laminates, pour-in-place foam panels, and the like. The foams described in the present disclosure may be panels such as spray-applied foam and floss. The foams, and particularly the thermoset foams disclosed herein, may be used in a wide variety of applications, with certain preferred In a preferred embodiment, the present disclosure provides foams for home appliances, such as refrigerator foams, freezer foams, and the like. , refrigerator / freezer foams, panel foams; and other low-temperature or cryogenic manufacturing applications. The disclosed appliance foam includes:

[0025] The foams of the present disclosure are particularly useful in the appliance industry, the refrigeration industry, the transportation industry, and the construction industry (e.g., building engineering). The foams described herein are all provided for use in the invention of the present disclosure. In addition to the low global warming potential associated with foams, the thermal insulation efficiency (especially thermoset foams) (in the case of a composite), one or more of the following characteristics may be considered: dimensional stability, compressive strength, thermal insulation properties over time, and flame retardancy. Offering exceptional features, characteristics and / or properties.

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

[0027] The blowing agent of the present disclosure may be present in an amount of about 2% by weight or more, and about 3% by weight or more, as a percentage of the total weight of the foamable composition. % 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 of these endpoints inclusive. The total weight of the foamable composition may be the total weight of the thermoplastic elastomer. Includes all components of foams and thermoset foams.

[0028] III. Methods for Forming Foams All currently known and available methods and systems for forming foams are within the scope of the present disclosure. It is contemplated that the present invention may be readily adapted for use in connection with compositions. The methods generally involve incorporating a blowing agent into the foamable composition, and then preferably The composition is foamed by a step or series of steps that causes a volume expansion of the blowing agent described. Generally, the systems and devices currently used for incorporating and forming the blowing agent are It is contemplated that the compositions disclosed herein can be readily used. The advantage of this method is that it provides an improved blowing agent that is generally compatible with existing foaming methods and systems. It is thought that this is the case.

[0029] Thus, the present disclosure provides a method for forming all types of foams, including thermoset and thermoplastic foams. It will be understood that the present disclosure includes methods and systems for achieving the same. , relating to the use of the blowing agents of the present invention in conjunction with conventional foaming equipment under conventional processing conditions. The process is therefore suitable for masterbatch type operations, blend type operations, third blowing agent addition, , and blowing agent addition in the mix head.

[0030] For thermoplastic foams, the preferred method generally involves adding a blowing agent to a thermoplastic material, preferably The compound is introduced into a thermoplastic polymer and then heated to conditions effective to cause foaming. and providing a plastic material.

[0031] For example, the step of introducing the blowing agent into the thermoplastic material may be carried out in an extruder containing the thermoplastic material. (e.g., a screw extruder) and introducing a blowing agent into the extruder. The process involves reducing the pressure on the thermoplastic material, thereby causing the blowing agent to expand, and the material This may include contributing to foaming of the material.

[0032] In particular, in light of the disclosure contained herein, the blowing agents of the present disclosure may be formed and / or expanded. The order and manner in which the foaming composition is added 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, Furthermore, the components of the foamable composition do not have to be mixed prior to introduction into the extrusion equipment. Alternatively, or even further, the components may not be added to the same location in the extrusion apparatus. can be introduced either directly or as part of a premix and then It is further added to other parts of the foamable composition.

[0033] Thus, by this means the components come together in the extruder and / or In the hope of effectively operating, one or more components of the blowing agent are mixed with one or more of the blowing agent components. It is preferably introduced into the extruder at a first location upstream from the addition of the other ingredients. Nevertheless, it may be preferable to premix two or more components of the blowing agent and then and incorporated together into the foamable composition either directly or as part of a premix. It may be preferable to add the foaming agent to the other portions of the foamable composition.

[0034] The present disclosure relates to a thermosetting polymer such as polyurethane (PU) or polyisocyanurate (PIR). The present invention also relates to a method of forming a foam. The method generally comprises providing a blowing agent composition of the present disclosure, A blowing agent composition is added (directly or indirectly) to the foamable composition and is prepared in a manner known in the art. and reacting the foamable composition under conditions effective to form a foam or cellular structure, such as "Polyurethanes Chemistry and Te chnology,” Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York Any of the methods known in the art, such as those described in U.S. Pat. No. 6,299,499, ... may be used in accordance with the present disclosure. This is incorporated herein by reference. A particularly preferred method is to combine an isocyanate, a polyol or a mixture of polyols, the foaming agent of the present disclosure, and the the agent composition, and optionally other materials such as catalysts, surfactants, flame retardants, colorants or other additives. By combining the materials, a thermosetting material (e.g., polyurethane or polyisocyanurethane) can be obtained. The method includes preparing a polyimide foam.

[0035] For polyurethane or polyisocyanurate foams in pre-blended formulations It is convenient to provide the components. Most typically, pre-blended formulations consist of two The isocyanate and optionally certain surfactants are pre-blended into the components The first component, commonly referred to as the "A" component, is a polyol or polyol mixture. The surfactant, catalyst, and flame retardant comprise the second component, commonly referred to as the "B" component. The agent may be present in component A and / or component B. For example, if the blowing agent composition contains two blowing agents, If included, the first blowing agent may be present in the A component and the second blowing agent may be present in the B component. That's fine.

[0036] Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd The mixture of (Z)) and cyclopentane accounts for 100% of the total polyol preblend resin (component B). As a fraction, about 10% by weight or more, about 15% by weight or more, about 20% by weight or less, about 25% by weight or more 30% by weight or less, about 30% by weight or less, or any value encompassed by these endpoints. It may be present in the lupre-blend mixture (B component).

[0037] The polyol preblend mixture of the present disclosure may include additional components. The compound may also contain any other blowing agent, such as E-1-chloro-2,3,3,3-tetrafluoroethylene. Dichloropropene (HCFO-1224yd(E)), Z-1,1,1,4,4,4-hexyl Subfluoro-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 (1234ze(E), 2,3,3,3-tetrafluoropropene) Pen (HFO-1234yf), and 1,1-dichloro-2,2-difluoroethylene ( HFO-1112); hydrocarbons, such as iso-pentane and n-pentane; hydrofuran Fluorocarbons, such as 1,1,1,3,3-pentafluoropropane (HFC-24 5fa), 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, e.g., organic and / or inorganic flame retardants; surfactants (silicon Silicone or non-silicone); crosslinking agent; antifoaming agent; solubility enhancer; filler; dispersing agent; antibacterial agent; viscosity reducing agent vapor pressure modifiers; colorants; and pigments.

[0038] Suitable polyols include, for example, sucrose-containing polyols; phenols; Formaldehyde-containing polyols; glucose-containing polyols; sorbitol-containing polyols methyl glucoside-containing polyols; aromatic amine-containing polyols, e.g., ortho -Toluenediamine (ortho-toluene diamine, o-TDA)-containing polyols; aromatic polyols ester polyol;glycerol;ethylene glycol;diethylene glycol;propylene propylene glycol; one or more of (a) condensed with one or more of (b) Here, (a) is glycerin, ethylene glycol, diethylene glycol, Dimethylolpropane, ethylenediamine, pentaerythritol, soybean oil, lecithin, (b) is selected from tall oil, palm oil, and castor oil, and (b) is selected from ethylene oxide, propylene oxide, ethylene oxide, a mixture of ethylene oxide and propylene oxide, and combinations thereof. (a) or more of (a) above.

[0039] Suitable catalysts may include amine catalysts and / or metal catalysts. Amine catalysts include first The amines may include, but are not limited to, primary, secondary, or tertiary amines. Useful tertiary amine catalysts include, but are not limited to, N,N-dimethylcyclohexylamine, N, N-dimethylethanolamine, dimethylaminoethoxyethanol, N,N,N'-trimethylethanolamine N,N,N'-trimethyl-N'-hydroxyethanolamine Ethyl bisaminoethyl ether, tetramethyliminobispropylamine, 2-[[2 -[2-(dimethylamino)ethoxy]ethyl]methylamino]ethanol, pentamethyl Diethylenetriamine, Pentamethyldipropylenetriamine, N,N,N',N'' ,N''-pentamethyl-dipropylenetriamine, 1,1,4,7,10,10-hexyl N,N-bis(3-dimethylaminopropyl)-N- Isopropanolamine, N'-(3-(dimethylamino)propyl)-N,N-dimethylamine bis(3-dimethylaminopropyl)-N,N-dimethyl-1,3-propanediamine propanediamine, bis-(2-dimethylaminoethyl) ether, N,N',N'' -Dimethylaminopropyl hexahydrotriazine, tetramethyliminobispropyl amine, trimethyl-N', 2-hydroxyethyl-propylenediamine, bis-(3-aminopropyl) N,N-dimethyl-1,3-propanediamine, 1-(aminopropyl)-methylamine Dimethylamino)hexadecane, benzyldimethylamine, 3-dimethylaminopropyl Urea, dicyclohexylmethylamine; ethyldiisopropylamine; dimethylisopropyl Benzylamine; Methylisopropylbenzylamine; Methylcyclopentylbenzylamine ;Isopropyl-sec-butyl-trifluoroethylamine;Diethyl-(α-phenyl) ethylamine, tri-n-propylamine, or a combination thereof. Useful secondary amine catalysts include, but are not limited to, for example, dicyclohexylamine; tert- Butylisopropylamine;Di-tert-butylamine;Cyclohexyl-tert- Butylamine; Di-sec-butylamine, Dicyclopentylamine; Di-(α-triphenylamine) di-(α-phenylethyl)amine; di-(α-phenylethyl)amine; or combinations thereof This may include a combination of

[0040] Metal catalysts include, for example, potassium octanoate (Dabco K15) and potassium acetate. potassium catalysts such as Polycat 46; tin catalysts such as dibutyltin di Lauryl mercaptide (Dabco T120, Fomrez UL-1), dibutyl ether Diisooctyl maleate (Dabco T125), dimethyltin dilauryl mercury Dioctyltin dilauryl mercaptide (Fomrez UL-22), Dioctyltin dilauryl mercaptide Fomr ez UL-32), and dibutyltin di-(2-ethylhexyl thioglycolate) ( Fomrez UL-6); and bismuth carboxylates, e.g., Bicat 8 108, Bicat 8210, etc.

[0041] Suitable isocyanates include aliphatic and aromatic polyisocyanurates, or any organic polyisocyanurate that can be used in polyisocyanurate foam synthesis. Suitable organic polyisocyanurates include those well known in the field of polyurethane chemistry. These include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates. These are described, for example, in U.S. Pat. Nos. 4,868,224, 3,401,190, and 5,401,190. No. 3,454,606, No. 3,277,138, No. 3,492,330, No. Nos. 3,001,973, 3,394,164, 3,124.605, and No. 3,201,372.

[0042] Certain surfactants are added to act as foam stabilizers. Typical materials are sold under the names DC-193, B-8404, and L-5340. These are generally described in U.S. Pat. Nos. 2,834,748, 2,917,480 and 2,834,748. Polysiloxane polyoxyalkylene binders such as those disclosed in US Pat. No. 4,846,458. and block copolymers, each of which is incorporated herein by reference. Other optional additives for the Lupre blend include flame retardants, e.g., tri(2-chloro) ethyl)phosphate, tri(2-chloropropyl)phosphate, tri(2,3-dibutyl)phosphate tri(1,3-dichloropropyl) phosphate, tri(1,3-dichloropropyl) phosphate, etc. 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 oxides) Examples of suitable binders include ethylene glycol, aluminum trihydrate, and polyvinyl chloride.

[0043] Polyurethane or polyisocyanurate foams can be prepared by mixing the A and B side components together. Foams such as blocks, slabs, laminates, pour-in-place foam panels and other articles, spray The mixture is easily prepared by forming a coating foam, froth, etc. For large scale preparations, hand mixing or mechanical mixing techniques may be used.

[0044] The methods and systems of the present invention also include a one component thermoset foam containing a blowing agent according to the present disclosure. The method also includes forming a polymeric foam, preferably a polyurethane foam. or by dissolving in a foam-forming agent that is liquid at the pressure in the container. The foam-forming agent of the two-component foam may contain a second portion of the blowing agent in a separate gas phase. In such systems, the contained / dissolved blowing agent may be present as a predominantly The separate gas phase acts to provide a driving force to the foam former, causing the foam to expand. Such one component systems are typically packaged in aerosol-type cans, etc. Preferably, the foaming agent of the present disclosure is packaged in a container, and thus the foaming agent of the present disclosure is preferably Energy for expanding the body and / or transporting the foam / expandable material from the package, as well as Such systems and methods provide a fully formulated The package is filled with a system (preferably an isocyanate / polyol system) and the present invention The method includes introducing such a gaseous blowing agent into a package, preferably an aerosol-type can. obtain.

[0045] IV. Foam As mentioned above, surprisingly, Z-1-chloro-2,3,3,3-tetrafluoro Using a blowing agent containing pentene (HCFO-1224yd(Z)) and cyclopentane It was found that the foams formed exhibited low lambda values. Tan Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-1224 yd(Z)), as shown in Figure 1, Considering the high initial lambda values ​​of hydrocarbons in general and cyclopentane in particular, Considering this, Z-1-chloro-2,3,3,3-tetrafluoropentene (HCFO-12 The initial lambda value of 24yd(Z) is expected to increase immediately upon addition of cyclopentane. However, as disclosed herein, the initial lambda value may be up to about 3 It remains essentially unchanged upon addition of 3 wt. % cyclopentane.

[0046] Z-1-chloro-2,3,3,3-tetrafluoropentene (H A mixture of CFO-1224yd(Z) and cyclopentane is used to produce polyurethane or polyimide. When used as a blowing agent in sorbent foams, initial lambda (average temperature at 10°C) ) is 19mW / mK or more, 19.2mW / mK or more, 19.4mW / mK or more, 19 .6mW / mK or more, 19.8mW / mK or less, 20.0mW / mK or less, 20.2mW / mK or less, 20.4mW / mK or less, 20.5mW / mK or less, or It can be any value encompassed by the

[0047] The foams of the present disclosure may be in the form of, for example, blocks, slabs, or laminates. The disclosed foams are suitable for use in, for example, refrigerators, freezers, coolers, refrigerated trucks, rail cars, and hot water appliances. The foams of the present disclosure may be used as foam core metal parts. These foam core metal panels can be manufactured either continuously or discontinuously. The compounds can be prepared by either method, and both such methods are within the scope of this disclosure. In the building industry, such articles in the form of rigid panels are suitable for use in: It can be used as insulation in the building envelope of commercial structures.

[0048] “Polyurethanes Chemistry and Technology ,” Volumes I and II, Saunders and Frisch, 1 962, John Wiley and Sons, New York, NY Any of the methods known in the art, such as those described herein, may be used to form foams according to the present disclosure. can be used or adapted in accordance with the method described in US Pat. No. 6,49 ... which is 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)) are Formulated using the following starting materials: Stepanpol PS available from Stepan 2352 (Polyester polyol, hydroxyl value: 240 mg KOH / g, functionality :2); Voranol 490 (a sucrose / glycerin-initiated polyisoprene) available from Dow Polyether polyol, hydroxyl value: 490 mg KOH / g, functionality: 4.3);D Voranol 391 (amine (ortho-diaminotoluene) starting material) available from Polyol, hydroxyl value: 395 mg KOH / g, functionality: 4); available from Dow Suitable for Voranol 270 (glycerin-initiated polyether polyol, hydroxyl value: 238 mg KOH / g, functionality: 3); Terate available from Invista HT5510 ("HT5510") (aromatic polyester polyol, hydroxyl value: 2 60 mg KOH / g, functionality: 2); Tegostab B84210 ("B8421 0") (silicone surfactant from Evonik); Tegostab B8465 ( "B8465") (a silicone surfactant from Evonik); Dabco K15 ( "K15") (potassium octanoate in diethylene glycol from Evonik); P Polycat 8 (N,N-dimethylcyclohexylamine from Evonik); Po lycat 5 (pentamethyldiethylenetriamine from Evonik); Polyc at 41 (1,3,5-tris[3-(dimethylamino)propyl] from Evonik ]hexahydro-1,3,5-triazine); Lupranat available from BASF e M20 (polymeric isocyanate, 31.5% NCO, functionality: 2.7); TCPP (Tris(1-chloro-2-propyl)phosphate) Phosphorus content: 9.4% by weight; Chlorine content Amount: 33% by weight.

[0051] The foams were formulated by hand mixing based on the formulations set forth in the examples below. Using LaserComp FOX50, sample size 12'' x 12'' x 1'' The lambda value was recorded.

[0052] Example 1: Z-1-chloro-2,3,3,3-tetrafluoroethylene in polyurethane foam Oropropene (HCFO-1224yd(Z)) and cyclopentane Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd Various mixtures of (Z)) and cyclopentane as blowing agents in polyurethane foams The compositions of the different foams are shown in Table 1 below. , each component is listed as parts per hundred parts polyol (php).

[0053] [Table 1]

[0054] Each of the formed foams was then subjected to a filtration step using the method described in ASTM C518. Initial lambda was tested. Initial lambda values ​​ranged from 1% to 35% by weight of cyclopentane. and 65% to 99% by weight of Z-1-chloro-2,3,3,3-tetrafluoropentane (H When a mixture of CFO-1224yd(Z) was used as a blowing agent, the foam yield was approximately 19.5 These values ​​were below 100 mW / mK and began to increase with the addition of more cyclopentane. The results are shown in graphical form in FIG.

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

[0056] [Table 2]

[0057] Each of the foams formed was then tested for initial lambda. The initial lambda value was 1 % to 24% by weight of cyclopentane and 76% to 99% by weight of Z-1-chloro-2, A mixture of 3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) as a blowing agent When used as a 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 Z-1- Chloro-2,3,3,3-tetrafluoropentene (HCFO-1224yd(Z)) and A mixture of Z-1-chloro-2,3,3,3-tetrafluoropentane and cyclopentane was 1 weight based on the total weight of cyclopentane (HCFO-1224yd(Z)) and cyclopentane % to 35% by weight of cyclopentane and 65% to 99% by weight of Z-1-chloro-2,3 ,3,3-tetrafluoropentene (HCFO-1224yd(Z)) in an amount of foaming and a foamable composition.

[0059] In a second embodiment, the foam-forming agent is a polyurethane foam or a polyisocyanurate foam. The foamable composition according to embodiment 1 includes at least one of the following:

[0060] Embodiment 3 is the composition of any of embodiments 1 or 2, further comprising at least one surfactant. The foamable composition is as described above.

[0061] Aspect 4 is the foaming agent of any one of Aspects 1 to 3, further comprising at least one catalyst. It is a sexual composition.

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

[0063] Aspect 6 is a polymer modifier, toughening agent, colorant, pigment, solubility enhancer, rheology modifier , plasticizers, antibacterial agents, viscosity reduction regulators, fillers, vapor pressure adjusters, and any of these. or a combination of two or more thereof. 6. The foamable composition according to any one of Aspects 1 to 5, comprising:

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

[0065] In an eighth embodiment, the foam-forming agent comprises a polyurethane foam or a polyisocyanurate foam. 8. The foam of claim 7.

[0066] Aspect 9 is the foam of any one of aspects 7 to 8, wherein the foam has an initial lambda value of 20.5 mW / mK or less. The foam described herein is

[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 of the present invention relates to a foam according to any one of the seventh to ninth aspects, which is in the form of a foam for home appliances. be.

[0071] As used herein, "any range defined between any two of the preceding values" means The phrase "within a range" means that the values ​​are in a lower part of the list or in a higher part of the list. Any range, whether or not it is one of the values ​​listed before such clause, For example, a pair of values ​​means that two lower values, two higher values, The value may be selected from a lower value, a higher value, or a lower and a higher value.

[0072] As used herein, the singular forms "a," "an," and "the" are used where the context so requires. Furthermore, the term "quantity," "concentration," or other value or The parameter may be a range, a preferred range, or a list of upper and lower preferred values. When a range is given as either a Regardless of any upper range or upper preferred value and any lower range or lower preferred value, All ranges formed from any pair of Where a range of numerical values ​​is recited herein, unless otherwise stated, the range is The scope of the present disclosure is intended to include the endpoints of, and all integers and fractions within, the range. It is not intended to be limited to the specific values ​​recited when defining a range.

[0073] As used herein, "any range defined between any two of the preceding values" means The phrase "within a range" means that the values ​​are in a lower part of the list or in a higher part of the list. Any range, whether or not it is one of the values ​​listed before such clause, For example, a pair of values ​​means that two lower values, two higher values, The value may be selected from a lower value, a higher value, or a lower and a higher value.

[0074] It should be understood that the foregoing description is only illustrative of the present disclosure. Various alternatives and modifications can be devised by those skilled in the art without departing from the scope of the invention. Accordingly, this disclosure contemplates all such alternatives, modifications, and variations as fall within the scope of the appended claims. It is intended to cover modifications and variations.

Claims

1. A foam-forming agent comprising at least one of polyurethane foam and polyisocyanurate foam, and A foaming 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 Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane. A panel foam formed from [the following material].

2. The panel foam according to claim 1, wherein the panel foam is an in-situ injected foam panel.

3. The panel foam according to claim 1, wherein the panel foam is a foam core metal panel.

4. A method for forming a panel foam, To provide a foaming composition comprising (a) (i) a thermosetting foam-forming agent comprising an isocyanate and a polyol or a mixture of polyols, and (ii) a foaming 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 Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)) and cyclopentane, (b) To provide a panel foam having an initial lambda value of 20.5 mW / mK or less by foaming the foaming composition, Methods that include...

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