Foaming agents and compositions containing fluorine substituted olefins, and methods of foaming

Abstract

To provide a foaming agent having low ozone depletion potential and does not contain substantial amounts of chlorofluorocarbons (CFCs) or hydrochlorofluorocarbons (HCFCs).SOLUTION: A foaming agent comprises (a) at least one fluorocarbon represented by Formula I: XCFzR3-Z (I) (where X is a C1, C2, C3, C4 or C5 unsaturated, substituted or unsubstituted radical, each R is independently CI, F, Br, I or H, and z is 1 to 3; however, when Br is present in the compound, the compound includes no hydrogen) and (b) at least one adjuvant selected from the group consisting of co-blowing agents, surfactants, polymer modifiers, toughening agents, colorants, dyes, solubility enhancers, rheology modifiers, plasticizing agents, flammability suppressants, antibacterial agents, viscosity reduction modifiers, fillers, vapor pressure modifiers, nucleating agents, catalysts and combinations of two or three or more of these.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to compounds, methods and systems that are useful in many applications, particularly including heat transfer systems such as refrigeration devices. In a preferred aspect, the present invention relates to refrigeration compositions comprising at least one multi-fluorinated olefin of the present invention. [Background technology]

[0002] Fluorocarbon-based liquids have found widespread use in many commercial and industrial applications, including as aerosol propellants and blowing agents. Certain potential environmental concerns, including relatively high global warming potential, associated with the use of certain compositions heretofore used in these applications have led to the use of hydrofluorocarbons (HFCs). It has become increasingly desirable to use liquids with low or no ozone depletion potential, such as HFCs. It is therefore desirable to use liquids that are substantially free of chlorofluorocarbons (CFCs) or hydrochlorofluorocarbons (HCFCs). Furthermore, some HFC liquids have relatively high global warming potentials associated with them, and it is desirable to use hydrofluorocarbons or other fluorinated liquids that have as low a global warming potential as possible while maintaining desirable performance in service characteristics. In addition, single component liquids or azeotrope-like mixtures that do not substantially fractionate upon boiling and evaporation are desirable in certain situations.

[0003] As noted above, there has been growing concern in recent years about potential damage to the Earth's atmosphere and climate, and certain chlorine-based compounds have been recognized as being particularly problematic in this regard. For example, the use of chlorine-containing compositions (e.g., chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs)) as working fluids in heat transfer systems such as refrigeration and air conditioning systems has led to the development of a number of new and emerging technologies. Use of such compounds has become undesirable due to the ozone depleting properties associated with many of these compounds. Thus, there is an increasing need for new fluorocarbon and hydrofluorocarbon compounds and compositions that are attractive alternatives to the compositions heretofore used in these and other applications. For example, there is a need to replace chlorine-containing systems, such as blowing agent systems or refrigeration systems, with new fluorocarbon and hydrofluorocarbon compounds and compositions that will not deplete the ozone layer like hydrofluorocarbons (HFCs). It has become desirable to improve upon chlorine-containing compounds by replacing them with chlorine-free compounds. Industry at large is working to provide alternatives to CFCs and HCFCs and to develop environmentally safer substitutes. The search is on-going for new fluorocarbon-based mixtures that are considered to be alternatives to conventional fluorocarbons, but it is considered important in many cases that any potential replacement must also possess properties present in many of the most widely used liquids that impart good thermal insulation properties and other favorable foam properties when used as blowing agents, such as adequate chemical stability, low or no toxicity, and low or no flammability.

[0004] Furthermore, alternatives to CFC blowing agents represent a significant technological change to traditional foam production systems. It is generally considered desirable for the drug to be effective without Methods and compositions for making conventional foamed materials, such as thermoplastics and thermosets, have been known for a long time. These methods and compositions typically use chemical blowing agents and / or physical foams to form the foamed structure within a polymer matrix. Such blowing agents include, for example, azo compounds, various volatile organic compounds (VOCs), and chlorofluorocarbons. These chemical blowing agents typically include nitrogen, carbon dioxide, and They undergo a specific type of chemical change, involving a chemical reaction (often at a given temperature / pressure) with the substances that form the polymer matrix, which causes the release of gases such as carbon monoxide. One of the most frequently used chemical blowing agents is water. Physical blowing agents typically dissolve in the polymer or polymer precursor and expand in volume (again at a given temperature / pressure), contributing to the formation of the foam structure. Chemical blowing agents are used in conjunction with thermoplastic foams. Although physical blowing agents can be used in place of or in addition to physical blowing agents, physical blowing agents are used with thermoplastic foams. For example, chemical blowing agents are known to be used in connection with the formation of polyvinyl chloride-based foams. It is common to use chemical and / or physical blowing agents with thermoplastic foams. Of course, certain compounds and compositions that contain them include both chemical and physical blowing agents.

[0005] In the past, CFCs were commonly used as standard blowing agents in the preparation of isocyanate-based foams, such as rigid and flexible polyurethane and polyisocyanurate foams. For example, CCl3F (CFC-11) has become a standard blowing agent. However, when released into the atmosphere, The use of this substance was banned by international treaty on the grounds that it damages the stratospheric ozone layer. As a result, it is no longer common or common for pure CFC-11 to be used as the standard blowing agent for the formation of thermoset foams, such as isocyanate-based and phenolic foams.

[0006] Due to the problems associated with CFCs, hydrogen-containing chlorofluoroalkanes (HCFCs) are being used more frequently. For example, CHCl2CF3 (HCFC-123) and CH2ClCHClF (HCFC-141b) are They have a relatively short atmospheric lifetime. However, HCFCs are less harmful to the environment than CFCs as blowing agents. While these compounds are believed to be toxic, such compounds still contain some chlorine and therefore have an "ozone depletion potential" (called an "ODP"). Because they have a non-zero ODP, the ultimate elimination of HCFC use has been a goal.

[0007] Another class of known blowing agents are the non-chlorinated, partially hydrogenated fluorocarbons (referred to as "HFCs"). Certain HFCs currently used as blowing agents have at least one potentially significant problem: they generally have relatively high inherent thermal conductivity (i.e., poor thermal insulation). On the other hand, foams made from certain of the more recent HFC blowing agents, such as CF3CH2CF2H (HFC-245fa), exhibit improved thermal insulation, in part due to the low thermal conductivity of HFC-245fa vapor and in part due to the fine cell structure that HFC-245fa imparts to the foam. HFC-245fa is used in insulation applications and They have been widely used as fuels, particularly in refrigerators, freezers, refrigerator / freezers, and spray foam applications. However, many HFC liquids have relatively high global warming potentials. These and other disadvantages are shared, and it is desirable to use hydrofluorocarbons or other fluorinated liquids that have the lowest possible global warming potential while maintaining the desired performance in service characteristics. More recent HFCs, such as HFC-245fa, HFC-134a, HFC-365mfc, and others, exhibit higher global warming potentials than is desirable, although these are low compared to other HFCs. Thus, The use of HFCs as blowing agents in foam insulation, especially solid foam insulation, has resulted in HFCs becoming less preferred candidates as blowing agents in commercial foam insulation.

[0008] Hydrocarbon blowing agents are also known. For example, U.S. Pat. No. 5,182,309 to Hutzen describes the use of iso- and normal-pentane in various emulsion mixtures. The use of cyclopentane is taught in US Patent No. 5,096,933 to Volkert. Another example of a hydrocarbon blowing agent is cyclopentane. Many hydrocarbon blowing agents, such as cyclopentane and isomers of pentane, are non-ozone depleting agents and exhibit very low global warming potentials, but such materials do not provide the same insulation efficiency as foams made with, for example, HFC-245fa blowing agent. In addition, hydrocarbon blowing agents are undesirable because they are highly flammable. Also, some hydrocarbon blowing agents, in certain circumstances, do not have sufficient miscibility with the materials from which the foam is made, such as many of the polyester polyols commonly used in polyisocyanurate modified polyurethane foams. The use of these alkanes often requires the use of chemical surfactants to obtain a suitable mixture. It is said. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] U.S. Patent No. 5,182,309 [Patent Document 2] U.S. Pat. No. 5,096,933 Summary of the Invention

[0010] Accordingly, there has been an increasing need for new compounds and compositions that are attractive alternatives to compositions that have heretofore been used as blowing agents in these and other applications. Applicants have thus recognized the need for new fluorocarbon-based compounds and compositions that provide an effective replacement for CFCs and HCFCs and are considered environmentally safer substitutes for CFCs and HCFCs. However, any potential substitutes would at least lack the characteristics associated with the most widely used blowing agents, such as, inter alia, gas phase thermal conductivity (low k-factor), low or no toxicity, etc. It is generally considered highly desirable to have comparable properties to, or even to impart such properties to, the foam. Another potentially important property in many applications is flammability; that is, the use of low or non-flammable compositions is considered to be either important or essential in many applications, including, particularly, blowing agent applications. As used herein, the term "non-flammable" refers to a compound or composition that is determined to be non-flammable as measured in accordance with ASTM Standard E-681, 2002, incorporated herein by reference. Unfortunately, However, many HFCs that would be preferred for use in refrigerant compositions if they were nonflammable are not. For example, the fluoroalkane difluoroethane (HFC-152a) and the fluoroalkene 1,1,1-trifluoropropene (HFO-1234zf) are each flammable and therefore unsuitable for use in many applications.

[0011] In U.S. Patent No. 5,900,185 to Tapscott, the flammability of certain materials, including foaming agents, It has been proposed to use bromine-containing halocarbon additives to reduce CO2 emissions. The additives in this patent are argued to be characterized by high efficiency and short atmospheric lifetimes, i.e., low ozone depletion potential (ODP) and low global warming potential (GWP).

[0012] The brominated olefins described in Tapscott may have a certain level of effectiveness as anti-flammability agents in conjunction with certain materials; There is no disclosure of the use of such materials as blowing agents. Moreover, such compounds are believed to have certain drawbacks. For example, applicants have come to recognize that many of the compounds identified in Tapscott are relatively inefficient as blowing agents due to their relatively high molecular weight for such compounds. In addition, many of the compounds described in Tapscott face problems when used as blowing agents due to their relatively high boiling points for such compounds. Moreover, applicants have recognized that many highly substituted compounds may have undesirable toxicity properties and / or other undesirable properties, such as, for example, potentially environmentally undesirable bioaccumulation.

[0013] While Tapscott points out that bromine-containing alkenes having 2 to 6 carbon atoms may also contain fluorine substituents, the patent seems to suggest that fluorine-containing compounds are not entirely desirable from an environmental safety standpoint by noting that "fluorine-free bromoalkanes have very short atmospheric lifetimes due to reactions with hydroxyl free radicals in the troposphere" (col. 8, lines 34-39).

[0014] Additionally, substitutes for blowing agents may be used in conventional equipment and systems used in foam preparation and production. It is generally considered desirable to have this take effect without requiring major technological changes. Thus, applicants have recognized a need for compositions, particularly blowing agents, foamable compositions, foamed products, and methods and systems for producing foams that provide beneficial properties and / or avoid one or more of the above-mentioned disadvantages. Also, applicants have recognized a need for compositions, particularly blowing agents, that are potentially beneficial in numerous applications and / or avoid one or more of the above-mentioned disadvantages.

[0015] The present invention relates to compositions, methods and systems that have utility in numerous applications, including, inter alia, those relating to compositions, methods, systems and agents relating to polymeric foams. [Abstract] The applicant has addressed these and other needs by providing one or more fluoroalkenes having from 2 to 6 carbon atoms, more preferably one or more fluoroalkenes having from 3 to 5 carbon atoms, and even more preferably one or more fluoroalkenes having the following formula I: XCF z R 3-z (I) wherein X is a C1, C2, C3, C4, or C5 unsaturated, substituted or unsubstituted group, each R is independently Cl, F, Br, I, or H, and z is 1 to 3. It has been found that the present invention can be satisfactorily achieved by the blowing agent composition, foamable composition, foam and / or foamed article comprising a compound having the formula: Preferably, none of them is Br.

[0016] In embodiments where at least one Br substituent is present, it is preferred that the compound does not contain hydrogen. In such embodiments, it is also typically preferred that the Br substituent is on an unsaturated carbon, and more preferably, the Br is on a non-terminal unsaturated carbon. A particularly preferred compound of this type is CF3CBr=CF2, including all of its isomers.

[0017] In some embodiments, the compound of formula I has 3 to 5 fluorine substituents and the other substituents are It is highly preferred that propene, butene, pentene and hexene are either present or absent. In one preferred embodiment, none of R is Br, and preferably In the above, the unsaturated groups do not contain any Br substituents. Of these propenes, tetrafluoropropene (HFO-1234) and fluorochloropropenes (e.g., trifluoro, monochloropropene (HFCO-1233), and more preferably CF3CCl=CH2 (HFO-1233xf) and CF3CH=CHCl (HFO-1233zd)) are particularly preferred in certain embodiments.

[0018] In certain embodiments, pentafluoropropenes, particularly those containing pentafluoropropenes having a hydrogen on the terminal unsaturated carbon, such as CFCF=CFH (HFO-1225yez), are disclosed herein because Applicants believe that such compounds have at least a relatively low toxicity compared to CFCH=CF (HFO-1225zc). It has been found that the compound has the following structure:

[0019] In certain embodiments, among the butenes, fluorochlorobutenes are particularly preferred. The term "HFO-1234" is used herein to refer to all tetrafluoropropenes. Tetrafluoropropenes include 1,1,1,2-tetrafluoropropene (HFO-1234yf) and both cis- and trans-1,1,1,3-tetrafluoropropene (HFO-1234ze). The term "HFO-1234ze" is used herein to collectively refer to 1,1,1,3-tetrafluoropropene, whether cis- or trans-isomer. The terms "cisHFO-1234ze" and "transHFO-1234ze" are used herein to describe the cis- and trans-isomers of 1,1,1,3-tetrafluoropropene, respectively. Thus, the term "HFO-1234ze" includes within its scope cisHFO-1234ze, transHFO-1234ze, and all combinations and mixtures thereof.

[0020] The term "HFO-1233" is used herein to refer to any trifluoro, monochloropropene. Trifluoro, monochloropropenes include 1,1,1-trifluoro-2-chloropropene (HFCO-1233xf) and both cis- and trans-1,1,1-trifluoro-3-chloropropene (HFCO-1233zd). The term "HFCO-1233zd" is used herein to refer to 1,1,1-trifluoro-3, chloropropene, whether in the cis or trans form. The term "cisHFCO-1233zd" and "transHFCO-1233zd" are used herein to refer collectively to 1,1,1-trifluoro-3-chloropropene in its cis- and trans-form, respectively. Thus, the term "HFCO-1233zd" includes within its scope cisHFCO-1233zd, transHFCO-1233zd, and all combinations and mixtures thereof.

[0021] The term "HFO-1225" is used herein to refer to any pentafluoropropene. Such molecules include both cis- and trans-forms of 1,1,1,2,3 pentafluoropropene (HFO-1225yez). Thus, the term "HFO-1225yez" refers to this Here, 1,1,1,2,3 pentafluoro, whether cis or trans, is used. It is used to refer collectively to propene. Hence the term "HFO-1225yez." includes within its scope cisHFO-1225yez, transHFO-1225yez, and all combinations and mixtures thereof. The present invention also provides methods and systems that use the compositions of the present invention, including methods and systems for foam expansion. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] composition The compositions of the present invention may generally be in the form of a blowing agent composition or a foamable composition, in each case requiring at least one fluoroalkene compound as described herein and optionally other ingredients, some of which are described in more detail below. A. Fluoroalkenes A preferred embodiment of the present invention comprises at least one fluoroalkyl group containing from 2 to 6 carbon atoms, preferably from 3 to 5 carbon atoms, more preferably from 3 to 4 carbon atoms, and in certain embodiments most preferably 3 carbon atoms, and containing at least one carbon-carbon double bond. The fluoroalkene compounds of the present invention, when they contain at least one hydrogen, are sometimes referred to herein for convenience as hydrofluoroolefins, or "HFOs." It is contemplated that the HFOs of the present invention may contain two carbon-carbon double bonds. Although it is possible to use HFOs as substitutes for HFCO, such compounds are not currently considered preferred. The name HFCO is sometimes used herein for HFOs that also contain at least one chlorine atom.

[0023] As noted above, the compositions of the present invention comprise one or more compounds according to formula I. In some embodiments, the compositions of the present invention comprise one or more of the following formula II:

[0024] [ka]

[0025] wherein each R is independently Cl, F, Br, I, or H; R' is (CR2) n Y, Y is CRF2, and n is 0, 1, 2 or 3, preferably O or 1. In general, it is preferred that either Br is not present in the compound, or, if Br is present in the compound, the compound does not contain hydrogen.

[0026] In a highly preferred embodiment, Y is CF3, n is 0 or 1 (most preferably 0), and at least one remaining R is F, and preferably none of R is Br. When R is not present or Br is present, there are no hydrogens present in the compound. In certain cases, it is preferred that none of R in formula II is Br.

[0027] Applicants believe that, in general, the compounds of formula I and formula II identified above are generally effective and are believed to show utility in blowing agent compositions in accordance with the teachings contained herein. However, applicants have surprisingly and unexpectedly found that some compounds having the structure set forth in the above formula exhibit highly desirable low levels of toxicity as compared to other such compounds. As will be readily appreciated, this discovery is potentially highly advantageous and beneficial with respect to the formulation of blowing agent compositions. More specifically, applicants have found that compounds of formula I or formula II (preferably, where Y is CF3) in which at least one R on the terminal carbon of the unsaturation is H and at least one remaining R is F or Cl are suitable for use in blowing agent compositions. and n is 0 or 1), is believed to be associated with a relatively low level of toxicity. It is also believed that all structural isomers, geometric isomers and stereoisomers of such compounds are effective and advantageously have low toxicity.

[0028] In certain preferred embodiments, the compounds of the invention comprise a C3 or C4 HFO or HFCO, preferably includes a C3 HFO, and more preferably includes compounds according to formula I, where X is a C3 alkylene substituted with halogen and z is 3. In the formula, X is a C3 alkylene substituted with fluorine and / or chlorine, and Preferred in certain embodiments are C3 alkylene groups of the formula: -CH=CF-CH3 -CF=CH-CH3 -CH2-CF=CH2 -CH2-CH=CFH Accordingly, such embodiments include the following preferred compounds: CF3-CH=CF-CH3; CF3-CF=CH-CH3; CF3-CH2-CF=CH2; CF3-CH2-CH=CFH; and combinations thereof with each other and / or with other compounds according to Formula I or Formula II.

[0029] In certain preferred embodiments, the compounds of the invention comprise C3 or C4 HFCO, preferably C3 HFCO, and more preferably, wherein Y is CF3, n is 0, at least one R on the terminal carbon of the unsaturation is H, and at least one of the remaining R is Cl. , including compounds according to formula II. HFCO-1233 is an example of such a preferred compound.

[0030] In highly preferred embodiments, particularly those including the low toxicity compounds described above, n is 0. In certain highly preferred embodiments, the compositions of the present invention include one or more tetrafluoropropenes, including HFO-1234yf, (cis)HFO-1234ze, and (trans)HFO-1234ze, with HFO-1234ze generally being preferred, and transHFO-1234ze being highly preferred in certain embodiments. Although the properties of (cis)HFO-1234ze and (trans)HFO-1234ze differ in at least some respects, each of these compounds is suitable for use alone or together with other compounds, including their stereoisomers, in connection with each of the applications, methods, and systems described herein. For example, (trans)HFO-1234ze has a low boiling point (-19°C) and is Therefore, (cis)HFO-1234ze, which has a boiling point of +9°C, may be preferred in certain systems, while (cis)HFO-1234ze, which has a boiling point of +9°C, may be preferred in other applications. Combinations of isomers may be acceptable and / or preferred in many embodiments. Thus, by the terms "HFO-1234ze" and 1,3,3,3-tetrafluoropropene, it should be understood that both stereoisomers are referred to, and unless otherwise indicated, the term is used to indicate that each of the cis- and trans-forms is applicable and / or useful for the purposes described.

[0031] The HFO-1234 compound is a known material and is listed in the Chemical Abstracts database. The catalytic gas phase fluorination of various saturated and unsaturated halogen-containing C3 compounds to produce fluoropropenes such as CF3CH=CH2 is described in U.S. Patents 2,889,379, 4,798,818 and 4,465,786, each of which is incorporated herein by reference. In European Patent 974571, which is further incorporated herein by reference, 1,1,1,3,3-pentafluoropropane (HFC-245fa) is reacted with chromium-based catalysts at elevated temperatures in the gas phase to produce fluoropropenes. or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg(OH)2. By contacting the liquid with 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3- It is disclosed that the compound according to the present invention can be produced by a method for producing tetrafluoropropene. Furthermore, the method for producing the compound according to the present invention is generally described in the "Production of Fluoropropene" patent application Ser. No. H0003789 (26267) Related to pending U.S. patent application entitled "Process for Producing Fluorpropenes" No. 6,399,433, which is also incorporated herein by reference.

[0032] Other preferred compounds for use in accordance with the present invention include pentafluoropropene, including all its isomers (e.g., HFO-1225), tetra- and penta-fluorobutene, including all its isomers (e.g., HFO-1354 and HFO-1345).Of course, the compositions of the present invention may include combinations of two or more of any compounds within the broad scope of the present invention, or within any of the preferred scopes of the present invention.

[0033] The compositions of the present invention, particularly those containing HFO-1234 (including HFO-1234ze and HFO-1234yf), are believed to have advantageous properties for a number of important reasons. For example, applicants believe, based at least in part on mathematical modeling, that the fluoroolefins of the present invention have substantially no negative impact on atmospheric chemistry and contribute negligibly to ozone depletion compared to some of their halogenated counterparts. Thus, the preferred compositions of the present invention have the advantage that they do not substantially contribute to ozone depletion. Additionally, the preferred compositions do not substantially contribute to global warming compared to many of the hydrofluoroalkanes currently in use.

[0034] In one preferred embodiment, the compositions of the present invention have a Global Warming Potential (GWP) of about 1000 or less. More preferably, the compositions of the present invention have a global warming potential of about 500 or less, and even more preferably about 150 or less. In some embodiments, the compositions of the present invention have a GWP of about 100 or less, and even more preferably about 75 or less. As used herein, "GWP" refers to the global warming potential (GWP) of the compositions of the present invention, which is incorporated herein by reference. It is measured over a 100-year time horizon in relation to the GWP of carbon dioxide, as defined in The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project.

[0035] In certain preferred embodiments, the compositions of the present invention preferably have an Ozone Depletion Potential (ODP) of 0.05 or less, more preferably 0.02 or less, and even more preferably an Ozone Depletion Potential (ODP) of about zero. As used herein, "ODP" refers to any of the compounds of the present invention which are incorporated herein by reference. This is set out in the "Scientific Assessment of Ozone Depletion, 2002, Report of the Global Ozone Survey and Monitoring Project of the World Meteorological Organization" which was established in 2002.

[0036] In particular, the compound of formula I, which is HFO-1234, more preferably HFO-1234ze, is included in the compositions of the invention. The amount of the compound of formula I and / or formula II may vary widely depending on, among other things, the application, and compositions containing more than trace amounts and less than 100% of the compound are within the broad scope of the present invention. Furthermore, the compositions of the present invention may be azeotropic, azeotrope-like or non-azeotropic. In preferred embodiments, the compositions of the present invention, particularly the blowing agent compositions, contain from about 1% to about 99% by weight, more preferably from about 5% to about 95% by weight, and even more preferably from about 40% to about 90% by weight of the compound of formula I and / or formula II. It preferably contains HFO-1234, and more preferably contains HFO-1234ze and / or HFO-1234yf.

[0037] B. Other Compositions - Blowing Agent Compositions In one embodiment of the present invention, the blowing agent composition comprises one or more compounds according to Formula I herein. The compound may consist of, or consist essentially of, one or more compounds according to Formula I herein. Thus, the present invention includes methods and systems that involve the use of one or more of the compounds of the present invention as blowing agents without the substantial presence of any amount of additional compositions. However, one or more compounds or components not falling within the scope of Formula I or Formula II may be used, if desired, but are preferred. Such optional additional compounds may serve as blowing agents (hereinafter, for convenience and without limitation, referred to as co-blowing agents). Other compounds that also play a role include surfactants, polymer modifiers, reinforcing agents, colorants, dyes, solubility enhancers, rheology modifiers, plasticizers, flame retardants, antibacterial agents, viscosity reducers, and fillers. , vapor pressure modifiers, nucleating agents, catalysts, etc. In certain preferred embodiments, dispersants, cell stabilizers, surfactants and other additives may also be incorporated into the foam compositions of the present invention. Certain surfactants are optional but preferably added to serve as cell stabilizers. Some representative materials are sold under the names DC-193, B-8404 and L-5340, which are generally described in U.S. Pat. Nos. 2,834,748, 2,917,480 and 2,846,458, which are incorporated herein by reference. Other optional additives for the blowing agent mixture include, for example, tri(2-chloroethyl) phosphate, tri(2-chloropropyl) phosphate, tri(2,3-dibromopropyl) phosphate, tri(2,3-dibromopropyl) phosphate, and the like. The flame retardants may include such as phosphate, tri(1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.

[0038] As regards the nucleating agent, all known compounds and substances having nucleating function can be used in the present invention, including in particular talc. Of course, the compositions of the present invention may also contain other compounds and / or ingredients that modify specific properties of the composition (e.g., cost, etc.), and the presence of such compounds and ingredients is within the broad scope of the present invention.

[0039] Thus, preferred embodiments of the compositions of the present invention include, in addition to the compounds of formula I (including, in particular, HFO-1234ze and / or HFO-1234yf), one or more co-blowing agents. The co-blowing agents include physical blowing agents, chemical blowing agents (which in certain embodiments include, but are not limited to, or water) or a foaming agent having a combination of properties of physical and chemical blowing agents. The compositions of the present invention, which include a compound of formula I and a co-blowing agent, may include It will also be understood that the blowing agent may exhibit properties in addition to those required to be characterized as a blowing agent. For example, the blowing agent compositions of the present invention may contain compounds of formula I as described above, which also impart certain beneficial properties to the blowing agent composition or to the foamable composition to which it is added. For example, the compound of formula I or a co-blowing agent may include a component comprising: It is within the scope of the present invention that the copolymer may also serve as a polymer modifier or viscosity reducer.

[0040] While a wide variety of co-blowing agents are contemplated for use in accordance with the present invention, in certain embodiments, the blowing agent compositions of the present invention include one or more HFCs as co-blowing agents, more preferably Preferably, it comprises one or more HFCs having 1 to 4 carbon atoms, and / or one or More preferably, the blowing agent composition of the present invention comprises two or more hydrocarbons, more preferably hydrocarbons having 4 to 6 carbon atoms. For example, with respect to HFCs, the blowing agent composition of the present invention may comprise difluoromethane (HFC-32), fluoroethane (HFC-33), Fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-144), Fluoroethane (HFC-134), Pentafluoroethane (HFC-125), Pentafluoropropane (HFC-245), Hexafluoropropane (HFC-236), Heptafluoropropane (HFC-227ea), Pentafluoropropane (HFC-245), Hexafluoropropane (HFC-236), Heptafluoropropane (HFC-227ea), Trifluorobutane (HFC-365), hexafluorobutane (HFC-356) and the different derivatives of such HFCs. With respect to hydrocarbons, the blowing agent compositions of the present invention, in certain preferred embodiments, include, for example, iso, normal and / or cyclopentane for thermoset foams, and butane or isobutane for thermoplastic foams. Of course, water, CO2, CFCs (e.g., trichlorofluoromethane (CFC-11) and dichloromethane (DMF-11) are also included. CFC-12), hydrochlorocarbons (e.g., dichloroethylene ( Preferably, the HCFCs are trans-dichloroethylene, ethyl chloride, chloropropane, and other HCCs, HCFCs, alcohols having 1 to 5 carbon atoms (e.g., ethanol and / or propanol), and the like. Aldehydes having 1 to 4 carbon atoms, such as alcohol and / or butanol, Ketones having from 1 to 4 carbon atoms, ethers having from 1 to 4 carbon atoms (including ethers (e.g., dimethyl ether and diethyl ether), diethers (e.g., dimethoxymethane, diethoxymethane, etc.), and methyl formate, and any combination thereof, may be included, although such components are considered undesirable in many embodiments due to their negative environmental impact.

[0041] In certain embodiments, one or more of the following HFC isomers may be co-produced in the compositions of the present invention: Preferred for use as foaming agents: 1,1,1,2,2-Pentafluoroethane (HFC-125), 1,1,2,2-Tetrafluoroethane (HFC-134), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,3,3,3-Hexafluoropropane (HFC-236fa), 1,1,1,3,3-Pentafluoropropane (HFC-245fa), and 1,1,1,3,3-Pentafluorobutane (HFC-365mfc).

[0042] The relative amounts of any additional co-blowing agents referred to above, as well as the relative amounts of any additional components that may be included in the compositions of the present invention, may vary widely within the general broad scope of the present invention according to the particular application of the composition, and it is believed that all such relative amounts should be within the scope of the present specification. However, Applicants believe that one of the unique advantages of at least some of the compounds of formula I described in the present invention, such as HFO-1234ze, is that refers to such compounds having relatively low flammability. Thus, in some embodiments, the blowing agent compositions of the present invention include at least one co-blowing agent and a compound according to formula I in an amount sufficient to produce a blowing agent composition that is, as a whole, non-flammable. Thus, in such an embodiment, the co-development of the compound of formula I is preferably The relative amounts of blowing agents will depend, at least in part, on the flammability properties of the co-blowing agents.

[0043] The blowing agent compositions of the present invention may contain a wide range of amounts of the compounds of the present invention. However, preferred compositions for use as blowing agents according to the present invention comprise a compound according to Formula I, More preferably, the compound according to formula II is present in an amount of at least about 1% by weight of the composition, more preferably at least about 5% by weight, and even more preferably at least about 15% by weight. In certain preferred embodiments, the blowing agent comprises at least about 50% by weight of the blowing agent compound of the present invention, and in certain embodiments, the blowing agent is substantially composed of the compounds described in the present invention. In this regard, it is noted that the use of one or more co-blowing agents is not inconsistent with the novel and fundamental features of the present invention. For example, it is contemplated that water will be used in numerous embodiments either as a co-blowing agent or in combination with other co-blowing agents (such as, for example, pentane, particularly cyclopentane, etc.).

[0044] It is contemplated that the blowing agent compositions of the present invention may contain HFO-1234yf, cisHFO-1234ze, transHFO1234ze, or a combination of two or more thereof, preferably in an amount of at least about 15% by weight of the composition. In many preferred embodiments, a co-blowing agent comprising water is included in the composition, most preferably in compositions intended for use in thermoset foams. In certain preferred embodiments, the foam compositions of the present invention comprise a mixture of about 1:99 to about 50:50, More preferably, it comprises a combination of cisHFO-1234ze and transHFO1234ze in a cis:trans weight ratio of about 10:90 to about 30:70. In some embodiments, it may be preferred to use a combination of cisHFO-1234ze and transHFO1234ze in a cis:trans weight ratio of about 1:99 to about 10:90, more preferably about 1:99 to about 5:95. Of course, for example, in combination with a liquid blowing agent, In certain embodiments, such as with foamable compositions suitable for use in, it may be desirable to use combinations in which the cis-isomer is present in higher concentrations than the trans-isomer.

[0045] In one preferred embodiment, the blowing agent composition comprises from about 30% to about 95% by weight of a compound of formula I, More preferably, the compound of formula II is included, and even more preferably, one or more HFO-1234 compounds, and from about 5% to about 90%, more preferably from about 5% to about 65%, by weight of a co-blowing agent. In some of such embodiments, the co-blowing agent is selected from the group consisting of HO, HFCs, hydrocarbons, alcohols (preferably C2, C3 and / or C4 alcohols), CO2, and combinations thereof. and preferably consists essentially of

[0046] In a preferred embodiment in which the co-blowing agent comprises HO, the composition comprises from about 5% by weight of the total blowing agent composition HO in an amount of about 50% by weight, more preferably from about 10% to about 40% by weight, and even more preferably from about 10% to about 20% by weight of the total blowing agent.

[0047] In a preferred embodiment in which the co-blowing agent comprises CO2, the composition comprises from about 5% by weight of the total blowing agent composition More preferably, CO2 is included in an amount of about 60% by weight, more preferably from about 20% to about 50% by weight, and even more preferably from 40% to about 50% by weight of the total blowing agent.

[0048] In preferred embodiments where the co-blowing agent comprises an alcohol (preferably a C2, C3 and / or C4 alcohol), the composition comprises the alcohol in an amount of about 5% to about 40% by weight of the total blowing agent composition. More preferably, the total blowing agent is present in an amount of from about 10% to about 40% by weight, and even more preferably from 15% to about 25% by weight.

[0049] For compositions that include an HFC co-blowing agent, the HFC co-blowing agent (preferably C2, C3, C4 and / or C5 HFC), and more preferably difluoromethane (HFC-152a) (HFC-152a is an extrusion Particularly preferred for molded thermoplastics) and / or pentafluoropropane Pan (HFC-245) is preferably present in the composition in an amount of about 5% to about 80% by weight of the total blowing agent composition, more preferably about 10% to about 75% by weight of the total blowing agent, and even more preferably 25% to about 75% by weight. Further, in such embodiments, the HFC is preferably a C2-C4 HFC, and more preferably a C3 HFC, with pentafluorinated C3 HFCs such as HFC-245fa being highly preferred in certain embodiments. stomach.

[0050] For compositions containing a HC co-blowing agent, the HC co-blowing agent (preferably C3, C4 and / or C5 HC) is preferably present in the composition in an amount of about 5% to about 80% by weight of the total blowing agent composition, Most preferably, it is present in the composition in an amount of from about 20% to about 60% by weight of the total blowing agent.

[0051] C. Other Ingredients - Foamable Composition According to one aspect of the present invention, there is provided a foamable composition. As known to those skilled in the art, a foamable composition generally comprises one or more components capable of forming a foam. As used herein, the term "foam foaming agent" is used to refer to a component, or combination of components, capable of forming a foam structure, preferably a cellular foam structure. The foamable composition of the present invention comprises such a component and a blowing agent compound, preferably a compound of formula I, in the composition of the present invention. In some embodiments, the one or more components capable of forming a foam include a thermosetting composition capable of forming a foam and / or a foamable composition. Examples of thermosetting compositions also include polyurethane and polyisocyanurate foam compositions, and phenolic foam compositions. This reaction and foaming process may be facilitated by the use of various additives, such as catalysts and surfactant materials, which serve to control and adjust the cell size and stabilize the foam structure during formation. It is further contemplated that any one or more additional components described above with respect to the blowing agent compositions of the present invention may be incorporated into the foamable compositions of the present invention. In such thermosetting foam embodiments, one or more of the compositions of the present invention are included as part of the blowing agent in the foamable composition, or are preferably included as part of a two- or three-component foamable composition that includes one or more components that can react and / or foam under suitable conditions to form a foam or cell structure.

[0052] In certain other aspects of the invention, the one or more components capable of being foamed include thermoplastic materials, particularly thermoplastic polymers and / or resins. Examples of thermoplastic foam components include polyolefins, such as monovinyl aromatic compounds of the formula Ar-CHCH2, where Ar is a benzene-based aromatic hydrocarbon radical, such as polystyrene (PS). Other examples of polyolefin resins suitable for the invention include various ethylene resins, including ethylene homopolymers, such as polyethylene and ethylene copolymers, polypropylene (PP), and polyethylene terephthalate (PET). In certain aspects, the thermoplastic foamable polymers include polyolefins, such as monovinyl aromatic compounds of the formula Ar-CHCH2, where Ar is a benzene-based aromatic hydrocarbon radical, such as polystyrene (PS). Other examples of polyolefin resins suitable for the invention include various ethylene resins, including ethylene homopolymers, such as polyethylene and ethylene copolymers, polypropylene (PP), and polyethylene terephthalate (PET). The extrudable composition is an extrudable composition.

[0053] Methods and systems It is believed that currently known and available methods and systems for forming foams can be readily adapted for use in connection with the present invention. For example, the methods of the present invention generally require incorporating the blowing agent of the present invention into a foamable or foam-forming composition, and then frothing the composition, preferably by a step or series of steps including causing a volume expansion of the blowing agent of the present invention. In general, it is believed that currently used systems and equipment for incorporating blowing agents and for frothing can be readily adapted for use in the present invention. Indeed, it is believed that one of the advantages of the present invention is the improved blowing agent installation, which is generally compatible with existing frothing methods and systems.

[0054] It will therefore be understood by those skilled in the art that the present invention includes methods and systems for all types of foams, including thermoset foams, thermoplastic foams and formed-in-place foams. Accordingly, one aspect of the present invention is the use of the blowing agents of the present invention with conventional foaming equipment, such as polyurethane foaming equipment, under conventional processing conditions. Thus, the process of the present invention includes a masterbatch type operation, a mixing step, the addition of blowing agent in a third stream, and the foaming step at the foam head. Including the addition of foaming agents.

[0055] For thermoplastic foams, a preferred method involves adding a blowing agent according to the present invention to a thermoplastic material, preferably a thermoplastic polymer such as a polyolefin, and then exposing the thermoplastic material to conditions effective to cause foaming. For example, adding the blowing agent to the thermoplastic material may include adding the blowing agent to a screw extruder containing the thermoplastic material, and causing foaming includes reducing pressure on the thermoplastic material, which causes the blowing agent to expand and, as a result, the material becomes foamed.

[0056] It will be understood by those skilled in the art, particularly in light of the disclosure contained herein, that the order and manner in which the blowing agent of the present invention is 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, it is possible that the various components of the blowing agent and even the components of the foamable composition are not mixed prior to addition to the extrusion apparatus, or that the components are not even added to the same location within the extrusion apparatus. Furthermore, the blowing agent can be added either directly or as part of a premix that is then further added to other portions of the foamable composition.

[0057] Thus, in some embodiments, it may be desirable to add one or more components of the blowing agent at an initial location in the extruder, upstream of where the other one or more components of the blowing agent are added, in anticipation of the components of the blowing agent coming together in the extruder and / or operating more efficiently in this process. Nevertheless, in some embodiments, two or more components of the blowing agent are precombined and added together to the foamable composition, either directly or as part of a premix that is then further added to other portions of the foamable composition.

[0058] One aspect of the present invention relates to a method for forming foams, and preferably polyurethane and polyisocyanurate foams. As is well known in the art, the method generally includes providing a blowing agent composition of the present invention, adding the blowing agent composition (directly or indirectly) to a foamable composition, and reacting the foamable composition under conditions effective to form a foam or froth structure. Any method well known in the art can be used or adapted for use in accordance with the foam aspect of the present invention, such as the methods described in Polyurethanes Chemistry and Technology, Vols. 1 and 2, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, incorporated herein by reference. Generally, such preferred methods include preparing a polyurethane or polyisocyanurate foam by combining an isocyanate, a polyol or mixture of polyols, a blowing agent or mixture of blowing agents comprising one or more compositions of the present invention, and other materials such as, for example, a catalyst, a surfactant, and optionally, a flame retardant, a colorant, or other additives.

[0059] It is convenient in many applications to provide the ingredients for polyurethane or polyisocyanurate foams in a premixed formulation. Most typically, the foam formulation is premixed into two components. The isocyanate and optional surfactants and blowing agents are usually premixed in a "mixture" known in the art. The polyol or polyol mixture, surfactants, catalysts, blowing agents, flame retardants, and other isocyanate-reactive components constitute the first component, commonly referred to as the "B" component. Thus, the polyurethane or polyisocyanurate foam may be hand mixed for preparation of small quantities, or, preferably, formed into blocks, slabs, laminates, pour-in-place panels and other products, spray applied foams, bubbles, etc. To achieve this, the composition can be readily prepared by combining components A and B by mechanical mixing techniques. Optionally, for example, flame retardants, colorants, auxiliary blowing agents, and Additionally, other components such as other polyols may be added as additional streams to one or more of the mix heads or reaction locations, but most preferably these are all incorporated into the B component above.

[0060] The method and system of the present invention also includes forming a one-component foam, preferably a polyurethane foam, containing a blowing agent according to the present invention. In certain preferred embodiments, a portion of the blowing agent is included in the foam forming agent, preferably by dissolving it in the foam forming agent, which is liquid at the pressure in the container, and a second portion of the blowing agent is present as a separate gas phase. In such systems, the contained / dissolved blowing agent primarily causes the expansion of the foam, and the separate gas phase acts to provide a driving force for the foam forming agent. Such one-component systems are typically and preferably enclosed in a container, such as an aerosol can, and thus the blowing agent of the present invention preferably provides provision for the expansion of the blowing agent and / or provides energy to transport the foam material / foamable material from the package, preferably both. In certain embodiments, such systems and methods are carried out by dissolving the foam in a fully formulated system (preferably an isocyanate / polyol system) in a package. and incorporating the gas foam of the present invention into a package, preferably an aerosol can.

[0061] Any method well known in the art can be used or adapted for use in accordance with the foam-forming aspects of the present invention, such as those described in Polyurethanes Chemistry and Technology, Vols. 1 and 2, Saunders and Frisch, 1962, John Wiley and Sons, New York, New York, incorporated herein by reference.

[0062] It is also contemplated that it may be preferable to use the compositions of the present invention in a supercritical or near supercritical state as the blowing agent. Foam The present invention relates to any foam (including closed cell foam, open cell foam, etc.) prepared by a polymer foam formulation containing a blowing agent comprising the composition of the present invention. Applicants believe that one advantage of foams, particularly thermoset foams such as polyurethane foams according to the present invention, is the low thermal expansion coefficient, particularly and preferably under low temperature conditions, as measured, for example, by K-factor or lambda, in connection with the thermoset foam embodiment. It has been found that the ability to achieve very good thermal properties that can be achieved with the present invention is a key advantage. While it is contemplated that the foams of the present invention, and in particular the thermoset foams of the present invention, can be used in a variety of applications, in certain preferred embodiments, the present invention is directed to foams for use in refrigerators, freezer foams, refrigerator / freezer foams, panel foams, and other low temperature or cryogenic manufacturing equipment. , including the device foams described in the present invention.

[0063] In certain preferred embodiments, the foams described herein provide one or more highly advantageous features, properties, and / or characteristics, including thermal insulation efficiency (particularly for thermoset foams), dimensional stability, compressive strength, thermal insulation efficiency over time, in addition to the low ozone depletion potential and low global warming potential associated with many of the preferred blowing agents of the present invention. In certain highly preferred embodiments, the present invention provides thermoset foams, such as those foams formed into foam articles, that use the same blowing agents (or HFC-245fa, a commonly used blowing agent) in the same amounts, but that are not produced using the same blowing agents as those used in the present invention. The foams exhibit improved thermal conductivity compared to foams made without the compound of formula I described in . In certain highly preferred embodiments, the thermoset foams, and preferably the polyurethane foams of the present invention, have a K-factor (BTU in / hr ft ) of about 0.14 or less at 40° F. 2 °F) and Preferably, it is 0.135 or less, and more preferably, it is 0.13 or less. For example, the thermoset foam, and preferably the polyurethane foam of the present invention, has a viscosity of about 0.16 or less at 75° F. K-Factor below (BTU in / hr ft 2 °F), more preferably 0.15 or less, and even more preferably 0.145 or less.

[0064] In other preferred embodiments, the foams of the present invention exhibit improved mechanical properties as compared to foams produced with blowing agents outside the scope of the present invention. For example, certain preferred embodiments of the present invention have compressive strengths superior to, and preferably at least about 10% greater relative to, foams produced under substantially identical conditions using a blowing agent consisting of cyclopentane. and more preferably at least about 15% greater relative compressive strength. The present invention further provides a foam and a foam product comprising the foam, the foam and the foam product comprising the foam, the foam and the foam product comprising the foam, the foam and the foam product further ... further comprising the foam, the foam and the foam product further comprising the foam It is preferred that foams produced according to the present invention have compressive strengths comparable to those exhibited by foams made under substantially similar conditions on a commercial basis. In certain preferred embodiments, the foams of the present invention exhibit a yield (parallel and perpendicular) of at least about 12.5%, and more preferably at least about 13% yield. The diagram shows the respective directions as shown.

[0065] Working Example The following examples are offered for the purpose of illustrating the invention without limiting its scope. Example 1A - Polystyrene Foam This example illustrates the use of blowing agents in accordance with two preferred embodiments of the present invention, namely, HFO-1234ze and HFO-1234yf, and the production of polystyrene foam. Testing equipment and procedures have been established to aid in determining whether a particular blowing agent and polymer is capable of producing a foam, and the quality of the foam. Ground Polymer A polystyrene polymer (Dow Polystyrene 685D) and a blowing agent consisting essentially of HFO-1234ze are combined in a vessel. A schematic of the vessel is shown below. The vessel has a volume of 200 cm 3 and the vessel consists of two pipe flanges and a 2 inch diameter, schedule 40, 4 inch long section of stainless steel pipe. The vessel is placed in an oven with a set temperature of about 190°F to about 285°F, preferably 265°F for polystyrene, and left there until thermal equilibrium is reached.

[0066] [ka]

[0067] The pressure in the vessel is then released, instantly producing a foamed polymer. The blowing agent dissolves in the polymer, plasticizing it. Using this method, the densities of the two foams thus produced were compared to the densities of foams produced using trans-HFO-1234ze and HFO-1234yf. The data are given in Table 1. The data show that expanded polystyrene can be obtained according to the present invention. In this respect, the bulk density of polystyrene is about 1050 kg / m at room temperature. 3 That is 65.625 lb / ft 3 in It is noted that:

[0068] [Table 1]

[0069] Example 1B - Polystyrene Foam This example illustrates the performance of HFO-1234ze alone as a blowing agent for polystyrene foam made in a twin-screw extruder. The equipment used in this example is a Leistritz twin-screw extruder having the following characteristics: 30mm co-rotating screw L:D ratio = 40:1 The extruder was divided into 10 sections, each with an L:D ratio of 4:1. The polystyrene resin was placed in the first section, the blowing agent in the sixth section, and the extrudate exited in the tenth section. The extruder operated primarily as a melt / mix extruder. The subsequent cooling extruder was connected in series and had the following design characteristics: Leistritz twin screw extruder 40mm co-rotating screw L:D ratio = 40:1 Die: 5.0mm round Polystyrene resin, Nova Chemical - a typical extrusion quality polystyrene identified as Nova 1600 - is fed to the extruder under the conditions set forth above. The recommended melting point of the resin is 375°F-525°F. The extruder pressure at the die is about 1320 pounds per inch (psi) and the temperature at the die is about 115°C.

[0070] The blowing agent consisting essentially of transHFO-1234ze is used as a nucleating agent in an amount of about 0.5 parts by weight relative to the total blowing agent. % of talc is added at the above location in the extruder. Foams have been produced in accordance with the present invention using concentrations of blowing agent of 10%, 12% and 14% by weight. The density of the foams produced is about 0.1 g / cm 3 from 0.07g / cm 3 The foams, approximately 30 mm in diameter, are of very high quality in appearance and have very fine cell sizes. It is always fine and free of visible or obvious blowholes and voids.

[0071] Example 1C - Polystyrene Foam The process of Example 1B is repeated except that the foaming agent contains about 50% by weight transHFO-1234ze and 50% by weight HFC-245fa, and a nucleating agent in the concentrations shown in Example 1B. Styrene is prepared at blowing agent concentrations of about 10% and 12%. The density of the foam produced is about 0.09 g / cm 3 The size of the bubbles is about 200 μm. The foam with a diameter of about 30 mm is It is of very high quality to the eye, with a fine bubble structure and no visible or obvious voids.

[0072] Example 1D - Polystyrene Foam The steps of Example 1B are repeated except that the foaming agent contains about 80% by weight HFO-1234ze and 20% by weight HFC-245fa, as well as the nucleating agent in the concentrations shown in Example 1B. Expanded Polystyrene is prepared with blowing agent concentrations of about 10% and 12%. The density of the foam produced is about 0.08 g / cm 3 The size of the bubbles is about 120 μm. The foam has a diameter of about 30 mm and looks very It is of extremely high quality, has a fine bubble structure and has no visible or obvious voids.

[0073] Example 1E - Polystyrene Foam This step of Example 1B was repeated except that the foaming agent was about 80% by weight HFO-124ze and 20% by weight HFC-245fa, as well as Repeat Example 1B, but include the nucleating agent in the concentrations shown. is prepared with foaming agent concentrations of about 10% and 12%. The density of the foam is 0.1 g / cm 3 The foams, approximately 30 mm in diameter, were visually of very high quality, with a fine cell structure and visible No visible or obvious voids.

[0074] Example 1F - Polystyrene Foam The process of Example 1E is repeated except that the nucleating agent is omitted. The density of the foam is 0.1 g / cm 3 and the cell diameter size is about 400. The foams, approximately 30 mm in diameter, are visually of very high quality, with a fine cell structure and no visible or obvious voids.

[0075] Example 2 - Compressive Strength of Polyurethane Foam This example shows the performance of HFO-1234ze and its isomers used in combination with a hydrocarbon co-blowing agent, and in particular, the utility in polyurethane foam compressive strength performance of a composition including HFO-1234ze and a cyclopentane co-blowing agent.

[0076] A commercial, refrigerated type polyurethane foam formulation (foam former) is provided. The polyol blend consisted of commercial polyols, catalysts and surfactants. The formulation is suitable for use in conjunction with a gaseous blowing agent. Standard commercial polyurethane processing equipment is used for the foam production process. A gaseous blowing agent combination was formed containing approximately 60 mole % HFO-1234ze (including its isomers) and approximately 40 mole % cyclopentane, based on total blowing agent. This example illustrates the physical property performance of a combination of HFO-1234ze (including its isomers) in combination with a cyclopentane co-blowing agent. Table 2 below compares foams made using a blowing agent consisting of HFC-245fa and a blowing agent consisting of cyclopentane. In comparison, it represents the compressive strength of a similar machine made polyurethane foam using the blowing agent of the present invention.

[0077] [Table 2]

[0078] One unexpected result illustrated by this example is that HFO-1234ze and HFC-1234ze The advantage of the PO / HFC blends is that they can be processed in conventional foam processing equipment, and polyurethane processing equipment in particular, which is a potentially significant advantage since it allows for foam processing with a variety of systems and equipment, including mix-type blending equipment, gaseous blowing agent blending equipment, third stream blowing agent addition, or blowing agent addition at the foam head.

[0079] Example 3 - Polyurethane Foam K-Factor Polyurethane foams are prepared and adapted for use as commercial "appliance type" polyurethane formulations. The same foam formulations described in Example 2 are used in conjunction with the same standard commercial polyurethane processing equipment used in the foam formation process. Several systems are prepared, each using the same ingredients, systems, and equipment, apart from the blowing agent. In addition to the blowing agents of the present invention, HFC-134a, HFC-245fa, and cyclopentane are also each tested as blowing agents. Each In the system, the blowing agent is added to a polyol blend in substantially equimolar concentrations. The polyol blend is comprised of commercial polyols, catalysts, and surfactants. The foams are prepared according to standard commercial manufacturing processes, such as commercial processes for making foams for refrigeration applications. The k-factors of the preferred foams are evaluated, and the results are shown in Table 3 below. For comparison, foams were prepared with HFC-134a for which commercial data is available. The k-factor data for these foams is shown in Table 3.

[0080] [Table 3]

[0081] This example shows the k-factor performance of HFO-1234ze and its isomers when HFO-1234ze blowing agent is substituted into a polyurethane formulation. HFO-1234ze is at equimolar concentrations compared to the benchmark foam. The data in Table 3 show that the k-factor of HFO-1234ze foam is shows a significant improvement over the cyclopentane foam.

[0082] Example 4 - Polyurethane Foam K-Factor This example illustrates the use of various HFC co-blowing agents in conjunction with the preparation of polyurethane foams. The results are shown in Table 1. The foam formulation, equipment and process are similar to those used in Examples 2 and 3, except for the blowing agent. Approximately 80% by weight of HFO-1234ze (including its isomers) is used relative to the total blowing agent, and approximately 100% by weight of HFO-1234ze (including its isomers) is used relative to the total blowing agent. A blowing agent containing about 20% by weight of HFC-245fa is prepared. In addition to the blowing agents of the present invention, HFC-134a and cyclopentane were also tested as blowing agents. In each system, the blowing agent was added to the polyol blend at substantially the same molar concentration. The blowing agent is then used to form a foam, and the k-factor of the foam is measured. Table 4 below shows the k-factor performance of HFO-1234ze (including its isomers) when used in combination with an HFC co-blowing agent.

[0083] [Table 4]

[0084] One unexpected result demonstrated by this example is that HFO-1234ze and HFC-1234ze / HFC blends can be processed in conventional polyurethane processing equipment, which is a potentially great advantage since it allows for foam processing with a variety of systems and equipment including mix-type blending equipment, gaseous blowing agent blending equipment, third stream blowing agent addition, or blowing agent addition at the foam head.

[0085] Example 5 - Polyurethane Foam K-Factor This example further illustrates the unexpected performance of blowing agents according to the present invention used in the manufacture of polyurethane foams. Three appliance polyurethane foams are made, each formed using substantially identical materials, processes and equipment, except that a different blowing agent is used. The polyol systems are commercially available. An appliance-type device adapted for use with a liquid foaming agent. A blowing machine is used to form the foams. The blowing agents are used in essentially the same molar concentrations. After formation, the foams are each subjected to a suitable sample to measure the k-factor. The k-factors are shown in Table 5B below. The weight percentages of the blowing agent compositions are shown below in Table 5A.

[0086] [Table 5]

[0087] The results shown in Table 8C indicate that the use of a compound of the present invention (HFO-1234ze) in combination with cyclopentane and HFC-245fa as a co-blowing agent in thermoset foams at those levels did not adversely affect the k-factor performance of HFO-1234ze when used alone or with HFC-245fa. This was an unexpected result since, historically, the use of cyclopentane in substantial amounts in foam formulations has adversely affected k-factor performance. do.

[0088] Example 6 - Polyurethane Foam K-Factor The experiment was conducted using the same polyol formulation and isocyanate as in Example 5. Foams are prepared by hand mixing. The blowing agent consists of the compound set forth in Formula II, i.e., HFCO-1233zd (CF3CH=CHCl)*, at approximately the same mole percentage to the foamable composition as the blowing agent in Example 5. The K-factors are shown in Table 6 below.

[0089] [Table 6]

Claims

1. (a) Formula I: XCF Z R 3-Z (I) wherein X is a C1, C2, C3, C4, or C5 unsaturated, substituted or unsubstituted group, each R is independently Cl, F, Br, I, or H, and z is 1 to 3, with the proviso that when Br is included in the compound, the compound does not contain hydrogen. At least one fluoroalkene represented by (b) Co-foaming agents, surfactants, polymer modifiers, reinforcing agents, colorants, dyes, dissolution promoters, flow improvers at least one adjuvant selected from the group consisting of additives, plasticizers, flame retardants, antibacterial agents, viscosity reducers, fillers, vapor pressure modifiers, nucleating agents, and catalysts, and combinations of any two or more of these; A blowing agent comprising:

2. 2. The blowing agent of claim 1, wherein the at least one fluoroalkene comprises at least one three carbon and / or at least one four carbon alkene having from 3 to 5 fluorine substituents.

3. 2. The blowing agent of claim 1, wherein the at least one fluoroalkene comprises cisHFO-1234ze or transHFO-1234ze or a combination thereof.

4. 2. The blowing agent of claim 1, wherein said at least one fluoroalkene comprises at least one butene having from 3 to 5 fluorine substituents.

5. The at least one fluoroalkene has formula II: 【Chemistry 1】 wherein each R is independently Cl, F, Br, I, or H, and R′ is (CR 2 )nY, where Y is the CRF 2 and n is 0 or 1.

2. The blowing agent of claim 1, which is a compound of the formula:

6. Y is CF 3 The blowing agent according to claim 5, wherein

7. 6. The blowing agent of claim 5, wherein at least one R on the terminal carbon of the unsaturation is not F.

8. 6. The blowing agent of claim 5, wherein at least one R on the terminal carbon of the unsaturation is H.

9. 2. The blowing agent of claim 1, having a global warming potential (GWP) of about 150 or less.

10. 2. The blowing agent of claim 1, having an ozone depletion potential (ODP) of about 0.05 or less.

11. The fluoroalkene comprises an unsaturated terminal carbon having not more than one F substituent. Item 1. A blowing agent according to item 1.

12. 2. The blowing agent of claim 1, wherein said fluoroalkene comprises an unsaturated terminal carbon and at least one substituent on the unsaturated terminal carbon is H.

13. 2. The blowing agent of claim 1, wherein the compound of formula I is free of Br.

14. The blowing agent of claim 1 , wherein said compound contains at least one chlorine substituent.

15. 15. The blowing agent of claim 14, wherein the compound comprises HFCO-1233.

16. 15. The blowing agent of claim 14, wherein the HFCO-1233 comprises HFCO-1233xf.

17. 15. The blowing agent of claim 14, wherein the HFCO-1233 comprises HFCO-1233zd.

18. 10. The blowing agent of claim 1, wherein said at least one compound of formula I is present in said composition in an amount of from about 5% to about 95% by weight of the blowing agent.

19. The blowing agent of claim 1 , wherein the adjuvant comprises at least one co-blowing agent.

20. 20. The blowing agent of claim 19, wherein the at least one co-blowing agent comprises one or more C1-C4HFCs.

21. The one or more HFCs may be selected from the group consisting of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoroethane (HFC-250), tetrafluoroethane (HFC-260), tetrafluoroethane (HFC-270), tetrafluoroethane (HFC-272), tetrafluoroethane (HFC-274), tetrafluoroethane (HFC-276), tetrafluoroethane (HFC-278), tetrafluoroethane (HFC-279), tetrafluoroethane (HFC-280), tetrafluoroethane (HFC-282), tetrafluoroethane (HFC-284), tetrafluoroethane (HFC-285), tetrafluoroethane (HFC-286), tetra 21. The blowing agent of claim 20, wherein the blowing agent is selected from the group consisting of fluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), all isomers thereof, and combinations of two or more thereof.

22. 20. The method of claim 19, wherein the at least one co-blowing agent comprises one or more C4-C6 hydrocarbons. The blowing agent described.

23. 23. The blowing agent of claim 22, wherein the one or more hydrocarbons are selected from the group consisting of isopentane, normal pentane, cyclopentane, butane, and isobutane, and combinations of two or more thereof.

24. and a foam forming agent, the foaming agent being represented by Formula I: XCF Z R 3-Z (I) wherein X is a C1, C2, C3, C4, or C5 unsaturated, substituted group, each R is independently Cl, F, Br, I, or H, and z is 1 to 3, with the proviso that when Br is included in the compound, the compound does not contain hydrogen.

2. A foamable composition comprising at least one fluoroalkene represented by:

25. 25. The foamable composition of claim 24, wherein the foam former comprises at least one thermoset foam component.

26. 26. The foamable composition of claim 25, wherein the at least one thermosetting component comprises a composition capable of forming a polyurethane foam.

27. 26. The foamable composition of claim 25, wherein the at least one thermosetting component comprises a composition capable of forming a polyisocyanurate foam.

28. 26. The foamable composition of claim 25, wherein the at least one thermosetting component comprises a composition capable of forming a phenolic foam.

29. 25. The foamable composition of claim 24, wherein the foam former comprises at least one thermoplastic foam component.

30. 30. The foamable composition of claim 29, wherein said at least one thermoplastic foam component comprises a thermoplastic polymer.

31. 30. The foamable composition of claim 29, wherein said at least one thermoplastic component comprises a polyolefin.

32. 32. The foamable composition of claim 31, wherein the polyolefin is selected from the group consisting of monovinyl aromatic compounds, ethylene-based compounds, propylene-based polymers, and combinations thereof.

33. A foam premix composition comprising a polyol and a blowing agent, the blowing agent being represented by Formula I: XCF Z R 3-Z (I) wherein X is a C1, C2, C3, C4, or C5 unsaturated, substituted group, each R is independently Cl, F, Br, I, or H, and z is 1 to 3, with the proviso that when Br is included in the compound, the compound does not contain hydrogen.

2. A foam premix composition comprising at least one fluoroalkene represented by:

34. The foamable and / or foam composition comprises a compound of Formula I: XCF Z R 3-Z (I) wherein X is a C1, C2, C3, C4, or C5 unsaturated, substituted group, each R is independently Cl, F, Br, I, or H, and z is 1 to 3, with the proviso that when Br is included in the compound, the compound does not contain hydrogen. A method for forming a foam comprising adding a blowing agent comprising at least one fluoroalkene represented by the formula:

35. 1. A foam comprising a plurality of polymeric cells and a composition contained within at least one of the cells, the composition comprising: (a) Formula I: XCF Z R 3-Z (I) wherein X is a C1, C2, C3, C4, or C5 unsaturated, substituted group, each R is independently Cl, F, Br, I, or H, and z is 1 to 3, with the proviso that when Br is included in the compound, the compound does not contain hydrogen. At least one blowing agent comprising at least one fluoroalkene represented by 3. A foam comprising:

36. 36. The foam of claim 35 in the form of one or more of a block, a plate, a laminate, a rigid foam, an open cell foam, a closed cell foam, a flexible foam, a skinned foam, a refrigerator foam, and a freezer foam.

37. K-Factor at 40°F (BTU in / hr ft 2 36. The foam of claim 35, wherein the foam has a viscosity of about 0.14°F or less.

38. K-Factor at 75°F (BTU in / hr ft 2 36. The foam of claim 35, wherein the foam has a viscosity of about 0.16°F or less.

39. 36. The foam of claim 35, having a parallel compressive strength of at least about 12.5% ​​yield.

40. 36. The foam of claim 35, having a normal compressive strength of at least about 12.5% ​​yield.

41. The adjuvant is water, CO2, CFC, HCC, HCFC, C1-C5 alcohol, C1-C4 aldehyde 2. The blowing agent of claim 1, comprising at least one co-blowing agent selected from the group consisting of C1-C4 ketones, C1-C4 ethers, and combinations of two or more thereof.

42. 25. The foamable composition of claim 24, wherein the foam forming agent is a thermoplastic material and the blowing agent further comprises a compound selected from the group consisting of C1-C5 alcohols, C1-C4 ethers, and combinations of two or more thereof.

43. 25. The foamable composition of claim 24, wherein the foam former is a thermoplastic and the blowing agent further comprises ethanol.

44. 25. The foamable composition of claim 24, wherein the foam former is a thermoplastic material and the blowing agent further comprises a compound selected from the group consisting of dimethyl ether, diethyl ether, and combinations thereof.

45. 25. The foamable composition of claim 24, wherein said foam forming agent is a thermosetting material and said blowing agent further comprises methyl formate.

46. 2. The blowing agent of claim 1, wherein the compound of formula I has at least four halogen substituents. 。

47. 47. The compound according to claim 46, wherein said at least four halogen substituents include at least three F substituents. The foaming agent.

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