HK1178195A

HK1178195A - Fluoropropene compounds and compositions and methods using same

Info

Publication number: HK1178195A
Application number: HK13105091.2A
Authority: HK
Inventors: Rajiv R. Singh; Gary Knopeck; David J. Williams
Original assignee: Honeywell International Inc.
Priority date: 2009-10-01
Filing date: 2010-09-28
Publication date: 2013-09-06

Description

Fluoropropene compounds and compositions and methods using the same

Cross reference to related applications

This application claims priority from U.S. provisional patent application No. 61/247,816, filed on 1/10/2009, and U.S. application No. 12/890,143, filed on 24/9/2010, the contents of which are incorporated herein by reference.

The following additional priority statements are made only for entering the national phase of the united states. The present application also claims the benefit of priority of a continuation-in-part application, filed as part of the currently pending U.S. application No. 12/351,807, on 10/1/2009, which is incorporated by reference as if fully set forth herein. This application also claims the benefit of a continuation-in-part application as part of each of the following U.S. patent applications and is incorporated herein by reference: U.S. application Ser. No. 10/694,273 (now U.S. Pat. No. 7,534,366) filed on 27/10/2003; 11/385,259, now pending, filed on 20/3/2006, which is in turn a continuing application filed on 27/10/2003, now abandoned 10/695,212; 10/694,272 (now U.S. Pat. No. 7,230,146), filed on day 27 of 10/2003; 10/847,192 (now U.S. Pat. No. 7,046,871) filed on 8/29/2007, which in turn was a division of 10/837,525 (now U.S. Pat. No. 7,279,451) filed on 29/4/2004; 11/475,605 on pending date, submitted on 26.6.2006; and, pending 12/276,137, filed on 21/11/2008, which claims the benefits of U.S. provisional application No. 60/989,997, filed on 25/11/2007, and pending U.S. application No. 11/474,887, filed on 26/6/2006, and PCT application No. PCT/US07/64570, filed on 21/3/2007.

Technical Field

The present invention relates to compositions, methods and systems useful for a number of applications, including in particular heat transfer systems, such as refrigeration systems, blowing agents, foamable compositions, foams and articles made with or from foams, solvents, aerosols, propellants and cleaning compositions. In a preferred aspect, the present invention relates to such compositions comprising at least one halopropene compound having at least four halogen substituents.

Background

Fluorocarbon-based fluids have been widely used in many commercial and industrial applications, including as working fluids in systems such as air conditioning, heat pump and refrigeration systems, as aerosol propellants, as blowing agents, as heat transfer media, as solvents and cleaning agents, and as gaseous dielectrics. However, many of the previously used materials are associated with environmental concerns. One such problem is the relatively high global warming potential associated with the use of some compositions heretofore used for these purposes. Another problem is that many previously used materials have unacceptably high ozone depletion potentials.

Another problem associated with many previously used compounds is that such compounds are considered volatile organic compounds or VOCs. In many of the above applications, including in particular solvating and cleaning applications, it is possible that at least a portion of the compound is released into the atmosphere substantially at ground level before, during and/or after use. In the upper atmosphere, the presence of ozone, also known as stratospheric ozone, is useful because it absorbs ultraviolet radiation and protects the earth from harmful ultraviolet radiation. Ground level ozone or tropospheric ozone, on the other hand, has and/or is believed to have adverse consequences for human health and the environment. When ultraviolet light from the sun enters the atmosphere, it reacts with nitrogen oxides (NOx) from various sources, including automobiles, manufacturing plants, power generation facilities, and other sources. The presence of VOCs in the atmosphere affects the overall balance between ozone and NOx, whereby more ozone may accumulate in the atmosphere. While the presence of stratospheric ozone may have a positive effect on the environment, at ground level, the presence of ozone is considered to be detrimental to the environment, causing haze (haze) in the troposphere, and the like.

Many factors contribute to the VOC's in the atmosphere, including natural or "biological" sources such as trees and vegetation. Man-made sources, such as vehicle emissions, oil refining and combustion, also contribute to VOC levels. The use of organic solvents causes VOC emissions if evaporated into the air. Thus, applicants have recognized that alternative materials to refrigerants, blowing agents, solvents, etc., are most preferred if they do not contribute tropospheric ozone enhancement at all or only minimally, i.e., they are not considered VOC's.

In the united states, the environmental protection agency ("EPA") has established a general definition of VOCs, which is very broad. Indeed, it is claimed that for regulatory purposes, "any volatile compound of carbon" is classified as a VOC unless it appears in a list of compounds that have been specifically exempted. Thus, the EPA has disclosed two lists of compounds specifically exempted from VOC regulation, even though they are "carbon compounds". The first is a short list of compounds that have not historically been regulated as VOCs, such as carbon monoxide and carbon dioxide. The second list of compounds is classified by EPA as "negligible reactive" and therefore non-VOC, as studies indicate that these compounds do not significantly contribute to ozone formation. One of the compounds in this list is ethane.

New methods of evaluating and addressing air quality and reducing ground level ozone have recently been developed. This approach considers the relative photochemical reactivity of a compound as a way to distinguish whether a molecule is a VOC. One method of assessing the relative photochemical reactivity of a compound is the Maximum Incremental Reactivity (MIR) scale, which measures the relative photochemical reactivity of a solvent on a common continuous scale. While MIR values are typically expressed in grams of ozone formed per gram of reacted VOC, relative information is equally valuable in this regard.

Accordingly, applicants have recognized the value of developing alternative fluids that not only have as low a global warming potential as possible while maintaining the desired performance properties, but are also advantageously considered to be not VOCs. In addition, it is desirable in some instances to use single component fluids or azeotrope-like mixtures that do not substantially fractionate upon boiling and evaporation.

Examples of in-situ use (use-in-place) properties include, inter alia, excellent heat transfer properties for heat transfer fluids, suitable chemical stability, low or no toxicity, non-flammability and/or lubricant compatibility, and other desirable foam characteristics when used as a blowing agent.

Applicants have recognized that lubricant compatibility is particularly important in many applications. More particularly, it is highly desirable that the refrigerant fluid be compatible with the lubricant used in the compressor unit used in most refrigeration systems. Unfortunately, many non-chlorine-containing refrigeration fluids, including HFCs, are relatively insoluble and/or immiscible in the types of lubricants traditionally used with CFCs and HFCs, including, for example, mineral oils, alkylbenzenes, or poly (alpha-olefins). In order for the refrigeration fluid/lubricant combination to operate at a desired level of efficiency in compression refrigeration, air conditioning and/or heat pump systems, the lubricant should be sufficiently soluble in the refrigerant fluid over a wide operating temperature range. This solubility reduces the viscosity of the lubricant and makes it more likely to flow throughout the system. In the absence of such solubility, the lubricant tends to accumulate in the coils of the evaporator of the refrigeration, air conditioning or heat pump system, as well as other parts of the system, and thereby reduce the efficiency of the system.

In terms of efficiency of use, it is important to note that the loss of refrigerant thermodynamic performance or energy efficiency has a secondary environmental impact through the increase in fossil fuel usage caused by the increase in electrical energy demand.

In addition, it is generally considered desirable for CFC refrigerants and blowing agent substitutes to work effectively without significant engineering changes to conventional systems, such as vapor compression technology and foaming systems.

Methods and compositions for the manufacture of traditionally foamed materials, such as thermoplastics and thermosets, have long been known. These methods and compositions generally use chemical and/or physical blowing agents to form a foamed structure in a polymeric matrix. Such blowing agents include, for example, azo compounds, various Volatile Organic Compounds (VOCs), and chlorofluorocarbons (CFCs). Chemical blowing agents typically undergo some form of chemical change, including a chemical reaction with the material forming the polymer matrix (typically at a predetermined temperature/pressure), which results in the release of a gas, such as nitrogen, carbon dioxide or carbon monoxide. One of the most common chemical blowing agents is water. Physical blowing agents are typically dissolved in a polymer or polymer precursor material and then expanded in volume (still at a predetermined temperature/pressure) to aid in the formation of a foamed structure. Physical blowing agents are often used with thermoplastic foams, although for thermoplastic foams, chemical blowing agents may be used in place of or in addition to physical blowing agents. For example, for the formation of polyvinyl chloride based foams, it is known to use chemical blowing agents. For thermoset foams, chemical blowing and/or physical blowing agents are typically used. Of course, certain compounds and compositions containing them may constitute both chemical and physical blowing agents.

CFCs have been used in the past as standard blowing agents in the preparation of isocyanate-based foams, such as rigid and elastomeric polyurethane and polyisocyanurate foams. For example, from CFC materials, e.g. CCl₃Compositions of F (CFC-11) have become standard blowing agents. However, it is destroyed because of its release into the atmosphereThe ozone layer in the stratosphere, international treaties have banned the use of this material. Accordingly, pure CFC-11 is no longer commonly used as a standard blowing agent for forming thermoset foams, such as isocyanate-based foams and phenolic foams.

Flammability is another important property in many applications. That is, the use of compositions having low or no flammability is considered important or essential in many applications, including particularly in heat transfer and blowing agent applications. Thus, it is often beneficial to use non-flammable compounds in such compositions. The term "non-flammable" as used herein refers to a compound or composition that is non-flammable as measured according to ASTM standard E-681 (2002) incorporated by reference herein. Unfortunately, many HFCs that are otherwise suitable for use in refrigerant or blowing agent compositions are not non-flammable. For example, fluoroalkanedifluoroethane (HFC-152 a) and fluoroalkene 1,1, 1-trifluoropropene (HFO-1243 zf) are each flammable and therefore not useful for many applications.

Higher fluoroalkenes, i.e., fluoro-substituted alkenes having at least 5 carbon atoms, have been proposed for use as refrigerants. U.S. Pat. No. 4,788,352-Smutny relates to fluorinated C's having at least some degree of unsaturation₅To C₈Production of the compound. The Smutny patent identifies such higher olefins as known to be useful as refrigerants, pesticides, dielectric fluids, heat transfer fluids, solvents, and intermediates in various chemical reactions (see column 1, lines 11-22).

Another example of a relatively flammable material is the fluorinated ether 1,1, 22-tetrafluoroethyl methyl ether (which is referred to as HFE-254pc or sometimes HFE-254 cb), which has been measured to have a flammability limit (vol%) of about 5.4% to about 24.4%. Fluorinated ethers of this general class are disclosed for use as blowing agents in U.S. patent No. 5,137,932-behem et al, which is incorporated herein by reference.

It has been suggested in U.S. Pat. No. 5,900,185-Tapscott to use bromine-containing halocarbon additives to reduce the flammability of certain materials, including blowing agents. The additives are said in this patent to be characterized by high efficiency and short atmospheric lifetime, i.e., low Ozone Depletion Potential (ODP) and low Global Warming Potential (GWP).

The olefins described in Smutny and Tapscott are believed to have certain disadvantages. For example, some of these compounds tend to attack substrates, particularly general purpose plastics such as acrylic and ABS resins. In addition, the high olefin compounds described in Smutny are also undesirable in certain applications due to the potential toxicity of these compounds that may result from the pesticidal activity indicated in Smutny. These compounds also have boiling points that are too high for them to be useful as refrigerants in certain applications.

Bromofluoromethane and bromochlorofluoromethane derivatives, particularly bromotrifluoromethane (Halon 1301) and bromochlorodifluoromethane (Halon 1211) have been widely used as fire extinguishing agents in enclosed areas such as engine rooms and computer rooms. However, the use of various halogenated hydrocarbons (halons) is being phased out due to their high ozone depletion. Furthermore, since halogenated hydrocarbons are commonly used in occupied areas, suitable substitutes must also be safe to humans at concentrations necessary to suppress or extinguish fires.

Applicants have thus recognized the need for compositions, particularly heat transfer compositions, fire extinguishing/suppression compositions, blowing agents, solvent compositions, propellants, cleaning compositions, and compatibilizers, that may be useful in many applications, including vapor compression heating and cooling systems and methods, while avoiding one or more of the disadvantages described above.

Summary of The Invention

Applicants have found that compositions comprising one or more fluorinated alkene compounds, particularly including certain tetrafluoropropene compounds, preferably one or more of 1,1,1, 2-tetrafluoropropene (HFO-1234 yf), cis-1, 1,1, 3-tetrafluoropropene (cis HFO-1234 ze), and trans-1, 1,1, 3-tetrafluoropropene (trans HFO-1234 ze), and certain monochlorotrifluoropropene compounds, particularly including trans CF-1234 ze ₃CH = CClH (1233 zdE) and cis CF₃Compositions of CH = CClH (1233 zdZ), including heat transfer compositions, blowing agent compositions, foamsThe above needs and others are met by foam and foam premixes, solvent compositions, propellants, cleaning compositions, and compatibilizers. The applicant has found that, surprisingly, each of these compounds has the advantageous property of not being a VOC. As used herein, a compound is considered non-VOC if it has an MIR that is less than ethane. Accordingly, one aspect of the present invention relates to formulating a composition that has a favorable environment with reduced negative effects on ozone levels in the convection layer, processes including, inter alia, one or more of heat transfer compositions, blowing agent compositions, foams and foam premixes, solvent compositions, propellants, cleaning compositions, and compatibilizers, include using an amount, preferably a substantial amount, of one or more of the certain tetrafluoropropene compounds, preferably one or more of 1,1,1, 2-tetrafluoropropene (HFO-1234 yf), cis-1, 1,1, 3-tetrafluoropropene (cis HFO-1234 ze), and trans-1, 1,1, 3-tetrafluoropropene (trans HFO-1234 ze), and/or certain monochlorotrifluoropropene compounds, including, inter alia, trans CF, in such compositions. ₃CH = CClH (1233 zdE) and cis CF₃CH = CClH (1233 zdZ) to formulate such compositions with lower VOC compound mass. Applicants have found that in many embodiments, due to each of the above preferred compounds, trans-1, 1,1, 3-tetrafluoropropene (transHFO-1234 ze) and trans CF, in particular₃CH = CClH (1233 zdE) has a MIR value less than, preferably significantly less than, the MIR value of ethane, and the use of these compounds in the composition and/or according to the method described can significantly improve the environmental desirability of the composition.

The MIR values for certain compounds according to the invention are provided in table 1 below, in comparison with other compounds. The name HBA-2 is used to denote trans CF₃CH=CClH（1233zdE）。

TABLE 1

With respect to the monochlorotrifluoropropene compound, in a preferred embodiment, the compound is selected from the group consisting of:

trans CF₃CH=CClH (1233zdE);

Cis form CF₃CH=CClH (1233zdZ);

Trans-CHF₂CF=CClH (1233ydE);

Cis form CHF₂CF=CClH (1233ydZ);

Trans-CHF₂CH=CClF (1233zbE);

Cis form CHF₂CH=CClF (1233zbZ);

Trans-CHF₂CCl=CHF (1233xeE);

Cis form CHF₂CCl=CHF(1233xeZ);

CH₂FCCl=CF₂(1233xc);

trans-CHFClCF = CFH (1233yeE);

cis-CHFClCF = CFH (1233yeZ);

CH2ClCF=CF2 (1233yc);

CF2ClCF=CH2 (1233xf);

and combinations of two or more of these.

All such compounds as defined above are contemplated as being suitable for use in certain embodiments of the present invention. Preferred compounds of the compositions and methods according to the invention preferably exhibit one or more, preferably all, of the following properties: chemical stability; substantially free of Ozone Depletion Potential (ODP); a relatively high degree of miscibility with common contaminants, in particular mineral oils and/or silicone oils; low or no flammability; low or no toxicity; low or no Global Warming Potential (GWP); and non-VOCs.

Preferred compounds for use in the present compositions have been found to have several of these desirable beneficial properties simultaneously. More specifically, the preferenceThe compound has: an ODP that is substantially free of ozone depletion potential, preferably no greater than about 0.5, even more preferably no greater than about 0.25, and most preferably no greater than about 0.1; a GWP of not greater than about 150, and even more preferably not greater than about 50; and an MIR less than, and preferably significantly less than, ethane. Two examples of preferred compounds having this combination of desirable and unexpected properties are cis-and trans-1, 1,1, 3-tetrafluoropropene (HFO-1234 ze) and trans CF₃CH = CClH (1233 zdE) and cis CF₃CH=CClH（1233zdZ）。

In many preferred embodiments, the compounds of the present invention have a normal boiling point of from about 10 ℃ to about 60 ℃, even more preferably from about 15 ℃ to about 50 ℃, even more preferably from about 10 ℃ to about 25 ℃. The compounds also generally preferably have no Flash point as measured by one of the standard Flash point methods, such as ASTM-1310-86 "Flash point of liquids by tag Open-cup appatatus" and an atmospheric lifetime of no greater than about 100 days, and even more preferably no greater than about 50 days. Preferably, the compounds are also miscible with greater than 20% by weight of mineral and/or silicone oil, more preferably in a weight ratio of at least about 80:20 to about 20:80, and even more preferably in substantially all proportions.

Preferred compounds of the present invention exhibit relatively low toxicity values. ODPs as used herein are as specified in The report of The Scientific Assessment of Ozone Depletion, 2002, "World medical association, which is hereby incorporated by reference. GWP as used herein is defined relative to carbon dioxide and over a 100 year period and is defined in the same reference as the above-mentioned ODP. Miscibility as used herein is measured visually by the formation or separation of phases when two liquids are mixed together, as known to those skilled in the art.

The compositions of the present invention thus generally have properties and characteristics that are well suited for many different uses, including many different types of cleaning and stain removal uses.

In certain embodiments, the fluorinated olefin (hereinafter referred to as "fluoroalkene" for convenience and without limitation) has the following formula I: :

XCF_zR_3-z (I)

wherein X is C₂、C₃、C₄Or C₅Unsaturated substituted or unsubstituted groups, each R is independently Cl, F, Br, I or H, and z is 1 to 3, specifically including monochlorotrifluoropropene and tetrafluoropropene. In certain preferred embodiments, the fluoroalkenes of the present invention have at least four (4) halogen substituents, at least three of which are F. Preferably, in certain embodiments, none of the substituents is Br. In certain preferred embodiments, the compounds of formula I comprise compounds wherein each non-terminally unsaturated carbon has at least one halogen substituent, more preferably at least one substituent selected from chlorine and fluorine, preferably a three-carbon compound, with compounds having in certain embodiments at least three fluorine being particularly preferred.

In certain preferred embodiments, especially those involving heat transfer compositions, blowing agent compositions, solvent compositions, and cleaning compositions, the compound of formula I is a three carbon olefin, wherein z is 1 or 2. Thus, the compounds of formula I in certain embodiments comprise compounds of formula (IA):

CR’_wH_2-w =CR-CF_zR_3-z (IA)

wherein each R is independently Cl, F, Br, I or H, each R' is independently F or Cl, w is 1 or 2, preferably 1, and z is 1, 2 or 3, preferably 3.

In certain preferred compounds of formula IA, each R is F or H, examples of which are:

CF₂=CF-CH₂F (HFO-1234yc);

CF₂=CH-CF₂H (HFO-1234zc);

trans-CHF = CF-CF₂H (HFO-1234ye (E)); and

cis-CHF = CF-CF₂H (HFO-1234ye(Z))。

For embodiments of formula (IA) where at least one Br substituent is present, the compound is preferably hydrogen-free. In such embodiments, the Br substituent is also generally preferred on an unsaturated carbon, with the Br substituent even more preferably on a non-terminally unsaturated carbon. A particularly preferred embodiment within this class is CF₃CBr=CF₂Including all isomers thereof.

In certain embodiments, the fluoroalkene compounds of formula I very preferably contain propene, butene, pentene and hexene with 3 to 5 fluoro substituents, with or without other substituents. In certain preferred embodiments, none of R is Br, and the unsaturated group preferably contains no Br substituents. Of the propenes, tetrafluoropropene (HFO-1234) is particularly preferred in certain embodiments.

In certain embodiments, pentafluoropropenes are preferred, particularly including those in which a hydrogen substituent is present on the terminally unsaturated carbon, such as CF₃CF = CFH (HFO-1225 yeZ and/or yeE), in particular because the applicant has found that these compounds are associated with at least the compound CF₃CH=CF₂(HFO-1225 zc) is relatively less toxic than the corresponding compound.

Of the butenes, fluorochlorobutene is particularly preferred in certain embodiments.

The term "HFO-1234" is used herein to refer to all tetrafluoropropenes. Included among the tetrafluoropropenes are 1,1,1, 2-tetrafluoropropene (HFO-1234 yf), cis-and trans-1, 1,1, 3-tetrafluoropropene (HFO-1234 ze), CF₂=CF-CH₂F（HFO-1234yc）、CF₂=CH-CF₂H (HFO-1234 zc), trans-CHF = CF-CF₂H (HFO-1234 ye (E)) and cis-CHF = CF-CF₂H (HFO-1234 ye (Z)). The term HFO-1234ze is used generically herein to refer to 1,1,1, 3-tetrafluoropropene, whether it be in the cis-or trans-form. The terms "cis HFO-1234 ze" and "trans HFO-1234 ze" are used herein to describe the cis-and trans-forms of 1,1,1, 3-tetrafluoropropene, respectively. The term "HFO-1234 ze" is therefore included within its scopeIncluding cis HFO-1234ze, trans HFO-1234ze, and all combinations and mixtures of these. The term HFO-1234ye is used generically herein to denote 1,2,3, 3-tetrafluoropropene (CHF = CF-CF) ₂H) Whether it is in the cis-or trans-form. The terms "cis HFO-1234 ye" and "trans HFO-1234 ye" are used herein to describe the cis-and trans-forms of 1,2,3, 3-tetrafluoropropene, respectively. The term "HFO-1234 ye" thus includes within its scope cis HFO-1234ye, transHFO-1234 ye and all combinations and mixtures of these.

The term "HFO-1225" is used herein to refer to all pentafluoropropenes. Included among these molecules are 1,1,1,2,3 pentafluoropropene (HFO-1225 yez), their cis-and trans-forms. The term HFO-1225yez is therefore used generically herein to denote 1,1,1,2,3 pentafluoropropene, whether it is in the cis-or trans-form. The term "HFO-1225 yez" therefore includes within its scope cis HFO-1225yez, trans HFO-1225yez, and all combinations and mixtures of these.

In certain preferred embodiments, the composition comprises at least one monochlorotrifluoropropene compound and at least one additional fluorinated olefin, including tetrafluoropropene, each present in the composition in an amount from about 20% to about 80% by weight, more preferably from about 30% to about 70% by weight, and even more preferably from about 40% to about 60% by weight.

The invention also provides methods and systems for utilizing the compositions of the invention. In one aspect, the method includes a method and system for transferring heat, for retrofitting an existing heat transfer apparatus, and for replacing an existing heat transfer fluid in an existing heat transfer system. In other aspects, the present compositions are used in foaming, foam-forming and foam premix, solvating, cleaning, fragrance and fragrance extraction and/or delivery, aerosol generation, non-aerosol propellants and as bulking agents, and in methods of replacing or modifying each of said compositions and/or systems with compositions having reduced VOC content by replacing one or more active ingredients with the non-VOC compounds of the present invention in such use.

Detailed Description

A. Composition comprising a metal oxide and a metal oxide

The present compositions are believed to have advantageous properties for a number of important reasons. For example, applicants believe that, based at least in part on practical data and/or mathematical modeling, preferred compositions of the present invention have no significant adverse effect on atmospheric chemistry, have a negligible effect on ozone depletion compared to some other halide species, and are non-VOC. Preferred compositions of the invention therefore have the advantage of causing substantially no ozone depletion in the stratosphere and also no ozone generation in the troposphere, that is to say that they are not VOCs and preferably have an MIR less than ethane. The preferred compositions are substantially free of global warming compared to many of the hydrofluoroalkanes currently in use.

Of course, other compounds and/or components that modify certain properties of the composition (e.g., cost) may also be included in the present compositions, and the presence of all such compounds and components is within the broad scope of the present invention.

In certain preferred forms, the compositions of the present invention have a Global Warming Potential (GWP) of no greater than about 1500, more preferably no greater than about 1000, more preferably no greater than about 500, and even more preferably no greater than about 150. In certain embodiments, the GWP of the present compositions is not greater than about 100, and even more preferably not greater than about 75. "GWP" as used herein is as specified in The "report of The Scientific Association's Global Ozone Research and Monitoring Project", 2002, incorporated by reference herein, relative to carbon dioxide and measured over a period of 100 years.

In certain preferred forms, the present compositions also preferably have an Ozone Depletion Potential (ODP) of no greater than 0.05, more preferably no greater than 0.02, and even more preferably about 0. "ODP" as used herein is as specified in The "report of The Scientific Association's Global Ozone Research and Monitoring Project", 2002, which is incorporated herein by reference.

The fluorinated olefins contained in the present compositions are, in particular and preferably, 1,1,1, 2-tetrafluoropropene (HFO-1234 yf) and/or cis-1, 1,1, 3-tetrafluoropropene (cis HFO-1234 ze) and/or trans-1, 1,1, 3-tetrafluoropropene (trans HFO-1234 ze) and/or monochlorotrifluoropropene compounds, including in particular trans CF₃CH = CClH (1233 zdE) and cis CF₃The amount of CH = CClH (1233 zdff) can vary widely depending on the particular use, and compositions containing more than trace amounts and less than 100% of the compound are within the broad scope of the invention. In addition, the compositions of the present invention may be azeotropic, azeotrope-like or non-azeotropic.

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise trans-CF in an amount of from about 5% to about 99% by weight, and even more preferably from about 5% to about 95%₃CH=CClH (1233zdE)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise cis-CF in an amount of from about 5% to about 99% by weight, and even more preferably from about 5% to about 95% by weight₃CH=CClH (1233zdZ)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise trans-CHF in an amount of from about 5% to about 99% by weight, and even more preferably from about 5% to about 95% by weight ₂CF=CClH (1233ydE)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise cis CHF in an amount of from about 5% to about 99% by weight, and even more preferably from about 5% to about 95% by weight₂CF=CClH (1233ydZ)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise trans-chfci cf = CFH (1233yeE) in an amount of from about 5% to about 99% by weight, and even more preferably from about 5% to about 95%.

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise cis-chfci cf = CFH (1233yeZ) in an amount of from about 5% to about 99% by weight, and even more preferably from about 5% to about 95%.

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise trans-CF in an amount of at least about 50% by weight, and even more preferably at least about 70% by weight of the composition₃CH=CClH (1233zbE)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise cis-CF in an amount of at least about 50% by weight, and even more preferably at least about 70% by weight of the composition₃CH=CClH (1233ybZ)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise trans-CHF in an amount of at least about 50% by weight, and even more preferably at least about 70% by weight of the composition ₂CF=CClH (1233ydE)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise cis CHF in an amount of at least about 50% by weight, and even more preferably at least about 70% by weight of the composition₂CF=CClH (1233ydZ)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise trans-chfci cf = CFH (1233yeE) in an amount of at least about 50% by weight, even more preferably at least about 70% by weight of the composition.

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise cis chfci cf = CFH (1233yeZ) in an amount of at least about 50% by weight, and even more preferably at least about 70% by weight of the composition.

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise CH in an amount of at least about 50% by weight, even more preferably at least about 70% by weight of the composition₂ClCF=CF₂ (1233cf)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise CF in an amount of at least about 50% by weight, even more preferably at least about 70% by weight of the composition₂ClCF=CH₂ (1233yf)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise trans-CHF in an amount of at least about 50% by weight, and even more preferably at least about 70% by weight of the composition ₂CCl=CHF (1233xeE)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise cis CHF in an amount of at least about 50% by weight, and even more preferably at least about 70% by weight of the composition₂CCl=CHF (1233xeZ)。

In certain preferred embodiments, the present compositions, particularly blowing agent and heat transfer compositions, comprise CH in an amount of at least about 50% by weight, even more preferably at least about 70% by weight of the composition₂FCCl=CF₂ (1233xc)。

Many additional compounds or components may be included in the present compositions, including lubricants, stabilizers, metal deactivators, corrosion inhibitors, flame retardants, and other compounds and/or components that modify certain properties of the composition (e.g., cost), and the presence of all such compounds and components is within the broad scope of the present invention. In certain preferred embodiments, the present compositions include, in addition to one or more of the monochlorotrifluoropropene compound(s) mentioned above, one or more of:

trichlorofluoromethane (CFC-11);

dichlorodifluoromethane (CFC-12);

difluoromethane (HFC-32);

pentafluoroethane (HFC-125);

1,1,2, 2-tetrafluoroethane (HFC-134);

1,1,1, 2-tetrafluoroethane (HFC-134 a);

difluoroethane (HFC-152 a);

1,1,1,2,3,3, 3-heptafluoropropane (HFC-227 ea);

1,1,1,3,3, 3-hexafluoropropane (HFC-236 fa);

1,1,1,3, 3-pentafluoropropane (HFC-245 fa);

1,1,1,3, 3-pentafluorobutane (HFC-365 mfc);

water; and

CO₂。

the relative amounts of any of the above-described compounds of the present invention, as well as any additional components that may be included in the present compositions, may vary widely within the broad general scope of the present invention depending upon the particular use for which the composition is intended, and all such relative amounts are considered to be within their scope.

Accordingly, applicants have recognized that certain compositions of the present invention can be used with great advantage in a number of applications, including, for example, in the present invention, methods and compositions related to heat transfer applications, foam and blowing agent applications, propellant applications, sprayable composition applications, disinfectant applications, aerosol applications, compatibilizer applications, fragrance and fragrance applications, solvent applications, cleaning applications, expander applications, and the like. It is believed that one skilled in the art can readily adapt the present compositions for any and all such uses without undue experimentation.

The present compositions are generally useful as replacements for CFCs, such as dichlorodifluoromethane (CFC-12), HCFCs, such as chlorodifluoromethane (HCFC-22), HFCs, such as tetrafluoroethane (HFC-134 a), and combinations of HFCs and CFCs, such as the combination of CFC-12 and 1, 1-difluoroethane (HFC-152 a) (the combination of CFC-12: HFC-152a in a mass ratio of 73.8:26.2 is referred to as R-500) in refrigerants, aerosols, and other uses.

B. Heat transfer composition

The compositions of the present invention are generally suitable for use in heat transfer applications, i.e., as heating and/or cooling media, including as evaporative coolants.

For evaporative cooling applications, the composition of the present invention is brought into direct or indirect contact with the object to be cooled, and thereafter evaporates or boils while in such contact, preferably with the result that the boiling gas of the present composition absorbs heat from the object to be cooled. In such use, the compositions of the present invention, preferably in liquid form, are preferably used by spraying or otherwise applying the liquid to the object to be cooled. In other evaporative cooling applications, it may be preferred to have the liquid composition of the present invention escape from a relatively high pressure vessel to a relatively low pressure environment where the object to be cooled is in direct or indirect contact with the vessel in which the liquid composition of the present invention is enclosed, preferably without recovering or recompressing the escaping gas. One particular use of this type of embodiment is self-cooling of beverages, food products, new products (novelty items) and the like. Prior to the invention described herein, existing compositions, such as HFC-152a and HFC-134a, were used for these purposes. However, such compositions have recently been considered disadvantageous in such applications due to the adverse environmental effects caused by the release of these materials into the atmosphere. For example, the United States EPA has determined that the use of these existing chemicals in this application is unacceptable due to the high global warming properties of these chemicals and the deleterious effects on the environment that may result from their use. The compositions of the present invention have significant advantages in this regard due to their low global warming potential and low ozone depletion potential as described herein. In addition, the present compositions are also expected to be substantially useful for cooling of electrical or electronic components during manufacturing or during accelerated life testing. In the accelerated life test, the part was successively heated and cooled in rapid succession to simulate the use of the part. Such use is therefore particularly advantageous in the semiconductor and computer board manufacturing industries. Another advantage of the present compositions in this regard is that they are expected to exhibit desirable electrical properties when used in these applications. Another evaporative cooling application includes a method of temporarily discontinuing fluid flow through a conduit. These methods preferably comprise contacting a conduit, such as a water pipe through which water flows, with the liquid composition of the present invention and allowing the liquid composition of the present invention to evaporate while in contact with the conduit to freeze the liquid contained therein and thereby temporarily halt the flow of fluid through the conduit. These methods have significant advantages in allowing for servicing or other operations to be performed on such conduits or systems connected to such conduits at a location downstream of the location where the present composition is applied.

The relative amounts of hydrofluoroolefins used in accordance with the present invention are preferably selected to produce a heat transfer fluid having the desired heat transfer capacity, particularly refrigeration capacity, preferably while being non-flammable. The term non-flammable as used herein refers to a fluid that is non-flammable in air at all ratios as measured by ASTM E-681.

The compositions of the present invention may include other components for enhancing or providing certain functions to the composition or in some cases reducing the cost of the composition. For example, the refrigerant compositions of the present invention, particularly those used in vapor compression systems, include a lubricant in an amount generally from about 30 to about 50 weight percent of the composition. In addition, the composition may also include an auxiliary refrigerant or compatibilizer, such as propane, to aid in the compatibility and/or solubility of the lubricant. Such compatibilizers, including propane, butane, and pentane, are preferably present in an amount of about 0.5 to about 5 weight percent of the composition. Combinations of surfactants and solubilizers may also be added to the present compositions to aid in oil solubility as disclosed in U.S. Pat. No. 6,516,837, the disclosure of which is incorporated herein by reference. Conventional refrigeration lubricants used with Hydrofluorocarbon (HFC) refrigerants in refrigeration machinery, such as polyol esters (POE) and polyalkylene glycols (PAG), PAG oils, silicone oils, mineral oils, Alkylbenzenes (AB), and poly (alpha-olefins) (PAO), may be used with the refrigerant compositions of the present invention. Commercially available mineral oils include Witco LP 250 (registered trademark) from Witco, Zerol 300 (registered trademark) from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 from Calumet. Commercially available alkylbenzene lubricants include Zerol 150 (registered trademark). Commercially available esters include neopentyl glycol dipelargonate available as Emery 2917 (registered trade mark) and Hatcol 2370 (registered trade mark). Other useful esters include phosphate esters, dibasic acid esters, and fluorinated esters. In some cases, hydrocarbon-based oils have sufficient solubility with refrigerants that include iodocarbons (iodocarbons), and the combination of iodocarbons and hydrocarbon oils may be more stable than other types of lubricants. Such a combination is therefore advantageous. Preferred lubricants include polyalkylene glycols and esters. Polyalkylene glycols are highly preferred in certain embodiments because they are currently used in certain applications, such as automotive air conditioning. Of course, different mixtures of different types of lubricants may be used.

In certain preferred embodiments, the heat transfer composition comprises from about 10% to about 95% by weight of one or more monochlorotrifluoropropenes as described above and from about 5% to about 90% by weight of adjuvants, particularly auxiliary refrigerants (e.g., HFC-152, HFC-125 and/or CF) in certain embodiments₃I) In that respect The use of the term auxiliary refrigerant herein is not intended to be used in a limiting sense with respect to the relative performance of the monochlorotrifluoropropene compound, but is used to generally refer to other components of the refrigerant composition that contribute to the heat transfer characteristics of the composition that are desirable for the intended use. In certain such embodiments, the auxiliary refrigerant comprises, and preferably consists essentially of, one or more HFCs and/or one or more fluoroiodo C1-C3 compounds, such as trifluoroiodomethane, and combinations of these with each other and with other components.

In preferred embodiments where the auxiliary refrigerant comprises an HFC, preferably HFC-125, the composition comprises HFC in an amount from about 50% to about 95% by weight of the total heat transfer composition, more preferably from about 60% to about 90% by weight, and even more preferably from about 70% to about 90% by weight of the composition. In such embodiments, the monochlorotrifluoropropene compounds of the present invention preferably comprise from about 5% to about 50% by weight of the total heat transfer composition, more preferably from about 10% to about 40% by weight, and even more preferably from about 10% to about 30% by weight of the composition.

In a preferred embodiment wherein the auxiliary refrigerant comprises a fluoroiodocarbon, preferably CF3I, the composition comprises the fluoroiodocarbon in an amount of from about 15% to about 50% by weight of the total heat transfer composition, more preferably from about 20% to about 40% by weight, even more preferably from about 25% to about 35% by weight of the composition. In such embodiments, the monochlorotrifluoropropene compounds of the present invention preferably comprise from about 50% to about 90% by weight of the total heat transfer composition, more preferably from about 60% to about 80% by weight, and even more preferably from about 65% to about 75% by weight of the composition.

The present methods, systems and compositions are therefore useful in a wide variety of heat transfer systems in general, and in particular refrigeration systems, such as air conditioning (including stationary and automotive air conditioning systems), refrigeration, heat pump systems, and the like. In certain preferred embodiments, the compositions of the present invention are used in refrigeration systems originally designed to use HFC refrigerants, such as HFC-134a, or HCFC refrigerants, such as HCFC-22. Preferred compositions of the present invention tend to exhibit many of the desirable characteristics of HFC-134a and other HFC refrigerants, including a GWP as low or lower than conventional HFC refrigerants and a capacity as high or higher than those refrigerants and a capacity substantially similar to or substantially matching and preferably as high or higher than those refrigerants. In particular, applicants have recognized that certain preferred embodiments of the present compositions tend to exhibit relatively low global warming potentials ("GWPs"), preferably less than about 1000, more preferably less than about 500, and even more preferably less than about 150. Furthermore, the relatively constant boiling nature of certain of the present compositions, including azeotrope-like compositions described in the co-pending patent applications incorporated by reference herein, makes them more desirable than certain conventional HFCs, such as R-404A, or combinations of HFC-32, HFC-125 and HFC-134A (approximately 23:25:52 weight ratio of the combination HFC-32: HFC-125: HFC134A is referred to as R-407C), which are used as refrigerants in many applications. The heat transfer compositions of the present invention are particularly preferred as replacements for HFC-134, HFC-152a, HFC-22, R-12 and R-500.

In certain other preferred embodiments, the present compositions are used in refrigeration systems originally designed for use with CFC-refrigerants. Preferred refrigeration compositions of the present invention may be used in refrigeration systems containing lubricants conventionally used with CFC-refrigerants, such as mineral oil, polyalkylbenzenes, polyalkylene glycol oils, and the like, or may be used with other lubricants conventionally used with HFC refrigerants. As used herein, the term "refrigeration system" generally refers to any system or device that uses a refrigerant to provide cooling or any component or portion of such a system or device. Such refrigeration systems include, for example, air conditioners, refrigerators, freezers (including freezers that use centrifugal compressors), transport refrigeration systems, commercial refrigeration systems, and the like.

Many existing refrigeration systems are currently suitable for use in conjunction with existing refrigerants, and the compositions of the present invention are believed to be suitable for use in many such systems, with or without system modifications. In many applications, the compositions of the present invention may provide an advantage as a replacement in smaller systems that are currently based on certain refrigerants, such as those requiring small refrigeration capacities and therefore relatively small compressor capacities. Furthermore, in embodiments where it is desirable to use a lower capacity refrigerant composition of the present invention in place of a higher capacity refrigerant for reasons such as efficiency, these embodiments of the present composition provide potential advantages. Thus, in certain embodiments it is preferred to use the compositions of the present invention, particularly compositions comprising and in some embodiments consisting essentially of a significant proportion of the present composition, in place of existing refrigerants, such as: HFC-134 a; CFC-12; HCFC-22; HFC-152 a; a combination of pentafluoroethane (HFC-125), trifluoroethane (HFC-143 a) and tetrafluoroethane (HFC-134A) (the combination of HFC-125: HFC-143a: HFC134A in an approximate 44:52:4 weight ratio is referred to as R-404A); a combination of HFC-32, HFC-125, and HFC-134a (approximately a 23:25:52 weight ratio of the combination HFC-32: HFC-125: HFC134a is referred to as R-407C); a combination of difluoromethane (HFC-32) and pentafluoroethane (HFC-125) (approximately a 50:50 weight ratio of the combination HFC-32: HFC-125 is referred to as R-410A); a combination of CFC-12 and 1, 1-difluoroethane (HFC-152 a) (the combination in a weight ratio of 73.8:26.2, CFC-12: HFC-152a being referred to as R-500); and a combination of HFC-125 and HFC-143a (approximately 50:50 weight ratio of the combination HFC-125: HFC143a is referred to as R-507A). In certain embodiments, it may also be beneficial to use the present compositions in place of refrigerants formed from combinations of HFC-32: HFC-125: HFC134a in a weight ratio of approximately 20:40:40 (which is referred to as R-407A) or approximately 15:15:70 (which is referred to as R-407D). The present compositions are also believed to be suitable for replacing the above-described compositions in other uses as explained elsewhere herein, such as aerosols, blowing agents, and the like.

In certain applications, the refrigerants of the present invention may allow for the advantageous use of larger displacement compressors, thereby resulting in better energy efficiency than other refrigerants, such as HFC-134 a. Thus, the refrigerant compositions of the present invention provide the potential for refrigerant replacement applications, including automotive air conditioning systems and devices, commercial refrigeration systems and devices, freezers, residential refrigerators and freezers, general air conditioning systems, heat pumps, and the like, to achieve competitive advantages on an energy basis.

Many existing refrigeration systems are currently suitable for use in conjunction with existing refrigerants, and the compositions of the present invention are believed to be suitable for use in many such systems, with or without system modifications. In many applications, the compositions of the present invention may provide an advantage as a replacement in current systems based on refrigerants having relatively high capacity. Furthermore, in embodiments where it is desirable to use a lower capacity refrigerant composition of the present invention in place of a higher capacity refrigerant, for cost reasons, for example, these embodiments of the present composition provide potential advantages. Accordingly, it is preferred in certain embodiments to use the compositions of the present invention, particularly compositions comprising a significant proportion, and in some embodiments consisting essentially of HFO-1233, in place of existing refrigerants, such as HFC-134 a. In certain applications, the refrigerants of the present invention may allow for the advantageous use of larger displacement compressors, thereby resulting in better energy efficiency than other refrigerants, such as HFC-134 a. Thus, the refrigerant compositions of the present invention offer the possibility of achieving competitive advantages on an energy basis for refrigerant replacement applications.

The present compositions are also expected to have advantages in water chiller machines commonly used with commercial air conditioning systems (either in the original system or when used as a replacement for refrigerants such as CFC-11, CFC-12, HCFC-22, HFC-134a, HFC-152a, R-500 and R-507A). In certain such embodiments, it is preferred to include from about 0.5 to about 30%, in some cases, more preferably from 0.5% to about 15%, and even more preferably from about 0.5 to about 10%, of the supplemental flame retardant in the present compositions on a weight basis.

C. Blowing agents, foams and foamable compositions

The blowing agent may also comprise or consist of one or more of the present compositions. As mentioned above, the compositions of the present invention may include a wide range of amounts of the compounds of the present invention. However, it is generally preferred that for preferred compositions for use as blowing agents in accordance with the present invention, the one or more monochlorotrifluoropropene compounds are present in an amount of at least about 5% by weight, even more preferably at least about 15% by weight of the composition. In certain preferred embodiments, the blowing agent comprises at least about 50% by weight of the present composition, and in certain embodiments the blowing agent consists essentially of the present composition. In certain preferred embodiments, the blowing agent compositions of the present invention include one or more of co-blowing agents, fillers, vapor pressure modifiers, flame retardants, stabilizers, and similar adjuvants in addition to the monochlorotrifluoropropene compound. The co-blowing agent of the present invention may comprise a physical blowing agent, a chemical blowing agent (which in certain embodiments preferably comprises water), or a blowing agent having a combination of physical and chemical blowing agent properties. It will also be appreciated that the blowing agents included in the present compositions, including the compounds of formula I as well as co-blowing agents, may exhibit properties other than those desirable for characterizing the blowing agent. For example, the blowing agent compositions of the present invention are expected to include components that also provide some beneficial properties to the blowing agent composition or to the foamable composition to which it is added, including the compounds of formula I described above. For example, it is within the scope of the present invention for the compound of formula I or the co-blowing agent to also act as a polymer modifier or as a viscosity-reducing modifier.

For example, one or more of the following components may be included in widely varying amounts in certain preferred blowing agents of the present invention: hydrocarbons, Hydrofluorocarbons (HFCs), ethers, alcohols, aldehydes, ketones, methyl formate, formic acid, water, trans-1, 2-dichloroethylene, carbon dioxide, and combinations of any two or more thereof. Among the ethers, ethers having 1 to 6 carbon atoms are preferably used in certain embodiments. Among the alcohols, alcohols having 1 to 4 carbon atoms are preferably used in certain embodiments. Among the aldehydes, aldehydes having 1 to 4 carbon atoms are preferably used in certain embodiments.

Certain adjuvants which may be used in accordance with the present invention are described below.

1. Ether compounds

In certain preferred embodiments, the present compositions, particularly blowing agent compositions, include at least one ether, preferably acting as a co-blowing agent in the composition.

The ethers used according to this aspect of the invention comprise Fluorinated Ethers (FE), more preferably one or more hydro-fluorinated ethers (HFE), still more preferably one or more of the hydrofluorinated ethers C3 to C5 according to the following formula (III):

C_aH_bF_c---O---C_dH_eF_f(III)

wherein

a = 1-6, more preferably 2-5, still more preferably 3-5,

b = 1-12, more preferably 1-6, still more preferably 3-6,

c = 1-12, more preferably 1-6, still more preferably 2-6,

d = 1-2

e = 0-5, more preferably 1-3

f = 0-5, more preferably 0-2,

and wherein said C_aOne of which is bondable to said C_dTo form a cyclic fluoroether on one of them.

Certain preferred embodiments of the present invention relate to compositions comprising at least one fluoroalkene, preferably in certain embodiments a chlorofluoroalkene, such as HFCO-1233xd, as described herein, and at least one fluoroether, more preferably at least one hydrofluoroether containing 2 to 8, preferably 2 to 7, even more preferably 2 to 6 carbon atoms, and in certain embodiments most preferably 3 carbon atoms. The hydrofluoroether compounds of the present invention, if they contain at least one hydrogen, are sometimes referred to herein for convenience as hydrofluoroethers or "HFEs".

Applicants believe that in general, the fluoroethers according to the present disclosure, and in particular according to formula (III) above, are generally effective and can be used with fluoroalkene compounds according to the teachings contained herein. Applicants have discovered, however, that hydrofluoroethers that are at least difluorinated, more preferably at least trifluorinated, and even more preferably at least tetrafluorinated, are preferably used in certain embodiments, particularly those involving blowing agent compositions and foams and foaming processes. Particularly preferred in certain embodiments are the fluoroethers tetrafluoride having from 3 to 5 carbon atoms, more preferably from 3 to 4 carbon atoms, still more preferably 3 carbon atoms.

In certain preferred embodiments, the ether compounds of the present invention comprise 1,1,2, 2-tetrafluoroethylmethyl ether (which is sometimes referred to herein as HFE-245pc or HFE-245cb 2), including any and all isomeric forms thereof.

The amount of the compound of formula III, particularly 1,1,2, 2-tetrafluoroethylmethyl ether, contained in the present compositions can vary widely depending on the particular application, and compositions containing more than trace amounts and less than 100% of the compound are within the broad scope of the present invention. In a preferred embodiment, the present compositions, particularly blowing agent compositions, comprise compounds of formula III, including preferred classes of compounds, in an amount from about 1% to about 99% by weight, more preferably from about 5% to about 95% by weight, and even more preferably from 40% to about 90% by weight.

One or more of the following compounds are preferably used according to certain preferred embodiments of the present invention:

CHF₂OCH₂F（HFE- 143E）；

CH₂FOCH₂F（HFE- 152E）；

CH₂FOCH₃（HFE- 161E）；

Ring-CF₂CH₂OCF₂O（HFE- c234fEαβ）；

Ring-CF₂CF₂CH₂O（HFE- c234fEβγ）；

CHF₂OCF₂CHF₂（HFE- 236caE）；

CF₃CF₂OCH₂F（HFE- 236cbEβγ）；

CF₃OCHFCHF₂（HFE- 236eaEαβ）；

CHF₂OCHFCF₃（HFE- 236eaEβγ）；

CHF₂OCF₂CH₂F（HFE- 245caEαβ）；

CH₂FOCF₂CHF₂（HFE- 245caEβγ）；

CF₃OCF₂CH₃（HFE- 245cbEβγ）；

CHF₂CHFOCHF₂（HFE- 245eaE）；

CF₃OCHFCH₂F（HFE- 245ebEαβ）；

CF₃CHFOCH₂F（HFE- 245ebEβγ）；

CF₃OCH₂CF₂H（HFE- 245faEαβ）；

CHF₂OCH₂CF₃（HFE- 245faEβγ）；

CH₂FCF₂OCH₂F（HFE- 254caE）；

CHF₂OCF₂CH₃（HFE- 254cbEαβ）；

CHF₂CF₂OCH₃（HFE- 254caEβγ）；

CH₂FOCHFCH₂F（HFE- 254eaEαβ）；

CF₃OCHFCH₃（HFE- 254ebEαβ）；

CF₃CHFOCH₃（HFE- 254ebEβγ）；

CHF₂OCH₂CHF₂（HFE- 254faE）；

CF₃OCH₂CH₂F（HFE- 254fbEαβ）；

CF₃CH₂OCH₂F（HFE- 254fbEβγ）；

CH₃OCF₂CH₂F（HFE- 263caEβγ）；

CF₃CH₂OCH₃（HFE- 263fbEβγ）；

CH₃OCH₂CHF₂（HFE- 272fbEβγ）；

CHF₂OCHFCF₂CF₃（HFE- 338mceEγδ）；

CHF₂OCF₂CHFCF₃（HFE- 338mceEγδ）；

CF₃CF₂OCH₂CF₃（HFE- 338mfEβγ）；

(CF₃)₂CHOCHF₂（HFE- 338mmzEβγ）；

CF₃CF₂CF₂OCH₃（HFE- 347sEγδ）；

CHF₂OCH₂CF₂CF₃（HFE- 347mfcEγδ）；

CF₃OCH₂CF₂CHF₂（HFE- 347mfcEαβ）；

CH₃OCF₂CHFCF₃（HFE- 356mecEγδ）；

CH₃OCH(CF₃)₂（HFE- 356mmzEβγ）；

CF₃CF₂OCH₂CH₃（HFE- 365mcEβγ）；

CF₃CF₂CH₂OCH₃（HFE- 365mcEγδ）；

CF₃CF₂CF₂OCHFCF₃（HFE- 42-11meEγδ）；

CF₃CFCF₃CF₂OCH₃；

CF₃CF₂CF₂CF₂OCH₃；

CF₃CFCF₃CF₂OCH₂CH₃；

CF₃CF₂CF₂CF₂OCH₂CH₃(ii) a And

CF₃CF₂CF₂OCH₃。

it should be understood that the inventors contemplate that any two or more of the above HFEs may be used in combination according to preferred aspects of the invention. For example, the material sold under the trade name HFE-7100, 3M, which is understood to be a mixture of from about 20% to about 80% methyl nonafluoroisobutyl ether and from about 20% to about 80% methyl nonafluorobutyl ether, is expected to be advantageously used in accordance with certain preferred embodiments of the present invention. As another example, 3M, a material sold under the trade name HFE-7200, which is understood to mean a mixture of about 20% to about 80% ethyl nonafluoroisobutyl ether and about 20% to about 80% ethyl nonafluorobutyl ether, is expected to be advantageously used in accordance with certain preferred embodiments of the present invention.

It is contemplated that any one or more of the above-listed HFEs may also be used in combination with other compounds, including other HFEs not specifically enumerated herein and/or other compounds known to form azeotropes with the specified fluoroether. For example, each of the following compounds are known to form azeotropes with trans-dichloroethylene, and it is contemplated that the use of these azeotropes is considered to be within the broad scope of the present invention:

CF₃CFCF₃CF₂OCH₃；

CF₃CF₂CF₂CF₂OCH₃；

CF₃CFCF₃CF₂OCH₂CH₃；

CF₃CF₂CF₂CF₂OCH₂CH₃(ii) a And

CF₃CF₂CF₂OCH₃。

2. hydrofluorocarbons

In certain embodiments, the compositions of the present invention, particularly blowing agent compositions of the present invention, preferably include one or more HFCs as co-blowing agents, more preferably one or more C1-C4 HFCs. For example, the present blowing agent compositions may include difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227 ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and one or more of all isomers of all of these HFCs.

In certain embodiments, one or more of the following HFC isomers are preferred for use as co-blowing agents in the compositions of the present invention:

Fluoroethane (HFC-161);

1,1,1,2, 2-pentafluoroethane (HFC-125);

1,1,2, 2-tetrafluoroethane (HFC-134);

1,1,1, 2-tetrafluoroethane (HFC-134 a);

1,1, 1-trifluoroethane (HFC-143 a);

1, 1-difluoroethane (HFC-152 a);

1,1,1,2,3,3, 3-heptafluoropropane (HFC-227 ea);

1,1,1,3,3, 3-hexafluoropropane (HFC-236 fa);

1,1,1,2,3, 3-hexafluoropropane (HFC-236 ea);

1,1,1,2, 3-pentafluoropropane (HFC-245 eb);

1,1,2,2, 3-pentafluoropropane (HFC-245 ca);

1,1,1,3, 3-pentafluoropropane (HFC-245 fa);

1,1,1,3, 3-pentafluorobutane (HFC-365 mfc); and

1,1,1,2,2,3,4,5,5, 5-decafluoropentane (HFC-43-10-mee).

3. Hydrocarbons

In certain embodiments, the compositions of the present invention, particularly including the blowing agent compositions of the present invention, preferably include one or more hydrocarbons, more preferably C3-C6 hydrocarbons. The present blowing agent compositions may include, for example: propane; iso-and n-butanes (each of these is preferably used as a blowing agent for thermoplastic foams); iso-, normal-, neo-, and/or cyclo-pentanes (each of these pentanes is preferably used as a blowing agent for thermoset foams); iso-and n-hexane; and heptane.

Certain preferred embodiments of the present compositions, including in particular blowing agent compositions, comprise one or more monochlorotrifluoropropenes, in particular HFCO-1233zd and at least one hydrocarbon selected from the group consisting of iso-pentane, n-pentane, cyclo-pentane, and combinations of these, with a combination comprising from about 50% to about 85% by weight of cyclo-pentane, and even more preferably from about 65% to about 75% by weight of cyclo-pentane being preferred.

4. Alcohol(s)

In certain embodiments, the compositions of the present invention, particularly including the blowing agent compositions of the present invention, preferably include one or more alcohols, preferably one or more C1-C4 alcohols. For example, the present blowing agent compositions, aerosol, cleaning and solvent compositions of the present invention may include one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol and octanol. Of the octanols, isooctanol (i.e., 2-ethyl-1-hexanol) is preferred for use in the blowing agent formulation and solvent composition.

The present compositions, including in particular certain preferred embodiments of blowing agent compositions, comprise one or more monochlorotrifluoropropenes, in particular HFCO-1233zd and at least one alcohol selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, and combinations of these.

5. Aldehydes

In certain embodiments, the compositions of the present invention, particularly including the blowing agent, aerosol, cleaning and solvent compositions of the present invention, preferably include one or more aldehydes, particularly C1-C4 aldehydes, including formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde.

6. Ketones

In certain embodiments, the compositions of the present invention, including in particular the blowing agent compositions, aerosol, cleaning and solvent compositions of the present invention, preferably comprise one or more ketones, preferably C1-C4 ketones. For example, the present blowing agent, aerosol, cleaning and solvent compositions may include one or more of acetone, methyl ethyl ketone, and methyl isobutyl ketone.

7. Chlorocarbon compounds

In certain embodiments, the compositions of the present invention, particularly including the blowing agent, aerosol, cleaning and solvent compositions of the present invention, preferably include one or more chlorocarbon compounds, more preferably C1-C3 chlorocarbon compounds. The present compositions may include, for example: 1-chloropropane; 2-chloropropane; trichloroethylene; perchloroethylene; dichloromethane; trans-1, 2 dichloroethylene and combinations of these, with trans-1, 2 dichloroethylene being particularly preferred in certain embodiments, particularly blowing agent embodiments.

8. Other Compounds

In certain embodiments, the compositions of the present invention, particularly including the blowing agent, aerosol, cleaning and solvent compositions of the present invention, preferably include one or more additional compounds, including water, CO₂Methyl formate, formic acid, Dimethoxymethane (DME) and combinations of these. Of the above materials, DME is particularly preferred for use in blowing agent compositions and as a propellant in aerosol compositions according to the present invention, particularly in combination with HFCO-1233 zd. Among the above materials, water and CO₂Particularly preferred for use in the blowing agent and as propellant according to the invention, especially in combination with HFCO-1233 zd.

It is contemplated that the relative amounts of any of the above-described additional compounds that function as co-blowing agents in certain embodiments, as well as any additional components that may be included in the present compositions, may vary widely within the broad general scope of the present invention depending upon the particular use of the composition, and all such relative amounts are considered to be within its scope. However, the applicant has noted that one particular advantage of at least some of the compounds of the present invention is the relatively low flammability and relatively low toxicity of these compounds. Thus, in certain embodiments, the compositions of the present invention preferably comprise at least one adjuvant and one or more monochlorotrifluoropropene compound(s) in an amount sufficient to produce an overall non-flammable composition. The term "adjuvant" as used herein is intended to mean any compound or compounds included in the composition to contribute to at least some aspect of the performance of the composition for its intended use. Thus, in these embodiments, the relative amount of adjuvant with respect to the one or more monochlorotrifluoropropene compound(s) depends, at least in part, on the desired properties of the composition, such as flammability of the adjuvant.

The compositions of the invention may include a wide range of amounts of the compounds of the invention. However, it is generally preferred that for preferred compositions used as blowing agents in accordance with the present invention, the monochlorotrifluoropropene compound is present in an amount of at least about 1% by weight, more preferably at least about 5% by weight, even more preferably at least about 15% by weight of the composition. In certain preferred embodiments, the blowing agent comprises at least about 50% by weight of the present blowing agent compounds, and in certain embodiments the blowing agent consists essentially of the compounds of the present invention. In this respect it is noted that the use of one or more co-blowing agents is in accordance with the novel and essential features of the present invention. For example, water is contemplated in a number of embodiments for use as a co-blowing agent or in combination with other co-blowing agents (e.g., pentane, especially cyclopentane).

Blowing agent compositions of the present invention are contemplated to comprise one or more monochlorotrifluoropropene compound(s), 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 directed to thermoset foam applications.

In certain embodiments, the blowing agent compositions of the present invention preferably comprise HFCO-1233zd, more preferably at least about 90 wt.% HFCO-1233zd, more preferably at least about 95 wt.% HFCO-1233zd, and even more preferably at least about 99 wt.% HFCO-1233 zd. In certain preferred embodiments, the blowing agent compositions of the present invention preferably comprise at least about 80%, and even more preferably at least about 90% by weight HFCO-1233zd, and even more preferably any one or more of cis-HFCO-1233 zd and trans-HFC-1233 zd.

The blowing agent compositions of the present invention in certain embodiments comprise a combination of cis-HFCO-1233 zd and trans-HFCO 1233 zd. In certain embodiments, the cis to trans weight ratio is from about 30:70 to about 5:95, even more preferably from about 20:80 to about 5:95, and in certain embodiments a ratio of 10:90 is especially preferred.

In certain preferred embodiments, the blowing agent composition comprises from about 30% to about 95%, more preferably from about 30% to about 96%, more preferably from about 30% to about 97%, even more preferably from about 30% to about 98%, even more preferably from about 30% to about 99%, by weight, of one or more monochlorotrifluoropropene compounds, and from about 5% to about 90%, more preferably from about 5% to about 65%, by weight, of a co-blowing agent comprising one or more fluoroethers. In certain such embodiments, the co-blowing agent comprises, and preferably consists essentially of, a material selected from H ₂O, HC, HE, HFC, HFE, hydrocarbons, alcohols (preferably C2, C3 and/or C4 alcohols), ketones, CO₂And combinations of any two or more thereof.

In other embodiments, the present invention provides foamable compositions. The foamable compositions of the present invention generally comprise one or more components capable of forming a foam. In certain embodiments, the one or more components comprise a thermoset composition and/or a foamable composition capable of forming a foam. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and phenolic foam compositions. With respect to foam types, particularly polyurethane foam compositions, the present invention provides rigid foams (closed cell, open cell, and any combination thereof), resilient foams, and semi-resilient foams, including integral skin foams. The present invention also provides one-component foams, including sprayable one-component foams.

Various additives, such as catalysts and surfactant materials for controlling and regulating cell size and stabilizing the foam structure during formation, may be used to enhance the reaction and foaming process. Furthermore, any one or more of the additional components described above with respect to the blowing agent compositions of the present invention are contemplated to be incorporated into the foamable compositions of the present invention. In such thermoset foam embodiments, one or more of the present compositions are included as a blowing agent in a foamable composition or a portion thereof or as part of a two or more component foamable composition, which preferably includes one or more components capable of reacting and/or foaming under the appropriate conditions to form a foam or cellular structure.

In certain other embodiments, the one or more components comprise a thermoplastic material, in particular a thermoplastic polymer and/or resin. Examples of thermoplastic foam components include polyolefins such as monovinylaromatic compounds of the formula Ar-CHCH2, wherein Ar is an aromatic hydrocarbon group of the benzene series, such as Polystyrene (PS), (PS). Other examples of suitable polyolefin resins according to the present invention include various ethylene resins including ethylene homopolymers such as Polyethylene (PE) and ethylene copolymers, polypropylene (PP) and polyethylene terephthalate (PET) and foams formed therefrom, preferably low density foams. In certain embodiments, the thermoplastic foamable composition is an extrudable composition.

The present invention also relates to foams, preferably closed cell foams, made from polymer foam formulations containing a blowing agent comprising the compositions of the present invention. In other embodiments, the present invention provides foamable compositions comprising thermoplastic or polyolefin foams, such as Polystyrene (PS), Polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET) foams, preferably low density foams.

D. Composition containing trifluoro-chloropropene

Applicants have developed several compositions comprising, as an essential component, one or more trifluoromonochloropropene compounds, including trans CF₃CH = CClH (1233 zdE), cis CF₃CH = CClH (1233 zdZ), trans CHF₂CF = CClH (1233 ydE), cis CHF₂CF = CClH (1233 ydZ), trans CHF2CH = CClF (1233 zbE), cis CHF2CH = CClF (1233 zbZ), trans CHF2CCl = CHF (1233 xeE), cis CHF2CCl = CHF (1233 xeZ), CH2FCCl = CF2 (1233 xc), trans CHFClCF = CFH (1233 yeE), cis CHF2CCl = CHF (1233 xeZ)ClCF = CFH (1233 yeZ), CH2ClCF = CF2 (1233 yc), including all combinations of these in all ratios, and at least one additional compound. In such compositions, the amount of the one or more trifluoromonochloropropenes can vary widely, in all cases including the balance of the composition after calculation of all other components in the composition. In certain preferred embodiments, the amount of each of the above-described trifluoromonochloropropenes in the composition, and any combination of any and all ratios of two or more thereof, may fall within the following ranges: about 1 wt% to about 99 wt%; about 80 wt% to about 99 wt%; about 1 wt% to about 20 wt%; about 1 wt% to about 25 wt%; about 1 wt% to about 30 wt%; and from about 1 wt% to about 50 wt%. Preferred compositions of this type are described in the following table, with respect to the additional compounds specified in the table, all percentages being by weight and are understood to be modified by the word "about". Furthermore, it is to be understood that table 2 below applies to each trans CF ₃CH = CClH (1233 zdE), cis CF₃CH = CClH (1233 zdZ), trans CHF₂CF = CClH (1233 ydE), cis CHF₂CF = CClH (1233 ydZ), trans CHF2CH = CClF (1233 zbE), cis CHF2CH = CClF (1233 zbZ), trans CHF2CCl = CHF (1233 xeE), cis CHF2CCl = CHF (1233 xeZ), CH2FCCl = CF2 (1233 xc), trans CHFClCF = CFH (1233 yeE), cis chfclccf = CFH (1233 yeZ), CH2ClCF = CF2 (1233 yc), and all combinations and ratios of these two compounds.

TABLE 2

Combination with HFCO-1233

In the presence of H₂In preferred embodiments of O, the composition comprises H in an amount of from about 5% to about 50% by weight of the total composition, more preferably from about 10% to about 40% by weight, even more preferably from about 10% to about 20% by weight of the total composition₂O。

Containing CO in the adjuvant₂In preferred embodiments, the composition comprises CO in an amount of from about 5% to about 60% by weight of the total composition, more preferably from about 20% to about 50% by weight, even more preferably from about 40% to about 50% by weight of the composition₂。

In preferred embodiments where the adjuvant comprises an alcohol (preferably a C2, C3, and/or C4 alcohol), the composition comprises the alcohol in an amount of from about 5% to about 40% by weight of the total composition, more preferably from about 10% to about 40% by weight, still more preferably from about 15% to about 25% by weight of the total composition.

For compositions including HFC coagents, HFC co-blowing agents (preferably C2, C3, C4, and/or C5 HFC), and even more preferably difluoromethane (HFC-152 a) (HFC-152 a is particularly preferred for compositions used as a blowing agent for extruded thermoplastics) and/or pentafluoropropane (HFC-245) are preferably present in the composition in an amount of from about 5% to about 80% by weight of the composition, more preferably from about 10% to about 75% by weight, and even more preferably from about 25% to about 75% by weight of the composition. Further, in such embodiments, the HFC is preferably a C2-C4 HFC, and even more preferably a C3 HFC, with a pentafluorinated C3 HFC, such as HFC-245fa, being highly preferred in certain embodiments.

For compositions comprising an HFE adjuvant, the HFE adjuvant (preferably C2, C3, C4, and/or C5 HFE), and even more preferably HFE-254 (including HFE-254pc in particular), is preferably present in the composition in an amount of from about 5% to about 80% by weight of the total composition, more preferably from about 10% to about 75% by weight, and even more preferably from about 25% to about 75% by weight of the composition. Further, in such embodiments, the HFE is preferably a C2-C4 HFE, even more preferably a C3 HFC, with a tetrafluoro C3 HFE being highly preferred in certain embodiments.

For compositions including HC adjuvants, the HC adjuvants (preferably C3, C4, and/or C5 HC) are preferably present in the composition in an amount of from about 5% to about 80% by weight of the total composition, and even more preferably from about 20% to about 60% by weight of the composition.

e. Method and system

1. Foam forming method

All currently known and available methods and systems for forming foam are contemplated as being readily adaptable for use in the present invention. For example, the process of the present invention generally requires incorporating the blowing agent of the present invention into a foamable or foaming composition and then foaming the composition by a step or series of steps including volume expansion of the blowing agent of the present invention. In general, the systems and devices currently used for incorporating blowing agents and for foaming are expected to be readily adaptable for use in the present invention. Indeed, it is believed that one advantage of the present invention is to provide improved blowing agents that are generally compatible with existing foaming processes and systems.

Accordingly, those skilled in the art will recognize that the present invention encompasses methods and systems for foaming all types of foams, including thermoset foams, thermoplastic foams, and form-in-place foams. One aspect of the present invention is therefore the use of the present blowing agents in conventional foaming equipment, such as polyurethane foaming equipment, under conventional processing conditions. The process thus includes a masterbatch type operation, a blend type operation, a third stream blowing agent addition, and a blowing agent addition at the foam head (foam head).

In the case of thermoplastic foams, the preferred method generally comprises incorporating the blowing agent of the present invention into a thermoplastic material, preferably a thermoplastic polymer such as a polyolefin, and then subjecting the thermoplastic material to conditions effective to cause foaming. For example, the step of introducing the blowing agent into the thermoplastic material may comprise introducing the blowing agent into a screw extruder containing the thermoplastic, and the step of foaming may comprise reducing the pressure on the thermoplastic material and thereby expanding the blowing agent and assisting in the foaming of the material.

Those skilled in the art will recognize, especially in view of the disclosure contained herein, that the order and manner in which the blowing agents of the present invention are formed and/or added to the foamable composition generally does not affect the operability of the present invention. For example, in the case of an extrudable foam, the various components of the blowing agent and even the components of the present composition may not be mixed prior to introduction into the extrusion apparatus, or the components may not be added to the same location in the extrusion apparatus. In addition, the blowing agent can be introduced directly or as part of a premix, which is then further added to other parts of the foamable composition.

Thus, in certain embodiments, it may be desirable to introduce one or more components of the blowing agent at a first location in the extruder that is upstream of the location of addition of one or more other components of the blowing agent, where it is desirable for these components to meet and/or thereby operate more efficiently in the extruder. However, in certain embodiments, two or more components of the blowing agent are combined in advance and introduced into the foamable composition directly or together as part of a premix that is subsequently added further to other parts of the foamable composition.

In certain preferred embodiments, dispersants, cell stabilizers, surfactants, and other additives may also be incorporated into the blowing agent compositions of the present invention. Optionally but preferably a surfactant is added to act as a cell stabilizer. Some representative materials are sold under the names DC-193, B-8404, and L-5340, which are typically polysiloxane polyoxyalkylene block copolymers such as those disclosed in U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458, each of which is incorporated herein by reference. Other optional additives for the blowing agent mixture include flame retardants such as tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2, 3-dibromopropyl) -phosphate, tris (1, 3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.

Any of the methods known in the art, such as those described in "Polyurethanes Chemistry and technology" volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, incorporated herein by reference, may be used or adapted for use in accordance with the foam embodiments of the present invention.

2. Propellant and aerosol composition

In another aspect, the present invention provides a propellant composition comprising or consisting essentially of the composition of the present invention. In certain preferred embodiments, such propellant compositions are preferably sprayable compositions, either alone or in combination with other known propellants.

In one aspect, the present compositions may be used to propel an object, including solids and/or liquids and/or gases, by applying a force generated by the present compositions to such object (e.g., generated by the expansion of the present compositions). For example, it is preferred that such force is provided at least in part by the phase change of the composition of the invention from the liquid phase to the gas phase, and/or by the force released by the significant pressure drop of the composition of the invention as it exits the pressurized vessel. Thus, the compositions of the present invention may be used to apply burst or sustained forces to an object to be propelled. Accordingly, the present invention encompasses systems, containers, and devices comprising the compositions of the present invention and configured to propel or move an object (liquid or solid or gas) with a desired amount of force. Examples of such uses include containers (such as pressurized tanks and similar devices) that can be used to unblock blockages in a drain, pipe, or conduit, channel, or nozzle by the force of a propellant. Another use includes the use of the present compositions to propel solid objects through the environment, particularly the ambient air, such as bullets, projectiles, grenades, nets, shot, bean bags, electrodes (electodes) or other independent tethered or untethered projectiles. In other embodiments, the present compositions may be used to provide motion to a gyroscope, centrifuge, toy, or other object to be rotated, such as spitting motion, or to provide propulsion to solid objects, such as fireworks, confetti, projectiles, munitions, and other solids. In other applications, the force provided by the compositions of the present invention may be used to propel or manipulate a moving body, including a rocket or other projectile.

The propellant composition of the present invention preferably comprises a material to be sprayed and a propellant comprising, consisting essentially of, or consisting of the composition of the present invention. Inert ingredients, solvents, and other materials may also be present in the sprayable mixture. The sprayable composition is preferably an aerosol. Suitable materials to be sprayed include, but are not limited to, cosmetic materials such as deodorants, fragrances, hair sprays, cleansing solvents and lubricants, and medical materials such as anti-asthmatics. The term medical material is used herein in its broadest sense to include any and all materials that are effective or at least believed to be effective in therapy, diagnostic methods, analgesia, and similar therapies, thus including, for example, drugs and biologically active substances. The medical material is in certain preferred embodiments suitable for inhalation. The drug or other therapeutic agent is preferably present in the composition in a therapeutic amount, with a significant portion of the balance of the composition comprising one or more monochlorotrifluoropropene compound of the present invention as described above.

Aerosol products for industrial, consumer or medical use typically contain one or more propellants together with one or more active ingredients, inert ingredients or solvents. The propellant provides the force to propel the product in aerosolized form. While some aerosol products are propelled with compressed gases, such as carbon dioxide, nitrogen, nitrous oxide, and even air, most commercial aerosols use liquefied gas propellants. The most commonly used liquefied gas propellants are hydrocarbons such as butane, isobutane and propane. Dimethyl ether and HFC-152a (1, 1-difluoroethane) may also be used, either alone or in blends with the hydrocarbon propellant. Unfortunately, all of these liquefied gas propellants are very flammable, and their incorporation into aerosol formulations typically results in flammable aerosol products.

Applicants have recognized that there remains a need for non-flammable liquefied gas propellants for use in the formulation of aerosol products. The present invention provides compositions of the invention, particularly and preferably compositions comprising HFCO-1233 as described above, for use in certain industrial aerosol products, including for example spray cleaners, lubricants and the like, and in medicinal aerosols, including for example aerosols for the delivery of drugs to the lungs or mucous membranes. Examples include Metered Dose Inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for the delivery of drugs to accessible mucous membranes or intranasally. The invention thus includes a method of treating ailment (ailment), disease and similar health related problems of an organism, such as a human or animal, comprising administering to the organism in need of treatment a composition of the invention containing a drug or other therapeutic component. In certain preferred embodiments, the step of applying the present composition comprises providing an MDI containing the composition of the present invention (e.g., introducing the composition into the MDI), and then discharging the present composition from the MDI.

The compositions of the present invention, particularly compositions comprising or consisting essentially of any one or more of the monochlorotrifluoropropenes of the present invention, are capable of providing non-flammable liquefied gas propellants and aerosols that do not substantially affect global warming. The present compositions are useful for formulating a variety of industrial aerosols or other sprayable compositions, such as contact cleaners, dedusting agents, lubricant sprays, and the like, and consumer aerosols, such as personal care products, household products, and automotive products. The medicinal aerosol and/or propellant and/or sprayable compositions of the invention will include, in many applications, in addition to the compounds of the invention, medicaments, such as beta-agonists, corticosteroids or other medicaments, and optionally other ingredients, such as surfactants, solvents, other propellants, flavorants and other excipients. Unlike many compositions previously used in these applications, the compositions of the present invention have good environmental properties and are not considered to be a potential contributor to global warming. The present compositions thus provide, in certain preferred embodiments, substantially non-flammable liquefied gas propellants having very low global warming potentials.

3. Perfumes and fragrances

The compositions of the present invention provide advantages when used as part of, and in particular as carriers for, fragrance and fragrance formulations. The suitability of the present compositions for this use was confirmed by the following test procedure: a predetermined amount of plant material, such as jasmone, is placed in a thick-walled glass tube and an amount of one or more compounds of the present invention is added to the glass tube. The tube is then frozen and sealed. After thawing the tube, the mixture was found to have a liquid phase, thereby confirming that the monochloro-tetrafluoropropene or monochloro-tetrafluoropropenes advantageously serve as carriers for fragrance preparations and fragrances. Its potential as an extractant for bioactive compounds (such as biomass) and fragrances, including extraction from plant matter, has also been determined. In certain embodiments, it is preferred to use the present compositions in extraction applications where the present fluid is in its supercritical state. This and other uses involving the use of the present compositions in the supercritical or near supercritical state are described below.

4. Expanding agent

One possible advantage of the composition of the present invention is that it is preferred that the composition is gaseous under most ambient conditions. This feature enables them to fill the space without significantly increasing the weight of the (spilled) space that is spilled. In addition, the compositions of the present invention can be compressed or liquefied for relatively easy transport and storage. Thus, for example, the composition of the invention may be contained (preferably but not necessarily in liquid form) in a closed container, such as a pressure tank, having a nozzle therein adapted to release the composition as a pressurised gas into another environment in which it will be present for at least some time. For example, such uses may include the present compositions in canisters suitable for attachment to tires, such as those used in transportation vehicles (including cars, trucks, and airplanes). Further examples according to this embodiment include the present compositions in a similar configuration for inflating a balloon or other bladder (including other protective balloons) adapted to contain gaseous material under pressure for at least a period of time. Instead of the use of a fixed container, such as an I-tank, the present composition may be applied according to this aspect of the invention via a hose or other system containing the present composition in liquid or gaseous form, through which it may be introduced into such a pressurized environment as required by the particular application.

F. Method and system

The compositions of the present invention are useful in a variety of methods and systems, including as heat transfer fluids in heat transfer methods and systems, such as refrigerants used in refrigeration, air conditioning and heat pump systems. The present compositions are also advantageously used in systems and methods for generating aerosols, preferably comprising or consisting of the aerosol propellant in such systems and methods. Also included in certain aspects of the invention are methods of forming foam and methods of extinguishing or suppressing a fire. The present invention also includes, in certain aspects, methods of removing residue from an article, wherein the present compositions are used as solvent compositions in such methods and systems.

1. Heat transfer method and system

Preferred heat transfer methods generally comprise providing a composition of the present invention and transferring heat to or from the composition by sensible heat transfer, phase change heat transfer, or a combination of these. For example, in certain preferred embodiments, the present methods provide refrigeration systems comprising the refrigerants of the present invention and methods of producing heating or cooling by condensing and/or evaporating the compositions of the present invention. In certain preferred embodiments, the cooling method, comprising directly or indirectly cooling another fluid or directly or indirectly cooling an object, comprises condensing a refrigerant composition comprising a composition of the present invention and thereafter evaporating said refrigerant composition in the vicinity of the article to be cooled. The term "object" as used herein is intended to mean not only non-living organisms, but also living tissues, including animal tissues in general, and human tissues in particular. For example, certain aspects of the invention relate to the application of the present compositions to human tissue for one or more therapeutic uses, such as an analgesic technique, as a preparatory anesthetic, or as part of a therapy involving lowering the temperature of the object being treated. In certain embodiments, application to an object comprises providing the present compositions in liquid form under pressure, preferably in a pressure vessel having a one-way discharge valve and/or nozzle, and releasing the liquid form from the pressure vessel by spraying or otherwise applying the composition to the object. As the liquid evaporates from the surface to be sprayed, the surface cools.

Certain preferred methods of heating a fluid or object comprise condensing a refrigerant composition comprising a composition of the present invention in the vicinity of the fluid or object to be heated, and thereafter evaporating said refrigerant composition. In light of the disclosure herein, those skilled in the art can readily heat and cool the articles of the present invention without undue experimentation.

Applicants have discovered that in the system and method of the present invention, many important refrigeration system performance parameters are relatively close to those of R-134 a. Since many existing refrigeration systems are designed for R-134a or for other refrigerants having properties similar to R-134a, those skilled in the art will recognize the substantial advantages of low GWP and/or low ozone depleting refrigerants that may be used as replacements for R-134a or similar refrigerants with relatively few modifications to the system. In certain embodiments the invention contemplates retrofitting methods comprising replacing a heat transfer fluid (e.g., a refrigerant) in an existing system with a composition of the invention without substantially modifying the system. In certain preferred embodiments, the replacement step is a drop-on replacement-a composition of the present invention can be adapted as a heat transfer fluid without requiring significant redesign of the system and without requiring replacement of major equipment items. In certain preferred embodiments, the method comprises a drop-on replacement, wherein the productivity of the system is at least about 70%, preferably at least about 85%, and even more preferably at least about 90% of the productivity prior to replacement. In certain preferred embodiments, the method comprises a drop-in replacement wherein the suction pressure and/or discharge pressure, and even more preferably both, of the system is at least about 70%, more preferably at least about 90%, and even more preferably at least about 95% of the suction pressure and/or discharge pressure prior to replacement. In certain preferred embodiments, the method comprises a drop-in replacement, wherein the mass flow rate of the system is at least about 80%, and even more preferably at least 90%, of the mass flow rate prior to replacement.

In certain embodiments, the present invention provides cooling by absorbing heat from a fluid or object, preferably by evaporating the present refrigerant composition in the vicinity of the object or fluid to be cooled to produce a vapor comprising the present composition. The process preferably includes the further step of compressing the refrigerant vapor, typically with a compressor or similar device, to produce a vapor of the present composition at a relatively high pressure. Typically, the step of compressing the vapor results in the addition of heat to the vapor, thereby increasing the temperature of the relatively high pressure vapor. Preferably in such embodiments, the process includes removing from such relatively high temperature, high pressure vapor at least a portion of the heat added by the evaporation and compression steps. The heat removal step preferably comprises condensing the high temperature, high pressure vapor while the vapor is under relatively high pressure conditions to produce a relatively high pressure liquid comprising the composition of the invention. This relatively high pressure liquid is preferably followed by a nominally isenthalpic depressurization to produce a relatively low temperature, low pressure liquid. In such embodiments, this reduced temperature refrigerant liquid is then vaporized by heat from the object or fluid to be cooled.

In another process embodiment of the invention, the composition of the invention may be used in a heating process comprising condensing a refrigerant comprising the composition in the vicinity of a liquid or object to be heated. Such a method as described above is typically a reverse cycle of the refrigeration cycle described above.

2. Foaming method

One embodiment of the present invention relates to a process for forming foams, preferably polyurethane and polyisocyanurate foams. The process generally comprises 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 known in the art to be effective to form a foam or cellular structure. Any of the methods known in the art, such as those described in "Polyurethanes Chemistry and technology" volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, incorporated herein by reference, may be used or adapted for use in accordance with the foam embodiments of the present invention. Generally, this preferred method comprises preparing a polyurethane or polyisocyanurate foam by combining an isocyanate, a polyol or polyol mixture, a blowing agent or blowing agent mixture comprising one or more of the present compositions, and other materials, such as catalysts, surfactants, and optionally flame retardants, colorants, or other additives.

It is convenient in many applications to provide the components of the polyurethane or polyisocyanurate foam in a pre-blended formulation. Most commonly, the foam formulation is pre-blended into two components. The isocyanate and optionally certain surfactants and blowing agents comprise the first component, often referred to as the "a" component. The polyol or polyol mixture, surfactant, catalyst, blowing agent, flame retardant and other isocyanate-reactive components comprise the second component, often referred to as the "B" component. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by combining the a and B components together by hand mixing and preferably mechanical mixing techniques for small articles to form blocks, boards (slab), laminates, cast-in-place boards and other articles, spray foams, froths (froth), and the like. Optionally, other ingredients, such as flame retardants, colorants, auxiliary blowing agents, and even other polyols may be added as a third stream to the mix head or reaction site. Most preferably, however, they are all incorporated into one B-component as described above.

Thermoplastic foams may also be made using the compositions of the present invention. For example, conventional polystyrene and polyethylene formulations may be combined with the composition in a conventional manner to produce rigid foams.

3. Cleaning method

The present invention also provides a method of removing soil from a product, part, component, substrate or any other article or portion thereof by applying the composition of the present invention to the article. For convenience, the term "article" is used herein to refer to all such products, components, assemblies, substrates, etc. and is further intended to refer to any surface or portion thereof. Furthermore, the term "contaminant" is intended to mean any unwanted material or substance present on the article, even if such a substance is intentionally placed on the article. For example, in the manufacture of semiconductor devices, it is common to deposit a photoresist material onto a substrate to form a mask for an etching operation and to subsequently remove the photoresist material from the substrate. The term "contaminant" as used herein is intended to encompass and include such photoresist materials.

In certain preferred methods, the cleaning step comprises the step of rinsing material, such as a lubricant, from the vessel or container in connection with the step of preparing the retrofit and/or regeneration system. Such a process is in certain embodiments associated with retrofitting or replacing an old refrigerant with a new refrigerant in an existing heat transfer system, such as a refrigeration or air conditioning system, and flushing the system with the composition of the present invention as part of the process, particularly to remove at least a portion, and preferably substantially all, of the previously used lubricant present in such a system.

A preferred method of the present invention comprises applying the present composition to an article. While many and various cleaning techniques are contemplated to be advantageous for use of the compositions of the present invention, it is considered particularly advantageous to use the present compositions in conjunction with supercritical cleaning techniques. Supercritical cleaning is disclosed in U.S. patent No.6,589,355, which is assigned to the assignee of the present invention and incorporated herein by reference. For supercritical cleaning applications, it is preferred in certain embodiments to include one or more additional components in addition to HFCO-1233 in the present cleaning compositions, such as: HFO-1234 (preferably any one or more of cis-HFO-1234 ze, trans-HFO-1234 ze, HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye (E), and HFO-1234ye (Z)), CO₂And is known for use in supercritical fluidsOther additional components for cleaning applications. It is also possible and desirable in certain embodiments to use the present cleaning compositions in conjunction with specific vapor degreasing and solvent cleaning methods.

4. Flammability reduction method

According to certain other preferred embodiments, the present invention provides a method of reducing the flammability of a fluid, said method comprising adding a compound or composition of the present invention to said fluid. Flammability associated with a variety of inherently flammable fluids may be reduced according to the present invention. For example, fluids such as ethylene oxide, flammable hydrofluorocarbons, and hydrocarbons, including: HFC-152a, 1,1, 1-trifluoroethane (HFC-143 a), difluoromethane (HFC-32), propane, hexane, octane, and the like. For purposes of the present invention, a combustible fluid may be any fluid that exhibits a combustible range in air as measured by any standard conventional test method, such as ASTM E-681 and the like.

Any suitable amount of the present compounds or compositions can be added to reduce the flammability of the fluids of the present invention. Those skilled in the art will recognize that the amount added will depend, at least in part, on the degree of flammability of the fluid and to what degree it is desired to reduce its flammability. In certain preferred embodiments, the amount of compound or composition added to the combustible fluid is effective to render the resulting fluid substantially non-combustible.

5. Flame suppression method

The present invention further provides a method of suppressing a flame comprising contacting the flame with a fluid comprising a compound or composition of the present invention. Any suitable method of contacting a flame with the present composition may be used. For example, the composition of the present invention may be sprayed, poured onto a flame, or at least a portion of a flame may be immersed in the composition. Various conventional flame suppression devices and methods may be readily adapted by those skilled in the art for use with the present invention in light of the teachings herein.

6. Disinfection method

Many articles, devices and materials, particularly for use in the medical field, must be sterilized prior to use for health and safety reasons, such as the health and safety of patients and hospital staff. The present invention provides methods of disinfecting comprising contacting an article, device or material to be disinfected with a compound or composition of the present invention comprising one or more HFCO-1233 compounds described herein in combination with one or more disinfectants. Although many sterilizing agents are known in the art and are believed to be suitable for use in the present invention, in certain preferred embodiments, the sterilizing agent comprises ethylene oxide, formaldehyde, hydrogen peroxide, chlorine dioxide, ozone, and combinations of these. In certain embodiments, ethylene oxide is a preferred sterilant. Those skilled in the art can readily determine, based on the teachings contained herein, the relative proportions of sterilant and the present compounds to be used in conjunction with the present disinfecting compositions and methods, and all such ranges are within their broad scope. As is known to those skilled in the art, certain sterilizing agents, such as ethylene oxide, are relatively flammable components and the compounds of the present invention are included in the present compositions in amounts effective, along with the other components present in the composition, to reduce the flammability of the disinfecting composition to acceptable levels.

The sterilization process of the present invention may be a high or low temperature sterilization of the present invention involving the use of the compounds or compositions of the present invention at temperatures of about 250F to about 270F, preferably in a substantially sealed chamber. The process is typically completed in less than about 2 hours. However, some articles, such as plastic articles and electrical components, cannot withstand such high temperatures and require low temperature sterilization. In a cryogenic sterilization process, the article to be sterilized is exposed to a fluid comprising the composition of the present invention at a temperature of from about room temperature to about 200 ° f, more preferably from about room temperature to about 100 ° f.

The cryogenic sterilization of the present invention is preferably at least a two-step process carried out in a substantially sealed, preferably airtight, chamber. In the first step (the sterilization step), the product that has been cleaned and wrapped in a breathable bag is placed in the chamber. Air is then evacuated from the chamber by drawing a vacuum and possibly by displacing the air with steam. In certain embodiments, it is preferred to inject steam into the chamber to achieve a relative humidity of preferably about 30% to about 70%. Such humidity may maximize the disinfecting efficacy of the disinfectant introduced into the chamber after the desired relative humidity is achieved. After a time sufficient for the sterilant to penetrate the package and reach the void in the article, the chamber is evacuated of sterilant and steam.

In a preferred second step of the process (aeration step), the article is aerated to remove disinfectant residues. Removal of such residues is particularly important in the case of toxic disinfectants, although this is optional in the case of the use of the substantially non-toxic compounds of the present invention. Typical aeration methods include air scrubbing, continuous aeration, and a combination of both. Air scrubbing is a batch process and typically involves evacuating the chamber for a relatively short period of time, for example 12 minutes, and then introducing air into the chamber at atmospheric pressure or higher. This cycle is repeated any number of times until the desired removal of the sterilant is achieved. Continuous aeration typically involves introducing air through an inlet on one side of the chamber and then drawing a vacuum through an outlet on the other side of the chamber by applying a slight vacuum to the outlet. Typically, the two methods are combined. For example, a common approach involves performing an air wash and subsequent aeration cycle.

7. Supercritical process

Many of the uses and methods described herein are generally contemplated as being performed with the present compositions in a supercritical or near supercritical state. For example, the present compositions may be used in the solvent and solvent extraction applications mentioned herein, particularly for materials such as alkaloids (typically derived from plant sources), for example caffeine, codeine and papaverine, for organometallic materials such as metallocenes, which may be used as catalysts in general, and for fragrances and perfumes such as jasmone.

The present compositions, preferably in their supercritical or near supercritical state, are useful in processes involving the deposition of catalysts, particularly organometallic catalysts, on solid supports. In a preferred embodiment, the methods comprise the step of forming finely divided catalyst particles, preferably by precipitating such catalyst particles from the present compositions in a supercritical or near supercritical state. It is expected that in certain preferred embodiments, the catalysts made according to the present methods exhibit excellent activity.

Certain MDI methods and devices described herein are also contemplated for use with drugs in finely divided form, in which case the present invention is contemplated to provide methods comprising the step of incorporating such finely divided drug particles, such as salbutamol, into the present fluid, preferably by dissolving such particles in the present composition, preferably in a supercritical or near supercritical state. If the solubility of the material is relatively low when the fluid is in a supercritical or near supercritical state, it is preferred to use an entraining agent, such as an alcohol.

The present compositions in the supercritical or near supercritical state are also expected to be useful for cleaning circuit boards and other electronic materials and articles.

Certain materials may have very limited solubility in the present compositions, particularly in the supercritical or near supercritical state. In these cases, the present compositions can be used as an anti-solvent for precipitating such low solubility solutes from a solution in another supercritical or near supercritical solvent, such as carbon dioxide. For example, supercritical carbon dioxide is commonly used in the extrusion of thermoplastic foams, and the present compositions can be used to precipitate certain materials contained therein.

It is also contemplated that in certain embodiments it may be desirable to use the present compositions in a supercritical or near supercritical state as a blowing agent.

The present method and system also includes a one-component foam, preferably a polyurethane foam, containing the blowing agent of the present invention. In certain preferred embodiments, a portion of the blowing agent is contained in the foam-forming agent, preferably by dissolving in a container of a foam-forming agent that is liquid under pressure, a second portion of the blowing agent being present as a separate gas phase. In such systems, the contained/dissolved blowing agent is primarily used to expand the foam, and the separate gas phase is used to provide the propulsive force for the foam-forming agent. Such one-component systems are typically and preferably packaged in a container, such as an aerosol can, and the blowing agent of the present invention thus preferably provides for foam expansion and/or energy for outputting foam/foamable material from the package, preferably both, and in certain embodiments such systems and methods comprise charging the package with a fully formulated system (preferably an isocyanate/polyol system) and adding the gaseous blowing agent of the present invention to the package, preferably an aerosol can.

Any of the methods known in the art, such as those described in "Polyurethanes Chemistry and technology" volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, which are incorporated herein by reference, may be used or adapted for use in accordance with the foaming embodiments of the present invention.

It is also contemplated in certain embodiments that it may be desirable to use the present compositions in a supercritical or near supercritical state as a blowing agent.

G. Foam

The present invention also relates to all foams (including but not limited to closed cell foams, open cell foams, rigid foams, resilient foams, integral skin foams, etc.) made from polymer foam formulations containing a blowing agent comprising the compositions of the present invention. Applicants have found that one advantage of the foams of the present invention, particularly thermoset foams such as polyurethane foams, is the ability to achieve (preferably in conjunction with thermoset foam embodiments) excellent thermal properties, as measured by the K-factor or λ, particularly and preferably under low temperature conditions. While the present foams, and particularly the thermoset foams of the present invention, are contemplated for use in a variety of applications, in certain preferred embodiments, the present invention includes appliance foams (appliance foams) according to the present invention, including refrigerator foams, freezer foams, refrigerator/freezer foams, dashboard (panel) foams, and other cold or low temperature manufacturing applications.

The foams of the present invention in certain preferred embodiments have low ozone depletion potential and low global warming potential 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 One or more excellent features, characteristics and/or properties are also provided, including: thermal insulation efficiency (especially for thermoset foams), dimensional stability, compressive strength, aging of thermal insulation properties. In certain highly preferred embodiments, the present invention provides thermoset foams, including such foams that are formed into foam articles, that exhibit improved thermal conductivity compared to foams made using the same amount of the same blowing agent (or the conventional blowing agent HFC-245 fa), but without the compound of formula I of the present invention. In certain highly preferred embodiments, the thermoset foams, preferably polyurethane foams, of the present invention exhibit a K-factor at 40 DEG F (BTU in/hr ft) of no greater than about 0.14, more preferably no greater than 0.135, still more preferably no greater than 0.13²F.). Further, in certain embodiments, the thermoset foams, preferably polyurethane foams, of the present invention exhibit a K-factor at 75 ° F (BTU in/hr ft) of no greater than about 0.16, more preferably no greater than 0.15, still more preferably no greater than 0.145² ℉）。

In other preferred embodiments, the present foams exhibit improved mechanical properties compared to foams made with blowing agents outside the scope of the present invention. For example, certain preferred embodiments of the present invention provide foams and foam articles having a compressive strength that is superior, preferably at least about 10 relative percent greater, and even more preferably at least about 15 relative percent greater, than foams made using a blowing agent comprised of cyclopentane under substantially the same conditions. Furthermore, in certain embodiments foams made according to the present invention preferably have a compressive strength that is on a commercial basis comparable to that produced by making the foam under substantially the same conditions except that the blowing agent is comprised of HFC-245 fa. In certain preferred embodiments, the foams of the present invention exhibit a compressive strength of at least about 12.5% yield (in both the parallel and perpendicular directions), and even more preferably at least about 13% yield in each of said directions.

Examples

The following examples are provided to illustrate the invention but not to limit its scope.

Example 1

Coefficient of performance (COP) is a recognized measure of refrigerant performance, and is particularly useful in expressing the relative thermodynamic efficiency of a refrigerant in a particular heating or cooling cycle involving evaporation or condensation of the refrigerant. In refrigeration engineering, the term denotes the ratio of the effective refrigeration to the energy applied by the compressor in compressing the vapor. The capacity of a refrigerant represents the amount of cooling or heating it provides and provides a measure of the compressor's ability to pump heat at a given volumetric flow rate of the refrigerant. In other words, given a particular compressor, a refrigerant with a higher capacity delivers a higher cooling or heating capacity. One way to estimate the COP of a refrigerant under specific operating conditions is from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, e.g., r.c. Downing, fluor corpon regenerative HANDBOOK, chapter 3, prenotice-Hall, 1988).

A refrigeration/air conditioning cycle system is provided wherein the condenser temperature is about 150 ° f and the evaporator temperature is about-35 ° f under nominally isentropic compression and the compressor inlet temperature is about 50 ° f. COP of compositions consisting essentially of the compounds specified in table 3 below were measured at a range of condenser and evaporator temperatures and found to each have a workable value for COP, capacity and discharge temperature (workable values).

TABLE 3

This example demonstrates that certain preferred compounds for use with the present compositions each have a viable energy efficiency, and that compressors using the present refrigerant compositions produce a viable discharge temperature.

Example 2

Refrigerant compositions comprising each of the compounds specified in table 3 above were tested for miscibility with various refrigeration lubricants. The lubricants tested were mineral Oil (C3), alkylbenzene (Zerol 150), ester Oil (Mobil EAL 22 cc and Solest 120), polyalkylene glycol (PAG) Oil (Goodwrench refining Oil for 134a system), and poly (. alpha. -olefin) Oil (CP-6005-100). For each refrigerant/oil combination, three compositions, namely 5, 20 and 50 wt.% lubricant, were tested, with the balance of each being the tested compound of the invention.

The lubricant composition was placed into a thick-walled glass tube. The tube is evacuated, the refrigerant compound of the present invention is added, and the tube is then sealed. The tube was then placed in an air bath environment chamber, the temperature of which was varied from approximately-50 ℃ to 70 ℃. The tube contents were visually inspected for the presence of one or more liquid phases at approximately 10 ℃ intervals. The mixture was found to have an acceptable level of miscibility.

Example 3 polyol foam

This example illustrates the use of a blowing agent according to a preferred embodiment of the present invention, i.e., the use of the compounds specified in table 3 above, and their use for making polyol foams according to the present invention. The components of the polyol foam formulation were prepared according to table 4 below:

TABLE 4

Polyol component PBW

Voranol 490 50

Voranol 391 50

0.5 part of water

B-8462 (surfactant) 2.0

Polycat 8 0.3

Polycat 41 3.0

HFO-1234ze 35

Total 140.8

Isocyanates

M-20S 123.8 index 1.10

Voranol 490 is a sucrose based polyol and Voranol 391 is a toluene diamine based polyol, each from Dow Chemical. B-8462 is a surfactant available from Degussa-Goldschmidt. Polycat catalysts are based on tertiary amines and are available from Air Products. Isocyanate M-20S is a product of Bayer LLC.

The foam is prepared by first mixing its ingredients without the addition of a blowing agent. Approximately 52.6 grams of each polyol mixture (without blowing agent) was charged into two Fisher-Porter tubes and sealed and placed in a refrigerator to cool and create a slight vacuum. Using a gas burette, approximately 17.4 grams of each HFCO-1233 compound in table 3 was added to each tube, which was then placed in an ultrasonic bath in warm water and allowed to stand for 30 minutes. About 87.9 grams of the isocyanate mixture was placed in a metal container and placed in a refrigerator and allowed to cool to about 50 ° f. The polyol tube was then opened and weighed into a metal mixing vessel (approximately 100 grams of polyol blend was used). The isocyanate from the cooled metal container was then immediately poured into the polyol and mixed with an air mixer with twin propellers at 3000 RPM for 10 seconds. The blend immediately began to foam with stirring and was then poured into an 8x8x4 inch box and allowed to foam. The foam was then allowed to cure at room temperature for 2 days. The foam was then cut into samples suitable for measuring physical properties and found to have acceptable density and K-factor.

Example 4 polystyrene foam

This example illustrates the use of a blowing agent according to two preferred embodiments of the present invention, namely the production of polystyrene foam using as blowing agent each of the HFCO-1233 compounds described herein. Test equipment and procedures have been established to aid in determining whether a particular blowing agent and polymer will produce foam and foam quality. The ground polymer (Dow Polystyrene 685D) and blowing agent consisting essentially of the respective HFCO-1233 compounds described herein were combined in a container. The vessel volume was 200 cubic centimeters and was made of two pipe flanges and a 2 inch diameter by 4 inch long section of schedule 40 stainless steel pipe. The container is placed in an oven set at a temperature of about 190F to about 285F, preferably 265F for polystyrene, and held there until temperature equilibrium is reached.

The pressure in the container is then released to rapidly produce the foamed polymer. The blowing agent plasticizes the polymer as it dissolves into it. The resulting densities of the two foams thus produced using this method were determined and found to be acceptable.

Example 5A polystyrene foam

This example demonstrates the performance of each of the HFCO-1233 compounds described herein alone as a blowing agent for polystyrene foams formed in a twin screw type extruder. The apparatus used in this example was a Leistritz twin screw extruder having the following characteristics:

30 mm co-rotating screw

L: D ratio = 40:1

The extruder was divided into 10 sections, each representing an L: D ratio of 4: 1. Polystyrene resin is introduced into the first section, blowing agent is introduced into the sixth section, and the extrudate exits the tenth section. The extruder is operated primarily as a melt/compounding extruder. The subsequent cooling extruders are connected in series, and the design characteristics are as follows:

leistritz double-screw extruder

40 mm co-rotating screw

L: D ratio = 40:1

Die head: 5.0 mm round

A polystyrene resin, Nova Chemical-general extrusion grade polystyrene, identified as Nova 1600, was fed into the extruder under the conditions described above. The resin has a recommended melt temperature of 375 DEG F-525 DEG F. The pressure at the extruder die was about 1320 pounds per square inch (psi) and the temperature at the die was about 115 ℃.

A blowing agent consisting essentially of each of the HFCO-1233 compounds described herein was added to the extruder at the indicated location alone, including talc as a nucleating agent in an amount of about 0.5% by weight of the total blowing agent. Foams were made according to the present invention using blowing agents at concentrations of 10 wt%, 12 wt% and 14 wt%. The resulting foam has a density in the range of about 0.1 g/cc to 0.07 g/cc and a cell size of about 49 to about 68 microns. Foams of about 30 mm diameter are visually of excellent quality, very fine cell size, with no visible or noticeable pores or voids.

Example 5B polystyrene foam

The procedure of example 5C was repeated except that the blowing agent contained approximately 50 weight percent of each of the HFCO-1233 compounds described herein and 50 weight percent HFC-245fa and the nucleating agent at the concentration shown in example 5. Expanded polystyrene was prepared at blowing agent concentrations of about 10% and 12%. The resulting foam had a density of about 0.09 g/cc and a cell size of about 200 microns. Foams of about 30 mm diameter are visually of excellent quality, fine cell size, with no visible or significant voids.

Example 5C-polystyrene foam

The procedure of example 5 was repeated except that the blowing agent contained approximately 80% of each of the HFCO-1233 compounds described herein and 20 wt% HFC-245fa and the nucleating agent at the concentration shown in example 5. Expanded polystyrene was prepared at blowing agent concentrations of about 10% and 12%. The resulting foam had a density of about 0.08 g/cc and a cell size of about 120 microns. Foams of about 30 mm diameter are visually of excellent quality, fine cell size, with no visible or significant voids.

Example 5D-polystyrene foam

The procedure of example 5 was repeated using each of the HFCO-1233 compounds described herein on its own, except that the nucleating agent was omitted. The foam had a density of 0.1 g/cc and a cell diameter of about 400 a. Foams of about 30 mm diameter are visually of excellent quality, fine cell size, with no visible or significant voids.

Example 6 polyurethane foam

This example demonstrates the performance of each of the HFCO-1233 compounds described herein in combination with a hydrocarbon co-blowing agent, particularly the use of a composition comprising each of the HFCO-1233 compounds described herein alone, and a cyclopentane co-blowing agent, to produce a polyurethane foam having acceptable compressive strength properties.

A commercially available refrigeration device type polyurethane foam formulation (foam forming agent) is provided. The polyol blend is comprised of a commercial polyol, a catalyst and a surfactant. Such formulations are suitable for use in combination with gaseous blowing agents. Standard commercial polyurethane processing equipment was used for the foam forming process. Forming a gaseous blowing agent combination comprising each of the HFCO-1233 compounds described herein at a concentration of about 60 mole% and cyclopentane at a concentration of about 40 mole% of the total blowing agent. This example illustrates the acceptable physical properties, including compressive strength and K-factor properties, of the combination of each of the HFCO-1233 compounds described herein with a cyclopentane co-blowing agent.

Example 7 polyurethane foam K-factor

This example demonstrates the performance of blowing agents comprising each of the HFCO-1233 compounds described herein, as well as each of the HFC co-blowing agents mentioned above, in the preparation of polyurethane foams. The same foam formulations, equipment and procedures used in examples 5 and 6 were used except for the blowing agent. Blowing agents were prepared comprising each of the HFCO-1233 compounds described herein in a concentration of about 80 weight percent of the total blowing agent and each of the HFC co-blowing agents mentioned above in a concentration of about 20 weight percent of the total blowing agent. This blowing agent was then used to form a foam, and the k-factor of the foam was measured and found to be acceptable.

Example 8 polyurethane foam K-factor

Another experiment was conducted using the same polyol formulation and isocyanate as in examples 5 and 6. The foam was prepared by hand mixing. This blowing agent consisted of a compound corresponding to each of the HFCO-1233 compounds described herein at about the same mole percent of the foamable composition as the blowing agent in examples 5 and 6. An acceptable foam is formed.

Example 9 polyurethane foam K-factor

Another experiment was conducted using the same polyol formulation and isocyanate as in examples 5 and 6. The foam was prepared by hand mixing. A series of blowing agents consisted of combinations of methanol, propanol, isopropanol, butanol, isobutanol, and tert-butanol, each at a 50:50 molar ratio to each HFCO-1233 compound described herein, each combination being present in the blowing agent composition at about the same molar percentage of the foamable composition as the blowing agents in examples 5 and 6. In each case an acceptable foam was formed.

Example 10 polyurethane foam K-factor

Another experiment was conducted using the same polyol formulation and isocyanate as in examples 5 and 6. The foam was prepared by hand mixing. A series of blowing agents consists of each HFCO-1233 compound described herein and each of the following additional compound combinations: iso-pentane, n-pentane, and cyclo-pentane. Three blowing agents were formed in combination with each additional compound at a molar ratio of HFCO-1233 to additional compound of 25:75, 50:50, and 75: 25. Each blowing agent composition was present at about the same mole percent of foamable composition as the blowing agent in examples 5 and 6. In each case an acceptable foam was formed.

Example 11 polyurethane foam K-factor

Another experiment was conducted using the same polyol formulation and isocyanate as in examples 5 and 6. The foam was prepared by hand mixing. A series of blowing agents consists of each HFCO-1233 compound described herein and each of the following additional compound combinations: water and CO₂. Three blowing agents were formed in combination with each additional compound at a molar ratio of HFCO-1233 to additional compound of 25:75, 50:50, and 75: 25. Each blowing agent composition was present at about the same mole percent of foamable composition as the blowing agent in examples 5 and 6. In each case an acceptable foam was formed.

Example 12 polyurethane foam K-factor

Another experiment was conducted using the same polyol formulation and isocyanate as in examples 5 and 6. The foam was prepared by hand mixing. A series of blowing agents is comprised of the combination of each HFCO-1233 compound described herein with each HFO-1234 ye-trans (E) (boiling point 15C) and HFO-1234 ye-cis (Z) (boiling point 24C) that are combined with each HFCO-1233 in a 50:50 molar ratio, each combination being present in the blowing agent composition at about the same molar percentage of the foamable composition as the blowing agent in examples 5 and 6. In each case an acceptable foam was formed.

Example 13 polyurethane foam K-factor

Another experiment was conducted using the same polyol formulation and isocyanate as in examples 5 and 6. The foam was prepared by hand mixing. The blowing agent consisted of a combination of each of the HFCO-1233 compounds described herein and trans-1, 2 dichloroethylene in a 75:25 molar ratio of HFCO-1233 to trans-1, 2 dichloroethylene, which blowing agent composition was about the same mole percent of the foamable composition as the blowing agent in examples 5 and 6. An acceptable foam is formed.

Example 14 polyurethane foam K-factor

Another experiment was performed using the same polyol formulation and isocyanate as in example 9. The foam was prepared by hand mixing. The blowing agent is comprised of a combination of 75:25 mole ratios of each HFCO-1233 compound and methyl formate described herein, present in the blowing agent composition at about the same mole percent of the foamable composition as the blowing agent in examples 5 and 6. In each case an acceptable foam was formed.

Example 15 silicon solvent

A series of compositions were prepared with each composition consisting of each HFCO-1233 compound described herein. Each composition was transferred to a glass container. A silicon lubricant, particularly a high viscosity (12,500 cP) silicone oil, is added to the composition to a concentration of about 10% by weight. This produced a homogeneous, single-phase solution, indicating that each HFCO-1233 compound dissolved the silicone-based lubricant.

Example 16-HFCO-1233/trans-1, 2-dichloroethylene

A series of compositions were prepared with each composition consisting of each HFCO-1233 compound and trans-1, 2-dichloroethylene described herein in a weight ratio of HFCO-1233: trans-1, 2-dichloroethylene of 25:75 and 50: 50. Each composition was then transferred to a glass container. A silicon lubricant, in particular a high viscosity (12,500 cP) silicone oil, was added to each solvent to a concentration of about 10% by weight. This produced a homogeneous single phase solution, indicating that this combination dissolved the silicone oil.

Example 17 detergent

A metal coupon was coated with a rosin-based flux and allowed to dry. The coupons were weighed and then dipped into a series of compositions consisting of each of the HFCO-1233 compounds described herein. The coupon was removed, allowed to dry, and reweighed to determine how much flux was removed. In two repeated tests (duplicate runs), an average of 25% by weight of flux was removed.

Example 18 HFCO-1233/methanol as detergent

A metal coupon was coated with a rosin-based flux and allowed to dry. The coupons were weighed and then immersed in a series of compositions of each of the HFCO-1233 compounds described herein and methanol at several different concentrations ranging from about 1% to about 10% (still more preferably from about 1% to about 5%) by weight, including about 1%, about 2%, about 3%, about 5%, and about 10%. The coupon was removed, allowed to dry, and reweighed to determine how much flux was removed. In two repeated experiments, the flux was removed.

Example 19 extractant

A medicine, especially plant-derived artemisinin, is extracted from herba Artemisiae Annuae plant and is used as antimalarial. The artemisinin sample was weighed into a vial. A series of compositions consisting of each HFCO-1233 compound described herein was added to the vial until artemisinin dissolved. The results indicate that drugs, particularly of botanical origin, such as artemisinin, are soluble in the respective HFCO-1233 compounds described herein, indicating that such compounds can be used to extract drugs from biomass.

Example 20 solvent mineral oil

A hydrocarbon lubricant, especially mineral oil, was added to vials containing a series of compositions consisting of each of the HFCO-1233 compounds described herein and methanol in a weight ratio of about 98:2, about 96:4, and HFCO-1233/methanol/pentane in a weight ratio of about 92:2:6, respectively. In all cases, at mineral oil concentrations of greater than 10 wt.%, a homogeneous single-phase solution was formed.

Example 21 Aerosol

A sprayable aerosol was prepared as follows: a series of compositions consisting of each of the HFCO-1233 compounds described herein were added to an aerosol can, the can sealed by crimping the aerosol valve in place, and HFC-134a propellant was added to a concentration of about 14 wt% 134a and about 76 wt% HFCO-1233. Hydraulic oil was applied to a metal test block with a cotton swab and the block weighed. Aerosols each containing HFCO-1233 were sprayed onto the metal substrate for 10 seconds. The test block was dried and reweighed. About 60% by weight of the hydraulic oil is removed.

Example 22 solvent-PAG

Synthetic lubricants, particularly polyalkylene glycol (PAG) lubricants, more particularly PAGs consisting essentially of 2 or more oxypropylene groups and having a viscosity of about 10 to about 200 centistokes at about 37℃ (Idemitsu Kosan is sold under the trade name ND-8) are added to vials containing a range of compositions consisting of each of the HFCO-1233 compounds described herein. At PAG concentrations greater than 10 wt%, a homogeneous single phase solution was formed. The properties of the synthetic lubricant ND-8 are specified in Table 5 below.

TABLE 5

ND-8 Properties

Properties of	The viscosity of the mixture is measured by the following method, 40℃ cSt	EO to PO ratio	Molecular weight
					42.3	0:1	930

Molecular weight is number average molecular weight.

Example 23-HFCO-1233 and Co-solvent

The PAG lubricant described in example 22 above was added to vials containing methanol in a weight ratio to (a) about 98:2 HFCO: methanol, respectively; (b) pentane in a weight ratio of about 96:4 HFCO to pentane; and (c) about a 92:2:6 HFCO: methanol to pentane weight ratio of methanol/pentane. In all cases, at PAG oil concentrations greater than 10 wt%, a homogeneous single phase solution was formed.

Example 24

This example illustrates the performance of one embodiment of the present invention wherein the refrigerant composition comprises each of the above-described HFCO-1233 compounds, wherein a major proportion, preferably at least about 75 weight percent, and even more preferably at least about 90 weight percent, of the refrigerant composition is each of said HFCO-1233 compounds. More particularly, this example demonstrates the use of such compositions as working fluids in refrigerant systems, high temperature heat pumps, and organic rankine cycle systems. One example of a first system is a system having an evaporation temperature of about 35 ° f and a condensation temperature of about 150 ° f. For convenience, such heat transfer systems, i.e., systems having an evaporator temperature of about 35F to about 50F and a CT of about 80F to about 120F, are referred to herein as "chillers" or "chiller AC" systems. For comparison, the respective operation of these systems was found to be acceptable when R-123 was used.

Example 25

This example illustrates the performance of one embodiment of the present invention wherein the refrigerant composition comprises each of the above-described HFCO-1233 compounds, wherein a major proportion, preferably at least about 75 weight percent, and even more preferably at least about 90 weight percent of the composition comprises each of the above-described HFCO-1233 compounds. More particularly, this composition is useful as a replacement for HFC-134a in four refrigerant systems. The first system is a system having an Evaporator Temperature (ET) of about 20 ° f and a Condenser Temperature (CT) of about 130 ° f. For convenience, such heat transfer systems, i.e., systems having an ET of about 0 to about 35 ° f and a CT of about 80 to about 130 ° f, are referred to herein as "medium temperature" systems. The second system is a system having an ET of about-10F and a CT of about 110F. For convenience, such heat transfer systems, i.e., systems having an evaporator temperature of about-20F to about 20F and a CT of about 80F to about 130F, are referred to herein as "refrigeration/freezing" systems. The third system is a system having an ET of about 35 ° f and a CT of about 150 ° f. For convenience, such heat transfer systems, i.e., systems having an evaporator temperature of about 30F to about 60F and a CT of about 90F to about 200F, are referred to herein as "automotive AC" systems. The fourth system is a system having an ET of about 40 ° f and a CT of about 60 ° f. For convenience, such heat transfer systems, i.e., systems having an evaporator temperature of about 35F to about 50F and a CT of about 80F to about 120F, are referred to herein as "chillers" or "chiller AC" systems. The operation of each such system using each composition was found to be acceptable compared to R-134 a.

Based on the above embodiments, many important refrigeration system performance parameters are relatively close to those of many previously used refrigerants, such as R-134 a. Since many existing refrigeration systems are designed for these refrigerants, including R-134a or for other refrigerants, those skilled in the art will recognize the substantial advantages of low GWP and/or low ozone depleting refrigerants that may be used as replacements for R-134a or similar refrigerants with relatively few modifications to the system. In certain embodiments the present invention contemplates retrofitting methods comprising replacing a refrigerant in an existing system with a composition of the present invention (preferably a composition comprising at least about 90% by weight of the aforementioned HFCO-1233 compound and/or consisting essentially of the aforementioned HFCO-1233 compound) without substantially modifying the system. In certain preferred embodiments, the replacement step is a drop-on replacement-no significant redesign of the system is required and no major equipment items need to be replaced to accommodate the refrigerant of the present invention.

Claims

1. A composition comprising:

(a) at least one fluorinated olefin having an MIR value less than ethane; and

(b) at least one additional component selected from the group consisting of Hydrofluorocarbons (HFCs), ethers, alcohols, aldehydes, ketones, methyl formate, formic acid, water, trans-1, 2-dichloroethylene, carbon dioxide, Dimethoxymethane (DME), a second fluoroalkene different from the first fluoroalkene, and combinations of any two or more of these.

2. The composition of claim 1, wherein the at least one additional component comprises from about 15% to about 85% by weight of at least one hydrocarbon selected from the group consisting of iso-pentane, n-pentane, cyclo-pentane, butane and iso-butane and combinations of these.

3. The composition of claim 1, wherein the fluorinated olefin comprises at least one monochlorotrifluoropropene present in the composition in an amount from about 20% to about 90% by weight of the composition.

4. The composition of claim 1, wherein the at least one additional component is selected from the group consisting of 2-ethyl-1-hexanol, trans-1, 2-dichloroethylene, dimethoxymethane, methyl formate, water, and CO 2.

5. The composition of claim 1 wherein the fluorinated olefin comprises a combination of trans-1, 1,1, trifluoro, 3-chloro-propene (trans HFCO-1233 zd) and cis-1, 1,1, trifluoro, 3-chloro-propene (cis HFCO-1233 zd) in a cis: trans weight ratio of from about 30:70 to about 5: 95.

6. The composition of claim 1, wherein the composition is provided as a blowing agent, aerosol, solvent, or heat transfer agent.

7. A composition comprising:

(a) at least one fluorinated olefin having an MIR value less than ethane and combinations of two or more of these; and

(b) at least one additional component selected from the group consisting of lubricants, stabilizers, metal deactivators, corrosion inhibitors, flammability inhibitors, trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2, 2-tetrafluoroethane (HFC-134), 1,1,1, 2-tetrafluoroethane (HFC-134 a), difluoroethane (HFC-152 a), 1,1,1,2,3,3, 3-heptafluoropropane (HFC-227 ea), 1,1,1,3,3, 3-hexafluoropropane (HFC-236 fa), 1,1,1,3, 3-pentafluoro-propane (HFC-236 fa), 1,1,1,3, 3-pentafluoro-ethane (HFC-134 a)Propane (HFC-245 fa), 1,1,1,3, 3-pentafluorobutane (HFC-365 mfc), water and CO₂And combinations of two or more of these.

8. A solvent extraction process comprising solvent extracting a material by contacting the material with at least one fluorinated olefin having an MIR value less than ethane.

9. The method of claim 8, wherein the material comprises at least one alkaloid derived from at least one plant source.

10. A method for depositing a catalyst on a solid support comprising precipitating particles of the catalyst from at least one fluorinated olefin having an MIR value less than ethane.