JP2014114456A - Foaming agents and compositions containing fluorine substituted olefins and ethers, and methods of foaming - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide safe and new fluorocarbon based mixture foaming agents which are non-chlorine-containing compounds that do not deplete the ozone layer and are ecological, which impart foam characteristics such as appropriate chemical stability, low or no toxicity, and low or no flammability, which are alternatives to CFCs and HCFCs, and which have as low global warming potentials as possible.SOLUTION: Provided are foaming agents for thermoset foams having compositions containing 30-99 wt.% of tetrafluoropropenes (HFO-1234) or trifluoro, monochloropropenes (HFCO-1233), and 1-70 wt.% of at least one fluorinated ether.

Description

The present invention has particular utility in many applications, including heat transfer systems such as cooling systems, and in blowing agents, foamable compositions, foams and articles made with or from foams, It relates to a method and a system. In a preferred embodiment, the present invention provides:
Compositions comprising at least one polyfluorinated olefin and at least one fluorinated ether of the present invention are directed.

Fluorocarbon-based fluids have found widespread use in many commercial and industrial applications, including applications as aerosol propellants and blowing agents. Including the relatively high global warming potential associated with the use of some compositions previously used in these applications,
Hydrofluorocarbons ("HFCs") for certain environmental concerns of concern
It has become increasingly desirable to use fluids that have a low or exactly zero ozone depletion potential, such as Therefore, substantial amounts of chlorofluorocarbons (“CFC
It is desirable to use fluids that do not contain hydrochlorofluorocarbons ("HCFCs"). In addition, some HFC fluids may have a relatively high global warming potential associated with them, having the lowest possible global warming potential while maintaining the desired performance in use characteristics. It is desirable to use a hydrofluorocarbon or other fluorinated fluid. As suggested above, there has recently been increased interest in the potential to damage the Earth's atmosphere and climate, and certain chlorinated compounds have been identified as being particularly problematic in this regard. The use of chlorine-containing compositions (eg, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), etc.) for many applications is the reason for the ozone depleting properties associated with many such compounds. It is disadvantageous.
Thus, there is a growing need for new fluorocarbon and hydrofluorocarbon compounds and compositions that are attractive alternatives to the compositions previously used in these and other applications. For example, chlorine-containing compounds are hydrofluorocarbons (HFCs)
By replacing it with chlorine-free compounds that do not deplete the ozone layer,
It has become desirable to improve chlorine-containing systems such as blowing agent systems or cooling systems. The industry generally provides alternatives to CFCs and HCFCs and is continually searching for new fluorocarbon-based mixtures that are considered environmentally safe alternatives.
However, what is often considered important is that any potential alternative is also present in most widely used fluids, with excellent thermal insulation, and when used as a blowing agent. In particular, it must have such properties as imparting other desirable foam properties such as adequate chemical stability, low or non-toxicity, low or non-flammability.

In addition, it is generally considered desirable for CFC blowing agent substitutes to be effective without significant technical changes to conventional foam production systems.

For example, methods and compositions for making conventional foam materials, such as thermoplastic materials and thermoset materials, have long been known. These methods and compositions typically utilize chemical and / or physical blowing agents to form a foam structure in the polymer matrix. Such foaming agents include, for example, azo compounds, various volatile organic compounds (
VOCs) and chlorofluorocarbons (CFCs). Chemical blowing agent
Some chemicals, including chemical reactions (typically at a given temperature / pressure) with the material that forms the polymer matrix that typically results in the release of gases such as nitrogen, carbon dioxide, or carbon monoxide. Undergo change. One of the most frequently used chemical blowing agents is water. The physical blowing agent typically dissolves in the polymer or polymer precursor material and then expands in volume (again at a given temperature / pressure), contributing to the formation of a foam structure. . Physical blowing agents are often used in connection with thermoplastic foams, but chemical blowing agents should be used in place of or in addition to physical blowing agents in connection with thermoplastic foams. Can do.
For example, it is known to use chemical blowing agents in connection with the formation of polyvinyl chloride foam. It is common to use chemical and / or physical blowing agents in connection with thermoset foams. Of course, certain compounds (s) and compositions (s) containing them can simultaneously constitute chemical and physical blowing agents.

In the past, it has been common to use CFCs as standard blowing agents in the preparation of isocyanate-based foams, such as rigid and flexible polyurethane and polyisocyanurate foams. For example, CCl ₃ F (CFC-11) has become a standard blowing agent. However, the use of this substance is prohibited by international treaties because its release into the atmosphere damages the ozone layer in the stratosphere. As a result, it is no longer usually common to use neat CFC-11 as a standard blowing agent to form thermoset foams such as isocyanate foams and phenolic foams.

Due to problems with CFCs, the use of hydrogen-containing chlorofluoroalkanes (HCFCs) has increased. For example, CHCl ₂ CF ₃ (HCFC-123), CH ₂ ClCHC
1F (HCFC-141b) has a relatively short life in the atmosphere. However, although HCFCs are considered to be environmentally friendly blowing agents compared to CFCs, such compounds still contain some chlorine and thus “ozone depletion potential” (“ ODP "
Called). Because of non-zero ODPs, HCFCs are subject to elimination from final use.

Another known class of blowing agents is a non-chlorinated partially hydrogenated fluorocarbon ("
Called HFCs). Certain HFCs currently used as blowing agents have at least one potentially significant problem, i.e. they are generally relatively high intrinsic thermal conductivity (i.e. poor thermal insulation). Have In contrast, CF ₃ CH ₂ CF ₂ H (H
Foams made with the latest specific HFC blowing agents, such as FC-245fa), are partly H
Due to the low thermal conductivity of FC-245fa vapor and in part due to the fine cell structure that HFC-245fa imparts to the foam, it provides improved thermal insulation. HFC-245f
a has been widely used for thermal insulation applications, particularly refrigerators, freezers, refrigerator / freezers and spray foam applications. Nonetheless, many HFC fluids have the common disadvantage of having a relatively high global warming potential, with the lowest possible global warming potential while maintaining the desired performance in use characteristics. It may be desirable to use hydrofluorocarbons or other fluorinated fluids. HFC-245fa, HFC-134a, HFC-365
Even the latest HFCs such as mfc, etc. show a higher global warming potential than is desirable, albeit lower than other HFCs. Thus, the use of HFCs as foaming agents in foam insulation, particularly hard foam insulation, results in a less desirable candidate for foaming agents in commercial foam insulation.

Hydrocarbon blowing agents are also known. For example, Hutzen U.S. Pat. No. 5,182,309 teaches the use of iso- and normal-pentane in various emulsion mixtures. Another example of a hydrocarbon blowing agent is cyclopentane, as taught by Volkert US Pat. No. 5,096,933. Many hydrocarbon blowing agents such as cyclopentane and the isomers of pentane are substances with zero ozone depletion potential and very low global warming potential, but the foams produced from these blowing agents are For example, HFC-245fa
Such a material is by no means desirable because it lacks thermal insulation efficiency as much as a foam made with a blowing agent. Furthermore, hydrocarbon blowing agents are extremely flammable, which is undesirable. Also, certain hydrocarbon blowing agents are not sufficient under certain circumstances with materials from which the foam is formed, such as many polyester polyols commonly used in polyisocyanurate modified polyurethane foams. Has miscibility. In the use of these alkanes, chemical surfactants are often necessary to obtain a suitable mixture.

Thus, there is a growing need for new compounds and compositions that are attractive alternatives to compositions previously used as blowing agents in these and other applications. Accordingly, Applicants have recognized the need for new fluorocarbon-based compounds and compositions that provide effective alternatives to CFCs and HCFCs and are considered more environmentally safe alternatives. Yes. However, any potential alternative has properties such as gas phase thermal conductivity (low k-factor), low or non-toxic, among others, at least comparable to those associated with many of the most widely used blowing agents. It is generally considered highly desirable to have or impart these properties to the foam.

In many applications, one of the other potentially important characteristics is flammability. That is, it is considered important or essential to use a composition that is low or non-combustible, especially in many applications, including the use of blowing agents. In this specification, “non-flammability (n
The term “onflammable)” refers to a compound or composition determined to be non-flammable, measured according to ASTM standard E-681, dated 2002, incorporated herein by reference. Unfortunately, many HFCs that would otherwise be used in foam blowing agent compositions are not non-flammable. For example, fluoroalkanedifluoroethane (HFC-152a) and fluoroalkene 1,1,1-trifluoropropene (HFO-1243zf) are each flammable and are therefore impractical to use in many applications. is there.

Another example of a relatively flammable material is fluorinated ether 1,1,2,2-tetrafluoroethyl methyl ether (which is sometimes referred to as HFE-254pc or sometimes HFE-254cb), about It has been measured to have a flammability limit (volume%) of 5.4% to about 24.4%. For this general type of fluorinated ether, Beheme et al. US Pat. No. 5,137,932, incorporated herein by reference, discloses its use as a blowing agent.

Tapscott U.S. Pat. No. 5,997,185 proposes the use of bromine-containing halocarbon additives to reduce the flammability of certain materials, including foam blowing agents. The additives in this patent are said to be characterized by high efficiency and short atmospheric lifetime, ie low ozone depletion potential (ODP) and low global warming potential (GWP).

Although the brominated olefins described in the Tapscott patent may have some effect as a combustion inhibitor in connection with certain materials, there is no disclosure of the use of such materials as blowing agents. Furthermore, such compounds are also believed to have certain disadvantages. For example, Applicants have come to realize that many of the compounds identified in the Tapscott patent have relatively low effectiveness as blowing agents because of the relatively high molecular weight of such compounds. . In addition, many of the compounds disclosed in the Tapscott patent will encounter problems due to the relatively high boiling point of such compounds when used as blowing agents. Furthermore, it is understood by Applicants that many compounds with a high degree of substitution have other undesirable properties such as undesirable toxicity and / or potentially environmentally undesirable bioaccumulation.

Although Tapscott shows that bromine-containing alkenes having 2 to 6 carbon atoms may also contain fluorine substituents, this patent states that "fluorine-free bromoalkanes react with tropospheric hydroxyl free radicals. Would have a very short atmospheric lifetime due to (column 8, lines 34-39), suggesting that fluorine-containing compounds are never completely desirable from an environmental safety standpoint. Seems to be.

Furthermore, it is generally desirable that blowing agent substitutes be effective without significant technical changes to conventional equipment and systems used in foam preparation and molding.

Applicants thus provide compositions, particularly foaming agents, foamable compositions, foamed articles, and methods of forming foams that provide advantageous properties and / or avoid one or more of the disadvantages described above. And came to recognize the need for the system. Accordingly, Applicants have recognized the need for a composition, particularly a blowing agent, that is potentially useful in many applications while avoiding one or more of the above disadvantages.

The present invention relates to compositions, methods and systems that have utility in a number of applications, particularly including applications related to compositions, methods, systems and materials associated with polymer foams.

Applicants believe that the above and other needs are one or more C2-C6 fluoroalkenes, more preferably one or more C3-C5 fluoroalkenes, and even more preferably one or more. Of the following compounds of formula I:
XCF _Z R _3-Z (I)
Wherein X is a C ₁ , C ₂ , C ₃ , C ₄ or C ₅ unsaturated, substituted or unsubstituted group, each R independently being Cl, F, Br , I or H, and z is 1 to
3)
It has been found that the composition can be filled with foaming agent compositions, foamable compositions, foams and / or foamed articles. Generally, the fluoroalkenes of the present invention have at least 4 halogen substituents, of which at least 3 are F, and even more preferably none of them are Br.

In embodiments where at least one Br substituent is present, it is preferred that the compound does not contain hydrogen. In such embodiments, it is also generally preferred that the Br substituent is on an unsaturated carbon, and even more preferably, the Br substituent is on a non-terminal unsaturated carbon. One particularly preferred compound of this class is CF ₃ CBr═CF ₂ which includes all its isomers.
It is.

In certain embodiments, the compound of Formula I has 3-5 fluorine substituents, and the other substituents are propene, butene, pentene, and hexene, which may or may not be present. preferable. In certain preferred embodiments, no R is Br and preferably the unsaturated group does not contain a Br substituent. Among the propenes, in certain embodiments, tetrafluoropropenes (HFO-1234) and fluorochloropropenes (
For example, trifluoro, monochloropropenes (HFCO-1233)), even more preferably CF ₃ CCl═CH ₂ (HFO-1233xf) and CF ₃ CH═CHCl (
HFO-1233zd)) is particularly preferred.

In certain _embodiments, CF 3 CF = particular a CFH (HFO-1225yez) pentafluoropropene such that the presence of hydrogen substituent on the terminal unsaturated carbon, such as, pentafluoropropene are preferred. Because, in particular, the Applicants find that such compounds have a relatively low degree of toxicity, at least compared to the compound CF ₃ CH═CF ₂ (HFO-1225zc). .

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

As used herein, the term “HFO-1234” refers to all tetrafluoropropenes. Some tetrafluoropropenes include both 1,1,1,2-tetrafluoropropene (HFO-1234yf) and cis- and trans-1,1,1,3-tetrafluoropropene (HFO-1234ze). It is. In this specification, HFO-1
The term 234ze, regardless of whether it is in cis or trans form,
, 1,3-tetrafluoropropene is commonly used to refer to. As used herein, the terms “cis HFO-1234ze” and “trans HFO-1234ze” are used to describe the cis and trans forms of 1,1,1,3-tetrafluoropropene, respectively. Thus, the term “HFO-1234ze” includes within its scope cis HFO-1234ze, trans HFO-1234ze, and all combinations and mixtures thereof.

As used herein, the term “HFO-1233” is used to refer to all trifluoro, monochloropropenes. Among trifluoro and monochloropropene, 1,1
, 1-trifluoro-2-chloropropene (HFCO-1233xf) and cis- and trans-1,1,1-trifluoro-3-chloropropene (HFCO-1233z)
Both of d) are included. As used herein, the term HFCO-1233zd is commonly used to refer to 1,1,1-trifluoro-3-chloropropene, whether in cis or trans form. As used herein, the terms “cis HFCO-1233zd” and “trans HFCO-1233zd” are used to describe the cis and trans forms of 1,1,1-trifluoro-3-chloropropene, respectively. The
Thus, the term “HFCO-1233zd” includes within its scope cis HFCO—
1233zd, trans HFCO-1233zd, and all combinations and mixtures thereof.

As used herein, the term “HFO-1225” is used to refer to all pentafluoropropenes. Among such molecules are 1,1,1,2,3-pentafluoropropene (HFO-1225yez), both its cis and trans forms. Thus, the term HFO-1225yez is generally used herein to refer to 1,1,1,2,3-pentafluoropropene, whether in cis or trans form. Therefore, the term “HFO-1225yez”
Included within the scope are cis HFO-1225yez, trans HFO-1225yez, and all combinations and mixtures thereof.

In certain preferred embodiments, the present invention provides one or more C2-C6 comprising any one or more preferred groups and / or preferred individual fluorinated alkene compounds referred to herein. Fluorinated alkenes, more preferably C3-C4 fluorinated alkenes, as well as one or more fluorinated ethers, more preferably one or more hydro-fluorinated ethers, even more preferably one or more C3-C5. Provided are foaming agent compositions, foamable compositions, foams and / or foamed articles comprising hydro-fluorinated ethers. In certain highly preferred embodiments, the fluorinated ether (s) used according to this aspect of the invention are of the following formula (III):
_{C a H b F c -O-} C d H e F f (III)
(Where
a = 1-6, more preferably 2-5, even more preferably 3-5,
b = 1-12, more preferably 1-6, even more preferably 3-6,
c = 1-12, more preferably 1-6, even more preferably 2-6,
d = 1-2,
e = 0 to 5, more preferably 1 to 3,
f = 0-5, more preferably 0-2,
One of said C _a may combine with one of said C _d to form a cyclofluoroether)
It is.

The present invention also provides methods and systems for using the compositions of the present invention, including methods and systems for foaming.

Compositions The compositions of the present invention can generally be in the form of a blowing agent composition or a foamable composition. In any case, the present invention requires at least one fluoroalkene compound as described herein, and optionally additional components, some of which are described in detail below.

A. Fluoroalkene Preferred embodiments of the present invention are 2-6, preferably 3-5 carbon atoms, more preferably 3-4 carbon atoms, in certain embodiments most preferably 3 carbon atoms. A composition comprising an atom and at least one fluoroalkene comprising at least one carbon-carbon double bond is intended. If the fluoroalkene compound of the present invention contains at least one hydrogen, it may be referred to herein as a hydrofluoro-olefin or “HFOs” for convenience. Although it is contemplated that the HFOs of the present invention may contain two carbon-carbon double bonds, such compounds are presently not considered preferred. For HFOs that also contain at least one chlorine atom, the symbol HFCO may be used herein.

（式中、各Ｒは独立に、Ｃｌ、Ｆ、Ｂｒ、ＩまたはＨであり、
Ｒ’は（ＣＲ_２）_ｎＹであり、
ＹはＣＲＦ_２であり、
ｎは、０、１、２または３、好ましくは０または１である）の１種または複数の化合物
であって、しかしながら、Ｂｒがこの化合物中に存在しないか、あるいは、Ｂｒがこの化
合物中に存在する場合は、水素が化合物中に存在しないことが一般に好ましい。 As indicated above, the composition of the present invention comprises one or more compounds according to Formula I. In a preferred embodiment, the composition has the following formula II:

Wherein each R is independently Cl, F, Br, I or H;
R ′ is (CR ₂ ) _n Y;
Y is CRF ₂ ,
n is 0, 1, 2 or 3, preferably 0 or 1, however Br is not present in this compound or Br is present in this compound When present, it is generally preferred that no hydrogen be present in the compound.

In a highly preferred embodiment, Y is CF ₃ , n is 0 or 1 (most preferably 0), at least one of the remaining Rs is F, and preferably R is Br If none or Br is present, no hydrogen is present in the compound. In some cases, it is preferred that R in Formula II is not Br.

Applicants generally recognize that the compounds of formulas I and II identified above are generally effective and useful in blowing agent compositions in accordance with the teachings contained herein. I think.
However, the Applicants have surprisingly and unexpectedly found that certain compounds having a structure according to the above formula exhibit a very desirable low level of toxicity compared to other such compounds. It was. As can be readily appreciated, this discovery is a potentially tremendous advantage and benefit over the formulation of blowing agent compositions. More particularly, Applicants have found that relatively low levels of toxicity are compounds of Formula I or Formula II (preferably where Y is CF ₃ and n is 0 or 1), wherein At least one R on the unsaturated terminal carbon
Is associated with a compound in which at least one of the remaining Rs is F or Cl. Applicants consider that all structural isomers, geometric isomers and stereoisomers of such compounds are also effective and advantageously of low toxicity.

In certain preferred embodiments, the compounds of the present invention are C ₃ or C ₄ HFO or H
FCO, preferably C ₃ HFO, more preferably a compound according to formula I, wherein X is a halogen-substituted C ₃ alkylene and z is 3. In certain such embodiments, X is fluorine and / or chlorine substituted C ₃ alkylene, and in certain embodiments, the following C ₃ alkylene groups are preferred:
-CH = CF-CH ₃
-CF = CH-CH ₃
—CH ₂ —CF═CH ₂
—CH ₂ —CH═CFH

Accordingly, such embodiments include the following preferred compounds: CF ₃ —CH═C
_{F-CH 3; CF 3 -CF} = CH-CH 3; CF 3 -CH 2 -CF = CH 2; CF 3 -C
H ₂ —CH═CFH; and combinations thereof with one other compound and / or other compound (s) according to Formula I or Formula II.

In certain preferred embodiments, the compound of the invention is a C3 or C4 HFCO, preferably a C3 HFCO, more preferably a compound according to Formula II wherein Y is CF ₃ and n is 0; At least one R on the unsaturated terminal carbon is H and at least one of the remaining R is Cl). HFCO-1233 is an example of such a preferred compound.

In highly preferred embodiments, particularly those comprising the low toxicity compounds described above, n is 0. In certain highly preferred embodiments, the composition of the present invention is HFO-1234yf.
, (Cis) HFO-1234ze and (trans) HFO-1234ze, including one or more tetrafluoropropenes, and in certain embodiments, HFO-1234
ze is generally preferred, and trans HFO-1234ze is very particularly preferred. (Cis) HF
Although the properties of O-1234ze and (trans) HFO-1234ze differ at least somewhere, each of these compounds, alone or in its steric form, is associated with the respective application, method and system described herein. It is contemplated that it is compatible for use with other compounds, including isomers. For example, (trans) HFO-1234ze may be preferred for use in certain systems because of its relatively low boiling point (−19 ° C.), while (cis) HFO-1234ze having a boiling point of + 9 ° C. It may be preferred for other applications. Of course, perhaps a combination of cis and trans isomers will be tolerated and / or preferred in many embodiments. Thus, the term “HFO-1234ze” and 1,3,3,3-tetrafluoropropene are understood to refer to both stereoisomers, and the use of this term is in the cis form and unless otherwise indicated. Each of the trans forms is
It is intended to indicate that it is applicable and / or useful for the stated purpose.

HFO-1234 compound is a known substance, and Chemical Abstract
Listed in s databases. Various saturated and unsaturated, halogen-containing C
The preparation of fluoropropenes such as CF ₃ CH═CH ₂ by catalytic gas phase fluorination of three compounds is described in US Pat. Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is incorporated herein by reference. Incorporated into. Also, EP 974571, which is incorporated herein by reference, includes 1,1,1,3,3-pentafluoropropane (HFC-245fa) at high temperature in the gas phase with a chromium-based catalyst or in the liquid phase. KOH, NaOH
By contacting with an alcohol solution of Ca (OH) ₂ or Mg (OH) ₂ ,
The preparation of 1,1,3-tetrafluoropropene is disclosed. Furthermore, the process for producing the compounds according to the invention has the agent reference number (H0003789 (26267)), “
It is generally described with respect to a pending US patent application entitled “Process for Producing Fluoroprenes”, which is also incorporated herein by reference.

Other preferred compounds for use in accordance with the present invention include all of its isomers (eg, H
Pentafluoropropene, including FO-1225), all its isomers (eg HFO)
Tetra- and penta-fluorobutene, including -1354 and HFO-1345). Of course, the compositions of the present invention may comprise a combination of any two or more compounds within the broad scope of the present invention or within the preferred scope of the present invention.

The compositions of the present invention, particularly HFO-1234 (HFO-1234ze and HFO-12
Those containing 34yf) are considered to have advantageous properties for several important reasons. For example, Applicants have found that, based at least in part on mathematical modeling, the fluoroolefins of the present invention are negligible for ozone depletion compared to some other halogenated species. Therefore, it is considered that the chemical action in the atmosphere has virtually no negative effect. Accordingly, preferred compositions of the present invention have the advantage that they do not substantially contribute to ozone layer destruction. This preferred composition does not contribute substantially to global warming compared to many hydrofluoroalkanes currently in use.

In certain preferred forms, the compositions of the present invention have a global warming potential (GWP) of about 1000 or less, more preferably about 500 or less, and even more preferably about 150 or less.
In certain embodiments, the GWP of the composition of the present invention is about 100 or less, even more preferably about 75 or less. As used herein, “GWP” is incorporated herein by reference,
"The Scientific Asset of Ozone Depl
etion, 2002, A report of the World Meteoro
logical Association's Global Ozone Resa
Measured over a 100-year time range compared to carbon dioxide GWP, as defined in "rch and Monitoring Project".

In certain preferred forms, the compositions of the present invention also preferably have an ozone depletion potential (ODP) of 0.05 or less, more preferably 0.02 or less, and even more preferably about 0. As used herein, “ODP” refers to “The Sci,” which is incorporated herein by reference.
ENTIFIC ASSESSMENT OF AZONE DEPLETION, 20
02, A report of the World Metalogical
Association's Global Ozone Research and
It is defined in “Monitoring Project”.

The amount of the compound of formula I, particularly HFO-1234, even more preferably HFO-1234ze, contained in the composition of the present invention can vary widely depending on the particular application, and the amount of this compound Compositions comprising more than and less than 100% are within the broad scope of the present invention. Furthermore, the compositions of the present invention can be azeotropic, azeotrope-like or non-azeotropic. In a preferred embodiment, the composition of the present invention, particularly the blowing agent composition, comprises about 1% by weight of a Formula I and / or Formula II compound, preferably HFO-1234 and more preferably HFO-1234ze and / or HFO-1234yf. To about 99% by weight, more preferably from about 5% to about 9%.
5% by weight, even more preferably 40% to about 90% by weight.

B. Certain preferred embodiments of fluoroether present invention, at least one fluoroalkene as described herein, 2-8, preferably 2-7, even more preferably 2 to 6 carbons Compositions comprising atoms and, in certain embodiments, most preferably comprising at least one fluoro-ether, more preferably at least one hydro-fluoroether, comprising 3 carbon atoms are directed. The hydro-fluoroether compounds of the present invention are sometimes referred to herein as hydrofluoro-ethers or “HFEs” for the sake of convenience when they contain at least one hydrogen.

Applicants are generally aware of the fluoroethers according to the present disclosure, in particular the formula (I
The fluoroethers according to II) are considered to be effective and useful overall when combined with the fluoroalkene compounds according to the teachings contained herein. However, Applicants have found that in certain embodiments, particularly those involving blowing agent compositions and foams and foaming methods, at least difluorinated, more preferably at least trifluorinated, from among fluoroethers. It has been found that it is preferred to use hydrofluoroethers, more preferably at least tetra-fluorinated hydrofluoroethers. Certain particularly preferred embodiments are tetrafluorinated fluoroethers having 3 to 5 carbon atoms, more preferably 3 to 4 carbon atoms, and even more preferably 3 carbon atoms.

In certain preferred embodiments, the compounds of the present invention include 1,1,2,2-tetrafluoroethyl methyl ether (herein referred to as HFE-), including any and all isomeric forms thereof. 245pc or HFE-245cb2).

The amount of Formula III compound, especially 1,1,2,2-tetrafluoroethyl methyl ether, contained in the composition of the present invention can vary widely depending on the particular application, Compositions that exceed the trace amount and contain less than 100% are within the broad scope of the present invention. In a preferred embodiment, the composition of the invention, in particular the blowing agent composition, comprises a formula II comprising a preferred group of compounds.
The I compound is included in an amount of from about 1% to about 99%, more preferably from about 5% to about 95%, and even more preferably from 40% to about 90%.

The following compound or compounds are preferred for use according to certain preferred embodiments of the invention:

The inventors have in accordance with a preferred embodiment of the present invention any two or more HFs indicated above.
It should be understood that it is contemplated that E's may be used in combination. For example, according to certain preferred embodiments of the present invention, from about 20% methyl nonafluoroisobutyl ether
It is contemplated that the material sold under the trade name HFE-7100 by 3M, which is understood to be a mixture of about 80% and about 20% to about 80% methyl nonafluorobutyl ether, can be used advantageously. As another example, according to certain preferred embodiments of the present invention,
The trade name HFE by 3M is understood to be a mixture of about 20% to about 80% ethyl nonafluoroisobutyl ether and about 20% to about 80% ethyl nonafluorobutyl ether.
It is contemplated that the material sold as -7200 may be used to advantage.

It is also contemplated that any one or more of the above listed HFEs may be used in combination with other compounds. This other compound includes other HFEs not specifically listed herein and / or other compounds known to form azeotropes with the indicated fluoroethers. Including. For example, each of the following compounds is known to form an azeotrope with trans-dichloroethylene, and for the purposes of this invention the use of such azeotropes falls within the broad scope of the invention. It is intended to be considered:

C. Other Component-Blowing Agent Compositions In certain specific embodiments of the invention, it is contemplated that the blowing agent composition consists of or consists essentially of one or more compounds according to Formula I of the present invention. Is done. Accordingly, the present invention includes methods and systems that include using one or more compounds of the present invention as a blowing agent in the absence of any substantial amount of additional components. However, one or more compounds or components not included within the scope of Formula I or Formula II are optionally but preferably included in the blowing agent composition of the present invention. Such optional additional compounds include, but are not limited to, other compounds that serve as blowing agents (hereinafter referred to as co-foaming agents for the sake of convenience but not limited). , Surfactant, polymer modifier, toughening agent, colorant, dye, dissolution accelerator, rheology modifier, plasticizer,
Combustion inhibitors, antibacterial agents, viscosity reduction regulators, fillers, vapor pressure regulators, nucleating agents, catalysts and the like are included. In certain preferred embodiments, dispersants, foam stabilizers, surfactants and other additives can also be added to the blowing agent composition of the present invention. Certain surfactants are optionally but preferably added to serve as a bubble stabilizer. Several representative materials are sold under the trade names DC-193, B-8404, and L-5340, which are generally U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458. Polysiloxane polyoxyalkylene block copolymers, as disclosed in each (herein incorporated by reference). Other optionally included additives for this blowing agent mixture are flame retardants such as tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate, tri (2,3-dibromopropyl) -phosphate. , Tri (1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.

With respect to nucleating agents, all known compounds and materials having a nucleating function are available for use in the present invention, particularly including talc.

Of course, other compounds and / or ingredients that modulate certain properties of the composition (eg, cost, etc.) may also be included in the compositions of the present invention and the presence of all such compounds and ingredients. Are within the broad scope of the present invention.

Accordingly, a preferred embodiment of the composition of the present invention is a compound of formula I (particularly HFO-1
234ze and / or HFO-1234yf) in addition to one or more co-blowing agents. Co-blowing agents according to the present invention can include physical blowing agents, chemical blowing agents (preferably including water in certain embodiments) or blowing agents having a combination of physical and chemical foaming properties. It is understood that the blowing agents included in the compositions of the present invention, including the compound of Formula I and the co-blowing agent, may exhibit properties in addition to those necessary to be characterized as a blowing agent. For example, the blowing agent composition of the present invention also includes components that impart advantageous properties to the blowing agent composition to which it is added or to the blowing composition, including the compounds of formula I above. It is contemplated. For example, it is within the scope of the present invention for the compound of formula I or co-foaming agent to serve as a polymer modifier or as a viscosity reduction modifier.

In accordance with the present invention, it is contemplated that a wide range of co-blowing agents may be used, but in certain embodiments, the blowing agent composition of the present invention has one or more HFCs as co-blowing agents. Preferably, one or more C1-C4 HFCs and / or one or more hydrocarbons, more preferably C4-C6 hydrocarbons. For example, with respect to HFCs, the blowing agent composition of the present invention comprises one or more difluoromethanes (HFC-3
2), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC) -245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea)
), Pentafluorobutane (HFC-365), hexafluorobutane (HFC-356)
) And all isomers of all such HFCs. With respect to hydrocarbons, the blowing agent compositions of the present invention include certain preferred embodiments, for example, for thermosetting foams, iso, normal and / or cyclopentane, and thermoplastic foams. For this purpose, butane or isobutane can be included. Of course, other materials such as water, CO ₂ , CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs, eg,
Dichloroethylene (preferably trans-dichloroethylene), ethyl chloride and chloropropane), HCFCs, C1-C5 alcohol (such as ethanol and / or propanol and / or butanol), C1-C4 aldehyde, C1-C4 ketone, C1-C4 Ethers (such as dimethyl ether and diethyl ether) ethers,
(Including diethers (such as dimethoxymethane and diethoxymethane)), and methyl formate, and any combination thereof, such components may be included in many embodiments to adversely affect the environment. It is considered undesirable.

In certain embodiments, one or more of the following HFC isomers are preferred for use as a co-blowing agent in the compositions of the present invention:
1,1,1,2,2-pentafluoroethane (HFC-125)
1,1,2,2-tetrafluoroethane (HFC-134)
1,1,1,2-tetrafluoroethane (HFC-134a)
1,1-difluoroethane (HFC-152a)
1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea)
1,1,1,3,3,3-hexafluoropropane (HFC-236fa)
1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365mfc).

The relative amounts of any of the above additional co-blowing agents, and any additional ingredients that can be included in the compositions of the present invention will vary depending on the particular application for this composition. All such relative amounts are considered to fall within the scope of this specification, which may vary widely over a wide range. However, Applicants note that one particular advantage of at least certain compounds of formula I according to the present invention, such as HFO-1234ze, is the relatively low flammability of such compounds. Thus, in certain embodiments, the blowing agent composition of the present invention comprises at least one co-blowing agent and a compound according to Formula I in an amount sufficient to produce a blowing agent composition that is generally non-flammable. It is preferable to include (single or plural). Thus, in such embodiments, the relative amount of co-foaming agent relative to the compound of Formula I is determined, at least in part, by the combustibility of the co-foaming agent.

The blowing agent composition of the present invention may comprise a wide range of amounts of the compound of the present invention. However, in preferred compositions for use as blowing agents according to the present invention, the compound (s) according to Formula I, even more preferably Formula II, is at least about 1% by weight of the composition,
It is generally preferred that it be present in an amount that is more preferably at least about 5% by weight, even more preferably at least about 15% by weight. In certain preferred embodiments, the blowing agent comprises at least about 50% by weight of the blowing agent compound (s) of the present invention, and in certain embodiments, the blowing agent is substantially the present invention. It consists of the compound by. In this regard, it should be noted that the use of one or more co-blowing agents is consistent with the novel and basic features of the present invention. For example, in many embodiments, it is contemplated to use water as a co-blowing agent or in combination with other co-blowing agents such as pentane, especially cyclopentane.

It is contemplated that the blowing agent composition of the present invention may comprise HFO-1234yf, cis HFO-1234ze, trans HFO1234ze, or a combination of two or more thereof, preferably in an amount of at least about 15% by weight of the composition. Is done. In many preferred embodiments,
A co-foaming agent comprising water is included in this composition, most preferably in a composition directed to using a thermosetting foam. In certain preferred embodiments, the blowing agent compositions of the present invention comprise a combination of cis HFOI 234ze and trans HFO 1234ze from about 1:99 to about 5.
0:50, more preferably in a cis: trans weight ratio of about 10:90 to about 30:70.
In certain embodiments, it may also be preferred to use a combination of cis HFO 1234ze and trans HFO 1234ze in a cis: trans weight ratio of about 1:99 to about 10:90, preferably about 1:99 to about 5:95. is there. Of course, in certain embodiments, combinations where the cis isomer is present at a higher concentration than the trans isomer, such as when used with effervescent compositions suitable for use with liquid blowing agents, for example. It may be desirable to use it.

In certain preferred embodiments, the blowing agent composition is about 30% to about 95% by weight.
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 a compound of formula I, more preferably a compound of formula II, even more preferably one or more HFO-1234 compounds, and about 5% to about 90% by weight,
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 is H ₂ O, HFC
S, HFE, hydrocarbons, alcohols (preferably C2, C3 and / or C4 alcohols), CO _2, and comprises a compound selected from the group consisting of any two or more thereof, preferably essentially Consist of them.

Table A below shows generally HFOs, and HFO-, according to certain preferred embodiments.
Several combinations of 1234 (more particularly HFO-1234ze) and HFE are shown (all percentages are percentages by weight).

In preferred embodiments where the co-blowing agent comprises H ₂ O, the composition comprises from about 5% to about 50%, more preferably from about 10% to about 40%, by weight of H ₂ O of the total blowing agent composition. %, Even more preferably, in an amount of about 10% to about 20% by weight of the total blowing agent.

In a preferred embodiment the co-blowing agent comprises CO _2, the composition is from about 5% to about 60 wt% of the total CO ₂ blowing agent composition, more preferably from about 20% to about 50 wt%, Even more preferably, it is included in an amount of about 40% to about 50% by weight of the total blowing agent.

In preferred embodiments where the co-blowing agent comprises an alcohol, preferably C2, C3 and / or C4 alcohol, the composition comprises from about 5% to about 40%, more preferably from alcohol to about 5% by weight of the total blowing agent composition. Is included in an amount of about 10% to about 40% by weight, and even more preferably about 15% to about 25% by weight of the total blowing agent.

In a composition comprising an HFC co-blowing agent, an HFC co-blowing agent (preferably a C2, C3, C4 and / or C5 HFC, even more preferably difluoromethane (HFC-152a)
(HFC-152a is particularly preferred for extruded thermoplastics), and / or pentafluoropropane (HFC-245)) is preferably from about 5% by weight of the total blowing agent composition
It is present in the composition in an amount of about 80% by weight, more preferably from about 10% to about 75%, even more preferably from about 25% to about 75% by weight of the total blowing agent. Further, in such embodiments, the HFC is preferably a C2-C4 HFC, and even more preferably C3.
HFCs of penta-fluorinated C3 such as HFC-245fa are highly preferred in certain embodiments.

In a composition comprising an HFE co-foaming agent, an HFE co-foaming agent (preferably a C2, C3, C4 and / or C5 HFE), even more preferably HFE-254 (especially HFE-25).
4 pc) is preferably about 5% to about 80%, more preferably about 10% to about 75%, even more preferably about 25% of the total blowing agent of the total blowing agent composition. ~ About 7
It is present in this composition in an amount of 5% by weight. Further, in such embodiments, the HFE is preferably C2-C4 HFE, even more preferably C3 HFC, and in certain embodiments, tetra-fluorinated C3 HFE is highly preferred.

In compositions comprising an HC co-blowing agent, the HC co-blowing agent (preferably C3, C4 and / or C5 HC) is preferably from about 5% to about 80% by weight of the total blowing agent composition, even more preferably Is present in the composition in an amount of from about 20% to about 60% by weight of the total blowing agent.

D. Other Components—Foaming Composition One aspect of the present invention provides a foamable composition. As is known to those skilled in the art, foamable compositions generally include one or more components that are capable of forming a foam. As used herein, the term “foam-forming substance” is used to refer to a component, or combination of components, that is capable of forming a foam structure, preferably generally a cellular structure. According to the present invention, the foamable composition of the present invention comprises such component (s) and a blowing agent compound, preferably a compound of formula I. In certain embodiments, the one or more components capable of forming a foam include a thermosetting composition and / or a foamable composition capable of forming a foam. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, as well as phenolic foam compositions. This reaction and foaming process can be facilitated through the use of various additives such as catalysts and surfactant materials that serve to control and regulate the bubble size during formation and stabilize the foam structure. it can. Further, it is contemplated that one or more additional ingredients as described above with respect to the blowing agent composition of the present invention can be added to the foamable composition of the present invention. In such thermoset foam embodiments, one or more of the compositions of the present invention is suitable as a foaming agent or as part of the foamable composition, or to form a foam or cellular structure. It is included as part of a two or more part foamable composition that preferably includes one or more components capable of reacting and / or foaming under mild conditions.

In certain other embodiments of the present invention, the one or more components that can be foamed include thermoplastic materials, particularly thermoplastic polymers and / or resins. Examples of thermoplastic foam components include, for example, the formula Ar—CHCH ₂ , wherein Ar is polystyrene (PS),
Polyolefins such as monovinyl aromatic compounds (which are benzene series aromatic hydrocarbon groups). Other examples of suitable polyolefin resins according to the present invention include various ethylene resins, including ethylene homopolymers and ethylene copolymers such as polyethylene, polypropylene (PP) and polyethylene terephthalate (PET). In certain embodiments, the thermoplastic foamable composition is an extrudable composition.

Methods and Systems All currently known and available methods and systems for forming foams are considered readily compatible for use in connection with the present invention. For example, the method of the present invention generally involves incorporating a blowing agent according to the present invention into a foamable composition or foam-forming composition, and then preferably expanding the volume of the blowing agent according to the present invention. Foaming the composition by a step or series of steps. In general, the systems and devices currently used to incorporate and foam foaming agents are considered readily compatible for use with the present invention. Indeed, it is believed that one advantage of the present invention is to provide an improved blowing agent that is generally compatible with existing foaming methods and systems.

Accordingly, those skilled in the art will appreciate that the present invention includes methods and systems for foaming all types of foams, including thermoset foams, thermoplastic foams and in-situ formed foams. . Accordingly, one aspect of the present invention is the use of the foaming agent of the present invention at conventional processing conditions in conjunction with conventional foaming equipment such as polyurethane foaming equipment. Thus, the method of the present invention includes masterbatch type operation, mixing type operation, third stream blowing agent addition, foaming agent addition at the foam head.

With regard to thermoplastic foams, preferred methods usually include the step of introducing the blowing agent according to the invention into a thermoplastic material, preferably a thermoplastic polymer such as a polyolefin, and then the effect of foaming the thermoplastic material. Subjecting to specific conditions. For example, introducing a foaming agent into a thermoplastic material includes introducing a foaming agent into a screw extruder that includes a thermoplastic resin, and foaming is achieved by reducing the pressure on the thermoplastic material. , Expanding the blowing agent to contribute to the foaming of the material.

Those skilled in the art will be able to form the blowing agent of the present invention and / or particularly in light of the disclosure contained herein.
It will also be appreciated that the order and method of addition to the foamable composition does not affect the overall viability of the invention. For example, in the case of an extrudable foam, the various components of the blowing agent, and even the components of the foamable composition, are not mixed prior to introduction into the extruder or are placed in the same location on the extruder. It is also possible not to add. Furthermore, the blowing agent may be added directly or as part of a premix that is then further added to other parts of the foamable composition.

Thus, in certain embodiments, one or more components of the blowing agent may be charged at an initial location of the extruder that is upstream of the addition location of one or more other components of the blowing agent. It may be desirable and these components are expected to come together in the extruder and / or work more effectively in this way. However, in certain embodiments,
Two or more components of the blowing agent are pre-combined and put together directly into the foamable composition or as part of a premix that is then further added to other parts of the foamable composition It is thrown.

One embodiment of the present invention relates to a method of forming foam, preferably polyurethane and polyisocyanurate foam. The method generally includes providing a blowing agent composition of the present invention, adding the blowing agent composition to the foamable composition (directly or indirectly), foaming, as is well known in the art, Reacting with the foamable composition under conditions effective to form a body or cellular structure. "Polyurethanes Chemis
try and Technology "Volumes I and II, Saunders and Fr
use any method well known in the art, such as those described in Isch, 1962, John Wiley and Sons, New York, NY (incorporated herein by reference) It may be adapted for use with the foam embodiments of the invention. In general, such preferred methods include isocyanates, polyols or mixtures of polyols, blowing agents or mixtures of blowing agents comprising one or more compositions of the invention, and catalysts, surfactants, and optionally difficult. It includes preparing polyurethane or polyisocyanurate foams by combining other materials such as flame retardants, colorants, or other additives.

In many applications, it is advantageous to provide the polyurethane or polyisocyanurate foam component in a preblend formulation. Most typically, the foam formulation is
Preblended into two components. Isocyanates and optionally certain surfactants and blowing agents constitute the first component, commonly referred to as the “A” component. The polyol or polyol mixture, surfactant, catalyst, blowing agent, flame retardant, and other isocyanate-reactive components constitute the second component, commonly referred to as the “B” component. Thus, polyurethane or polyisocyanurate foams can be mixed with this A and B subcomponents manually for small amounts, or preferably blocks, slabs, laminates, in-situ injection panels and other articles, It is easily prepared by bringing together by mechanical mixing techniques to form spray-applied foams, froths and the like. Optionally, other components such as flame retardants, colorants, auxiliary blowing agents, and even other polyols can be added to the mixing head or reaction site as one or more additional streams. Most preferably, however, they are all incorporated into one B-component as described above.

The method and system of the present invention also includes forming a one-component foam, preferably a polyurethane foam, comprising a blowing agent according to the present invention. In certain preferred embodiments, a portion of the blowing agent is included in the foam-forming material, preferably dissolved in the foam-forming material that is liquid at the pressure in the container. The second part of the blowing agent is present as a separate gas phase. In such systems, the contained / dissolved blowing agent is mainly
It functions to expand the foam, and the separated gas phase serves to provide a driving force to the foam-forming material. Such one-component systems are typically and preferably packaged in containers such as aerosol-type cans, and therefore the blowing agent of the present invention is preferably expanded and / or from this packaging container. The energy carrying the foam / foamable material, preferably both, is provided. In certain embodiments, such systems and methods include filling a packaging container with a fully formulated system (preferably an isocyanate / polyol system);
Incorporating the gaseous blowing agent according to the invention into a packaging container, preferably an aerosol-type can.

"Polyurethanes Chemistry and Technology
I and II, Saunders and Frisch, 1962, John Wil
Use any method well known in the art, such as those described in ey and Sons, New York, NY (incorporated herein by reference), or foam formation of the present invention It may be adapted for use according to the embodiment.

In certain embodiments, it may be desirable to use a composition of the invention when in the supercritical or near supercritical state as a blowing agent.

Foams The present invention also includes all foams prepared from polymer foam formulations, including but not limited to closed cell foams, including foaming agents comprising the compositions of the present invention.
Open cell foam, hard foam, soft foam, integral skin (in
tegral skin) etc.). Applicants have noted that one advantage of a thermoset foam, such as a polyurethane foam, in particular a polyurethane foam, according to the present invention, preferably in connection with the thermoset foam embodiment, is a K-factor or lambda. It has been found that exceptional thermal performance can be achieved, particularly preferably under cryogenic conditions, as can be measured by: Although it is believed that the foam of the present invention, particularly the thermosetting foam of the present invention, can be used in a variety of applications, in certain preferred embodiments, the present invention provides a foam for a refrigerator, for a freezer. Includes appliance foams according to the present invention, including foams, refrigerator / freezer foams, panel foams, and other low or cryogenic manufacturing applications.

In certain preferred embodiments, the foams according to the present invention have a thermal insulation efficiency (especially with respect to thermoset foams), dimensional stability, compressive strength, aging of thermal insulation (all of which are many preferred of the present invention In addition to the low ozone depletion potential and low global warming potential associated with blowing agents)
One or more distinct features, characteristics, including
providing the logistics and / or properties. In certain highly preferred embodiments, the present invention uses the same blowing agent (or commonly used blowing agent HFC-245fa) in the same amount, but without the compound of formula I according to the present invention. Compared to, provide thermosetting foams (including such foams formed in foamed articles) that exhibit improved thermal conductivity. In certain highly preferred embodiments, the thermoset foams of the present invention, preferably polyurethane foams, at about 4.4 ° C. (40 ° F.) are about 0.
79 W / m ² K (0.14 BTU / hr · ft ² · ° F.) or less, more preferably 0.77
W / m ² K (0.135 BTU / hr · ft ² · ° F.) or less, and still more preferably
A K-factor of 74 W / m ² K (0.13 BTU / hr · ft ² · ° F.) or less is shown. Further, in certain embodiments, the thermoset foam, preferably the polyurethane foam of the present invention, is about 0.91 W / m ² K (0.16 BTU / hr) at 23.9 ° C. (75 ° F.).・ F
t ² · ° F) or less, more preferably 0.85 W / m ² K (0.15 BTU / hr · ft ²⁾
· ° F) or less, still more preferably 0.82 W / m ² K (0.145 BTU / hr · f
It is preferable to show a K-factor of t ² · F or less.

In other preferred embodiments, the foams of the present invention 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 preferably have at least about 10 relative percentages (%), even more preferably than foams made at substantially the same conditions by using a blowing agent consisting of cyclopentane. Provide foams and foam articles having a compressive strength that is at least about 15 relative percent (%) superior. Further, in certain embodiments, the foam made according to the present invention has a foaming agent of HF.
It is preferred to have a compressive strength comparable on a commercial basis to the compressive strength provided by making the foam under substantially the same conditions except that it consists of C-245fa. In certain preferred embodiments, the foam of the present invention has a compression ratio of at least about 12.5% yield (in the parallel and vertical directions), and even more preferably at least about 13% yield ratio in each of the aforementioned directions. Indicates strength.

The following examples are provided for the purpose of illustrating the invention, but are not intended to limit the scope thereof.

Example 1A-Polystyrene Foam This example illustrates the use of a blowing agent according to two preferred embodiments of the present invention, i.e. HFO-
The use of 1234ze and HFO-1234yf and the production of polystyrene foam are illustrated. Test equipment and procedures have been established to help determine if a particular blowing agent and polymer can produce a foam and can produce the quality of that foam. A foaming agent consisting essentially of ground polymer (Dow Polystyrene 685D) and HFO-1234ze is mixed in a container. A sketch of this container is shown below. The container has a volume of 200 cm ³ and is made of Schedule 40 stainless steel pipe with a length of 10.2 cm (4 inches) with two pipe flanges and a cross section of 5.08 cm (2 inches) in diameter. . The container is about 87.8 ° C. to about 140.6.
° C (about 190 ° F to about 285 ° F), preferably 129.4 ° C for polystyrene (
Store in an oven set at a temperature of 265 ° F. and stay there until temperature equilibrium is reached.

次いで、この容器中の圧力を放出して、発泡ポリマーを急速に生じさせる。この発泡剤
はポリマー中に溶解するにつれてポリマーを可塑化する。この方法を用いてこのようにし
て作製された２種の発泡体の得られた密度を、トランス−ＨＦＯ−１２３４ｚｅおよびＨ
ＦＯ−１２３４ｙｆを用いて作製された発泡体の密度として表１に示す。このデータは、
発泡体ポリスチレンが本発明により得られることを示す。これに関して、ポリスチレンの
嵩密度は、ほぼ室温で１０５０ｋｇ／ｍ^３または６５．６２５ｌｂ／ｆｔ^３であることに
留意されたい。

The pressure in the container is then released to produce the foamed polymer rapidly. This blowing agent plasticizes the polymer as it dissolves in the polymer. The resulting densities of the two foams thus produced using this method are expressed as trans-HFO-1234ze and H
It shows in Table 1 as a density of the foam produced using FO-1234yf. This data
It shows that foam polystyrene is obtained by the present invention. In this regard, it should be noted that the bulk density of polystyrene is 1050 kg / m ³ or 65.625 lb / ft ³ at approximately room temperature.

Example 1B-Polystyrene Foam This example illustrates the performance of HFO-1234ze alone as a blowing agent for polystyrene foam formed in a twin screw type extruder. The equipment used in this example is a Leistritz twin screw extruder having the following characteristics:
30 mm co-rotating screw L: D ratio = 40: 1

The extruder is divided into 10 sections, each showing a 4: 1 L: D.
The polystyrene resin is charged into the first compartment, the blowing agent is charged into the sixth compartment, and the extrudate becomes the tenth.
Came out of the parcel. The extruder operated primarily as a melt / mixing extruder. Subsequent cooling extruders are connected in tandem (vertical row) and the design characteristics for this are as follows.
Leistritz twin screw extruder:
40 mm co-rotating screw L: D ratio = 40: 1
Die: 5.0mm circle

A polystyrene resin, namely Nova Chemical general purpose extrusion grade polystyrene (identified as Nova 1600) is fed to the extruder under the conditions described above. The resin has a proposed melting temperature of 191 ° C. to 274 ° C. (375 ° F. to 525 ° F.). The extruder pressure in the die is about 9.1 MPa (1320 lb / in ² (psi)) and the temperature in the die is about 115 ° C.

A blowing agent consisting essentially of trans HFO-1234ze and containing about 0.5 wt% talc based on the total blowing agent as a nucleating agent is added to the extruder from the above location. In accordance with the present invention, foams are made using blowing agents at concentrations of 10%, 12%, and 14% by weight. The density of the produced foam is in the range of about ^{0.1g / cm 3 ~0.07g / cm 3} , having a cell size of about 49 to about 68 microns. This foam, approximately 30 millimeters in diameter, is a very fine bubble size with a visually very good quality and has no visible or obvious blow holes or voids.

Example 1C-Polystyrene foam blowing agent is about 50 wt% trans HFO-1234ze and 50 wt% HFC-
This procedure of Example 1B is repeated except that 245fa and the concentration of nucleating agent shown in Example 1B are included. Expanded polystyrene is prepared at blowing agent concentrations of approximately 10% and 12%. The density of the foam produced is about 0.09 g / cm ³ and has a cell size of about 200 microns. This foam, approximately 30 millimeters in diameter, is a very fine cellular structure with very good visual quality and no visible or obvious voids.

Example 1D-Polystyrene foam blowing agent is about 80 wt% HFO-1234ze and 20 wt% HFC-245f.
This procedure of Example 1B is repeated except that a and the concentration of nucleating agent shown in Example 1B are included. Expanded polystyrene is prepared at blowing agent concentrations of approximately 10% and 12%. The density of the foam produced is about 0.08 g / cm ³ and has a cell size of about 120 microns. This foam, approximately 30 millimeters in diameter, is a very fine cellular structure with very good visual quality and no visible or obvious voids.

Example 1E-Polystyrene foam blowing agent is about 80 wt% HFO-1234ze and 20 wt% HFC-245f.
This procedure of Example 1B is repeated except that a and the concentration of nucleating agent shown in Example 1B are included. Expanded polystyrene is prepared at blowing agent concentrations of approximately 10% and 12%. The density of this foam was in the range of 0.1 g / cm ³ . This foam, approximately 30 millimeters in diameter, is a very fine cellular structure with very good visual quality and no visible or obvious voids.

Example 1F- This procedure of Example 1E is repeated except that the polystyrene foam nucleating agent is omitted. The density of the foam was in the range of 0.1 g / cm ³ and the bubble size was about 400 microns. Approximately 30 diameters
This foam of millimeters is a very fine cellular structure of very good quality visually and has no visible or obvious voids.

Example 2-Compressive Strength of Polyurethane Foam This example is a HFO-1234ze used in combination with a hydrocarbon co-foaming agent,
And the performance of its isomers, and in particular, the compressive strength performance of polyurethane foams.
Illustrates the utility of a composition comprising FO-1234ze and a cyclopentane co-blowing agent.

Prepare a commercially available cooling appliance type polyurethane foam formulation (foam-forming material). The polyol blend is composed of commercially available polyol (s), catalyst (s), and surfactant (s). This formulation is suitable for use in conjunction with a gaseous blowing agent. Standard commercial polyurethane processing equipment is used for the foam formation process. HFO-123 at approximately 60 mol% concentration of total blowing agent
A gaseous blowing agent combination was formed containing 4ze (including its isomers), and cyclopentane at a concentration of approximately 40 mole%. This example illustrates the physical properties of a combination of HFO-1234ze (including its isomers) in combination with a cyclopentane co-blowing agent. Table 2 below shows a polyurethane foam made with the same machine using the foaming agent of the present invention compared to a foam made with a foaming agent consisting of HFC-245fa and a foaming agent consisting of cyclopentane. The compressive strength of is reported.

One unexpected result illustrated in this example is HFO-1234ze, and HFC
-1234ze / HFC blends can be processed in conventional foam processing equipment, especially polyurethane processing equipment. This means that this process can be achieved with various types of systems and equipment, including master batch type mixing equipment, gaseous blowing agent mixing equipment, third stream addition of blowing agent, or foaming agent addition at the foam head. This is a potentially great advantage in that it allows processing.

Example 3-Polyurethane Foam K-Factor Polyurethane Foam was prepared and adapted for use as a commercial "appliance type" polyurethane formulation. For foam formation, the foam formulation described in Example 2 is used on the same standard commercial polyurethane processor. Several systems are prepared, and each system uses the same components, systems, and equipment except the blowing agent. In addition to the blowing agent according to the invention,
HFC-134a, HFC-245fa, and cyclopentane were also tested as blowing agents, respectively. In each system, the blowing agent is added to the polyol blend at substantially the same molar concentration.
This polyol blend consists of commercially available polyol (s), catalyst (s), and surfactant (s). The foam is prepared by standard commercial manufacturing operations, such as commercial operations for making foams for cooling applications. The prepared foam was evaluated for k-factor and this information is reported in Table 3 below. For reference,
For comparison purposes, foams were prepared with HFC-134a, for which commercial data can be consulted. The k-factor data for these foams is shown in Table 3.

This example illustrates the k-factor performance of HFO-1234ze, and its isomers, when the HFO-1234ze blowing agent is replaced in a polyurethane formulation. HFO-
1234ze was replaced at the same molar concentration as the reference foam. The data in Table 3 is HFO
Illustrates that the k-factor of the -1234ze foam is significantly improved over HFC-134a or cyclopentane foam.

Example 4-Polyurethane Foam K-Factor This example is a foam comprising a combination of HFO-1234ze (including its isomers) and various HFC co-foaming agents used in connection with the preparation of polyurethane foams. The performance of the agent is illustrated.
The same foam formulation, equipment and procedures used in Examples 2 and 3 are used, except for the blowing agent. A blowing agent is prepared comprising HFO-1234ze (including its isomer) at a concentration of approximately 80% by weight of the total blowing agent and HFC-245fa at a concentration of approximately 20% by weight of the total blowing agent. In addition to the blowing agent according to the invention, HFC-134a and cyclopentane were also tested as blowing agents, respectively. In each system, this blowing agent was added to the polyol blend at substantially the same molar concentration. The foaming agent is then used to form a foam and the foam k
-Measure the factors. Table 4 below shows HFO-1234z when used in combination with an HFC co-foaming agent.
2 illustrates the k-factor performance of a combination of e (including its isomers).

One unexpected result illustrated in this example is HFO-1234ze, and HFC
The -1234ze / HFC blend can be processed in conventional polyurethane processing equipment. This means that this process can be achieved with various types of systems and equipment, including master batch type mixing equipment, gaseous blowing agent mixing equipment, third stream addition of blowing agent, or blowing agent addition at the foam head. This is a potentially great advantage in that it allows processing.

Example 5-Polyurethane Foam K-Factor This example further illustrates the unexpected performance of the blowing agent according to the present invention when used in the production of polyurethane foam. Three appliance polyurethane foams are made, each formed using substantially the same materials, procedures, and equipment, except that different blowing agents were used. This polyol system is a commercially available appliance type formulation suitable for use with liquid blowing agents. A foaming machine is used to form the foam. The blowing agent is used at a substantially equimolar concentration. After forming, each foam was cut into samples suitable for measuring the k-factor, and the k-factor was found to be as shown in Table 5B below. The composition of this blowing agent is disclosed in Table 5A below in weight percentage (%) based on total blowing agent.

This result, reported in Table 5B, shows that for the thermosetting foam, the compound of the present invention (HFO-1
234ze) as co-foaming agents at these concentrations of cyclopentane and HFC-245
When used in combination with fa, it demonstrates that when used alone or with HFC-245fa, it did not deleteriously affect the performance of the k-factor of HFO-1234ze.
This is an unexpected result because, in the past, the use of significant amounts of cyclopentane in blowing agent formulations had a detrimental effect on k-factor performance.

Example 6-Polyurethane Foam K-Factor Other experiments were conducted using the same polyol formulation and isocyanate as in Example 5. The foam is prepared by manual mixing. This blowing agent is a compound according to formula II, ie HFCO-1233zd, in molar percentage (%) of the foamable composition, similar to the blowing agent in Example 5.
(CF ₃ CH═CHCl) ^* . The K-factor was found to be as shown in Table 6 below.

Claims (52)

(A) at least one fluoroalkene of formula I XCF _Z R _3-Z (I)
Wherein X is a C ₁ , C ₂ , C ₃ , C ₄ or C ₅ unsaturated, substituted or unsubstituted group, each R independently being Cl, F, Br , I or H, and z is 1 to
3), and (b) a blowing agent comprising at least one fluorinated ether. Additional co-foaming agent (s), surfactant (s), polymer modifier (s), toughening agent (s), colorant (s), dye (s) ), Dissolution enhancer (s), rheology modifier (s), plasticizer (s), combustion inhibitor (s), antibacterial agent (s), viscosity reduction modifier ( Singular (s), filler (s), vapor pressure modifier (s), nucleating agent (s), catalyst (s) and any combination of two or more thereof The composition of claim 1 further comprising at least one adjuvant selected from the group. The blowing agent of claim 1, wherein the at least one fluoroalkene comprises at least 3 carbons and / or at least 4 carbons alkenes having from 3 to 5 fluorine substituents. The blowing agent of claim 1, wherein the at least one fluoroalkene comprises cis HFO-1234ze, or trans HFO-1234ze, or a combination thereof. The blowing agent of claim 1, wherein the at least one fluoroalkene comprises at least one butene having 3 to 5 fluorine substituents. The at least one fluoroalkene is a compound of formula II

Wherein each R is independently Cl, F, Br, I or H;
R ′ is (CR ₂ ) _n Y;
Y is CRF ₂ ,
n is 0 or 1)
The foaming agent according to claim 1, wherein The blowing agent according to claim 6, wherein Y is CF ₃ .   7. The blowing agent of claim 6, wherein at least one R on the unsaturated terminal carbon is not F.   The blowing agent of claim 6, wherein at least one R on the unsaturated terminal carbon is H.   The blowing agent of claim 1 having a global warming potential (GWP) of about 150 or less.   The blowing agent of claim 1 having an ozone depletion potential (ODP) of about 0.05 or less. The blowing agent of claim 1, wherein the fluoroalkene comprises an unsaturated terminal carbon having no more than one F substituent. The blowing agent of claim 1, wherein the fluoroalkene comprises an unsaturated terminal carbon and at least one substituent on the unsaturated terminal carbon is H.   The blowing agent according to claim 1, wherein the compound of formula I does not contain Br.   The blowing agent of claim 1, wherein the compound comprises at least one chlorine substituent.   The blowing agent of claim 15, wherein the compound comprises HFCO-1233. The blowing agent of claim 15, wherein the HFCO-1233 comprises HFCO-1233xf. The blowing agent of claim 15, wherein the HFCO-1233 comprises HFCO-1233zd. The blowing agent of claim 1, wherein the at least one compound of formula I is present in the composition in an amount of about 5% to about 95% by weight of the blowing agent.   The blowing agent of claim 1, wherein the adjuvant comprises at least one additional co-blowing agent. 21. The blowing agent of claim 20, wherein the at least one additional co-blowing agent comprises one or more C1-C4 HFCs. The one or more HFCs are difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (H
FC-143), tetrafluoroethane (HFC-134), pentafluoroethane (H
FC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), 3. All selected from the group consisting of all these isomers and combinations of two or more thereof.
1. The foaming agent according to 1. 21. The blowing agent of claim 20, wherein the at least one additional co-blowing agent comprises one or more C4-C6 hydrocarbons. 24. The blowing agent of claim 23, wherein the one or more hydrocarbons are selected from the group consisting of isopentane, normal pentane, cyclopentane, butane and isobutane, and combinations of two or more thereof. A foamable composition comprising a foam-forming substance and a foaming agent, wherein the foaming agent comprises:
At least one fluoroalkene of formula I XCF _Z R _3-Z (I)
Wherein X is a C ₁ , C ₂ , C ₃ , C ₄ or C ₅ unsaturated, substituted group, each R independently being Cl, F, Br, I or H And z is 1 to 3), and a composition comprising at least one fluorinated ether. 26. The foamable composition of claim 25, wherein the foam-forming substance comprises at least one thermosetting foam component. 27. The foamable composition of claim 26, wherein the at least one thermosetting component comprises a composition capable of forming a polyurethane foam. 27. The foamable composition of claim 26, wherein the at least one thermosetting component comprises a composition capable of forming a polyisocyanurate foam. 27. The foamable composition of claim 26, wherein the at least one thermosetting component comprises a composition capable of forming a phenolic foam. 26. The foamable composition of claim 25, wherein the foam-forming material comprises at least one thermoplastic foam component. 32. The foamable composition of claim 30, wherein the at least one thermoplastic foam component comprises a thermoplastic polymer. 32. The foamable composition of claim 30, wherein the at least one thermoplastic component comprises a polyolefin. 33. The foamable composition according to claim 32, wherein the polyolefin is selected from the group consisting of monovinyl aromatic compounds, ethylene-based compounds, propylene-based polymers, and combinations thereof. Polyols, and at least one fluoroalkene of formula I XCF _Z R _3-Z (I)
Wherein X is a C ₁ , C ₂ , C ₃ , C ₄ or C ₅ unsaturated, substituted group, each R independently being Cl, F, Br, I or H And z is 1 to 3), and a foam premix composition comprising a blowing agent comprising at least one fluorinated ether. At least one fluoroalkene of formula I XCF _Z R _3-Z (I)
Wherein X is a C ₁ , C ₂ , C ₃ , C ₄ or C ₅ unsaturated, substituted group, each R independently being Cl, F, Br, I or H And z is 1 to 3), and a method of forming a foam comprising adding a foaming agent comprising at least one fluorinated ether to the foamable and / or foamed composition. A foam comprising a plurality of polymer bubbles and a composition contained in at least one of the bubbles, wherein the composition comprises:
(A) at least one fluoroalkene of formula I XCF _Z R _3-Z (I)
Wherein X is a C ₁ , C ₂ , C ₃ , C ₄ or C ₅ unsaturated, substituted group, each R independently being Cl, F, Br, I or H And z is 1 to 3), and (b) a foam comprising at least one blowing agent comprising at least one fluorinated ether. Claims for one or more forms of blocks, slabs, laminates, rigid foams, open cell foams, closed cell foams, soft foams, integral skin foams, refrigerator foams, and freezer foams Item 37. The foam according to Item 36. About 0.79 W / m ² K (0.14 BTU / hr · ft) at 4.4 ° C. (40 ° F.)
37. A foam according to claim 36 having a k-factor of ² ° F or less. About 0.91 W / m ² K (0.16 BTU / hr · f) at 23.9 ° C. (75 ° F.)
37. Foam according to claim 36, having a k-factor of t ² · F or less. 37. A compressive strength of at least about 12.5% yield in the parallel direction.
The foam described in 1. 37. A compressive strength of at least about 12.5% yield in the vertical direction.
The foam described in 1. The auxiliary agent, _water, CO 2, CFC compounds, HCC compounds, HCFC compounds, C1 to C5 alcohols, C1 -C4 aldehydes, C1 -C4 ketones, C1 -C4 ethers, the group consisting of combinations of two or more thereof The foaming agent according to claim 1, comprising at least one co-foaming agent selected from: 26. The foamable composition of claim 25, wherein the foam-forming substance is thermoplastic and the foaming agent further comprises a compound selected from the group consisting of C1-C5 alcohols. The foam-forming material is thermoplastic and the blowing agent further comprises ethanol.
5. The foamable composition according to 5. 26. The foamable composition of claim 25, wherein the foam-forming material is thermoplastic and the foaming agent further comprises a compound selected from the group consisting of dimethyl ether, diethyl ether, and combinations thereof. The foam-forming material is thermoplastic and the blowing agent further comprises methyl formate.
5. The foamable composition according to 5. The blowing agent of claim 1, wherein the compound of formula I has at least 4 halogen substituents. 5. The at least four halogen substituents comprise at least three F substituents.
The foaming agent according to 7. The blowing agent of claim 1, wherein the fluorinated ether comprises at least one hydro-fluorinated ether. The blowing agent of claim 1, wherein the fluorinated ether comprises at least one C3-C5 hydro-fluorinated ether. The fluorinated ether has the following formula (III)
_{C a H b F c -O-} C d H e F f (III)
(Where
a = 1 to 6,
b = 1 to 12,
c = 1-12,
d = 1-2,
e = 0-5,
f = 0 to 5,
One of the C _a may combine with one of the C _d to form a cyclofluoroether)
The foaming agent according to claim 1, wherein The fluorinated ether is CHF ₂ OCH ₂ F (HFE-143E), CH ₂ FOCH.
_{2 F (HFE-152E),} CH 2 FOCH 3 (HFE-161E), cycloalkyl _-CF 2 C
_{H 2 OCF 2 O (HFE-} c234fEαβ), cycloalkyl _{-CF 2 CF 2 CH 2 O (} HFE
-C234fEβγ), CHF ₂ OCF ₂ CHF ₂ (HFE-236caE), CF ₃ C
F ₂ OCH ₂ F (HFE-236cbEβγ), CF ₃ OCHFCHF ₂ (HFE-23
6eaEαβ), CHF ₂ OCHFCF ₃ (HFE-236eaEβγ), CHF ₂ OC
F ₂ CH ₂ F (HFE-245caEαβ), CH ₂ FOCF ₂ CHF ₂ (HFE-24
5caEβγ), CF ₃ OCF ₂ CH ₃ (HFE-245cbEβγ), CHF ₂ CHF
OCHF ₂ (HFE-245eaE), CF ₃ OCHFCH ₂ F (HFE-245ebE)
αβ), CF ₃ CHFOCH ₂ F (HFE-245ebEβγ), CF ₃ OCH ₂ CF ₂
H (HFE-245faEαβ), CHF ₂ OCH ₂ CF ₃ (HFE-245faEβγ)
), CH ₂ FCF ₂ OCH ₂ F (HFE-254caE), CHF ₂ OCF ₂ CH ₃ (H
FE-254cbEαβ), CHF ₂ CF ₂ OCH ₃ (HFE-254caEβγ), C
H ₂ FOCHFCH ₂ F (HFE-254eaEαβ), CF ₃ OCHFCH ₃ (HFE
-254ebEαβ), CF ₃ CHFOCH ₃ (HFE-254ebEβγ), CHF ₂
OCH ₂ CHF ₂ (HFE-254faE), CF ₃ OCH ₂ CH ₂ F (HFE-254
fbEαβ), CF ₃ CH ₂ OCH ₂ F (HFE-254fbEβγ), CH ₃ OCF ₂
CH ₂ F (HFE-263caEβγ), CF ₃ CH ₂ OCH ₃ (HFE-263fbE)
βγ), CH ₃ OCH ₂ CHF ₂ (HFE-272fbEβγ), CHF ₂ OCHFCF
₂ CF ₃ (HFE-338mceEγδ), CHF ₂ OCF ₂ CHFCF ₃ (HFE-3
38mceEγδ), CF ₃ CF ₂ OCH ₂ CF ₃ (HFE-338mfEβγ), (C
_{F 3) 2 CHOCHF 2 (HFE} -338mmzEβγ), CF 3 CF 2 CF 2 OCH 3
(HFE-347sEγδ), CHF ₂ OCH ₂ CF ₂ CF ₃ (HFE-347mfcE
γδ), CF ₃ OCH ₂ CF ₂ CHF ₂ (HFE-347mfcEαβ), CH ₃ OCF
₂ CHFCF ₃ (HFE-356 mecEγδ), CH ₃ OCH (CF ₃ ) ₂ (HFE-
356 mmz Eβγ), CF ₃ CF ₂ OCH ₂ CH ₃ (HFE-365mcEβγ), C
F ₃ CF ₂ CH ₂ OCH ₃ (HFE-365mcEγδ), CF ₃ CF ₂ CF ₂ OCHF
CF ₃ (HFE-42-11meEγδ), CF ₃ CFCF ₃ CF ₂ OCH ₃ , CF ₃ C
F ₂ CF ₂ CF ₂ OCH ₃ , CF ₃ CFCF ₃ CF ₂ OCH ₂ CH ₃ , CF ₃ CF ₂ CF
_{2 CF 2 OCH 2 CH 3,} CF 3 CF 2 CF 2 OCH 3, and is selected from the group consisting of any two or more thereof, the blowing agent of claim 1.