CN103627019A

CN103627019A - Foaming agents and compositions containing fluorine substituted olefins and ethers, and methods of foaming

Info

Publication number: CN103627019A
Application number: CN201310175062.1A
Authority: CN
Inventors: J.M.博曼; D.J.威廉斯
Original assignee: Honeywell International Inc
Current assignee: Honeywell International Inc
Priority date: 2006-03-21
Filing date: 2007-03-21
Publication date: 2014-03-12
Also published as: WO2007109748A3; JP2017078176A; KR20090013759A; CN101448913A; JP2018159074A; EP1996668A2; CA2646990C; JP2009530489A; JP2015212387A; WO2007109748A2; KR20140116455A; JP2014114456A; KR20150080632A; CA2646990A1; MX2008011943A

Abstract

Various uses of fluoroalkenes, including tetrafluoropropenes, particularly (HFO-1234) in a variety of applications, including as blowing agents are disclosed, particularly in combination with one or more fluorinated ethers.

Description

Contain the whipping agent that fluorine replaces unsaturated olefin

The application divides an application, and its female case is to be on March 21st, 2007 applying date, and application number is 200780018514.8, and denomination of invention is the application of " containing the whipping agent that fluorine replaces unsaturated olefin ".

Invention field

The present invention relates in many application (particularly including the heat-transfer system of for example refrigeration system) and at whipping agent, foamable composite (foamable composition), foam (foams) with useful composition, method and system in foam or the article made by foam.Aspect preferred, the present invention relates to such composition, its alkene that comprises at least one polyfluoro of the present invention (multi-fluorinated) and at least one fluorinated ether.

Background

Find, the fluid based on fluorohydrocarbon is commonly used in many commercial and industrial application, comprises as aerosol propellant (aerosol propellants) with as whipping agent.Because some shady (suspected) environmental problem, comprise relatively high global warming potential (use that has been used composition so far to some in these application is relevant), the fluid that use has low even zero ozone depletion potential (ozone depletion potential) becomes and more and more caters to the need, hydrogen fluorohydrocarbon (hydrofluorocarbons, " HFC ") for example.Therefore, using is not desirable containing a large amount of Chlorofluorocarbons (CFCs) (" CFC ") or the fluid of Hydrochlorofluorocarbons (hydrochlorofluorocarbons, " HCFC ").And some HFC fluid may have relative relatively high global warming potential, and using hydrogen fluorohydrocarbon or other fluorinated fluids with alap global warming potential, maintain the performance of wanting in character of use simultaneously, is desirable.As indicated above, recent years, about more and more to the concern of the Latent destruction of earth Atmosphere and climate, in this, some chlorine-containing compound has been determined to be problem especially severe.The use of chlorine-containing component (for example Chlorofluorocarbons (CFCs) (CFC), Hydrochlorofluorocarbons (HCF) etc.) in many application becomes and is not popular, because many such compounds have ozone-depleting character.So, more and more need new fluorohydrocarbon and hydrogen fluorocarbon compound and composition, as be used the attractive substitute of composition so far in these application and other application.For example, by the non-chlorine-containing compound with can not depletion, for example hydrogen fluorohydrocarbon (HFC), replaces chlorine-containing compound, thereby (retrofit) the chloride system of improvement (for example foaming agent system or refrigeration system) becomes and caters to the need.Generally speaking, the new mixture based on fluorohydrocarbon of industrial just constantly searching, it can replace CFC and HCFC, and is considered to the substitute to the safer CFC of environment and HCFC.But, be considered in many cases importantly, any possible substitute must also have those and be present in the character in the most widely used many fluids, for example give fabulous thermal insulating properties, with other foam characteristics wanted (foam characteristic) when being used as whipping agent, for example suitable chemical stability, hypotoxicity or nontoxicity, low combustible or without combustibility, etc.

In addition, it has been generally acknowledged that desirablely, do not need that conventional foam generating system is done to very large design and change the CFC whipping agent substitute that can play a role.

For example, method and composition for the manufacture of conventional foam materials (thermoplastic material and thermosetting material) is well known for a long time.These method and compositions are used chemical foaming agent and/or pneumatogen to form foamy structure in polymeric matrix conventionally.Such whipping agent comprises, for example, and azo-compound, various volatile organic compounds (VOC) and Chlorofluorocarbons (CFCs) (CFC).Chemical foaming agent stands the chemical transformation of some form conventionally, comprises and the material generation chemical reaction (conventionally carrying out under predetermined temperature/pressure) that forms polymeric matrix, and this causes discharging gas, for example nitrogen, carbonic acid gas or carbon monoxide.One of the most frequently used chemical foaming agent is water.Pneumatogen is dissolved in polymkeric substance or polymer precursor material conventionally, and volumetric expansion subsequently (or carrying out under predetermined temperature/pressure) is to contribute to form foamy structure.Pneumatogen is usually for thermoplastic foam, although chemical foaming agent also fungible things haircut infusion be used in or be used in thermoplastic foam together with pneumatogen.For example, the known chemical foaming agent that uses when the foam forming based on polyvinyl chloride.Chemical foaming agent and/or pneumatogen are generally used in thermosetting foams.Certainly, possible some compound and the composition that contains them constitutional chemistry whipping agent and pneumatogen at once.

In the past, CFC is generally used as for example, standard whipping agent in the preparation of the foam (hard and flexible PU foam and polyisocyanurate foam) based on isocyanic ester.For example, CCl ₃f (CFC-11) has become standard whipping agent.But the use of this material is forbidden by international treaties, can destroy the ozonosphere in stratosphere because it is discharged into the atmosphere.Thereby, use pure CFC-11 for example, as the standard whipping agent that is used to form thermosetting foams (foam based on isocyanic ester and phenolic foams) no longer general.

Using more frequently of the fluorochloroparaffins (chlorofluoroalkanes, HCFC) that the problem that CFC brings causes containing hydrogen.For example, CHCl ₂cF ₃(HCFC-123), CH ₂clCHClF (HCFC-141b) has the relatively short life-span in atmosphere.But although relative CFC, HCFC is considered to the whipping agent of environmental protection, such compound still contains some chlorine, so have " ozone depletion potential " (being called " ODP ").Because non-zero odp, HCFC has been determined finally to get rid of from use.

The whipping agent of another kind of Known Species is non-chlorination, partially hydrogenated fluorohydrocarbon (being called as " HFC ").Current some HFC that is just being used as whipping agent has at least one potential serious problems, and they have relatively high inherence (intrinsic) thermal conductivity (i.e. poor heat insulating ability) conventionally.On the other hand, for example, with some HFC whipping agent more recently (CF ₃cH ₂cF ₂h (" HFC-245fa ")) foam of manufacturing, partly due to the low heat conductivity of HFC-245fa steam, and partly gives the meticulous cell structure (cell structure) of foam due to HFC-245fa, thereby the heat insulating ability of improvement is provided.HFC-245fa in thermal insulation application, particularly, in refrigerator, refrigerator, refrigerator/refrigerator and spraying foam (spray foam) application, is widely used.Yet many HFC fluids have the shortcoming of the global warming potential that tool is relatively high, desirable, use and there is the hydrogen fluorohydrocarbon of alap global warming potential or the fluid that other are fluoridized, maintain the performance of wanting in character of use simultaneously.Even HFC more recently, for example HFC-245fa, HFC-134a, HFC-365mfc and other, also show the global warming potential higher than desirable level (although other HFC are lower relatively).Therefore, HFC in foam insulation body, particularly in rigid foam thermal insulator as the use of whipping agent, cause HFC to become whipping agent more undesirable in commercial foam thermal insulator.

Hydrocarbon blowing agent is also known.For example, authorize the United States Patent (USP) the 5th of Hutzen, instructed iso-pentane in different milk sap mixtures and the purposes of Skellysolve A for 182, No. 309.As authorize the United States Patent (USP) the 5th of Volkert, and to instruct for 096, No. 933, another example of hydrocarbon blowing agent is pentamethylene.Although many hydrocarbon blowing agents, for example the isomer of pentamethylene and pentane is zero ozone depletion agent and shows low-down global warming potential, but such material is not desirable completely, because of the foam that these whipping agents of serving as reasons are produced, lack and the heat insulating ability of using the foam same degree that for example HFC-245fa whipping agent is manufactured.And hydrocarbon blowing agent is extremely inflammable, this is undesirable.In addition, some hydrocarbon blowing agent has and forms the inadequate miscibility of material of foam in some cases, and described material is the polyester polyol in many polyurethane foams that are generally used in poly-isocyanurate modification for example.The use of these alkane usually needs chemical surfactant to obtain suitable mixture.

Therefore, more and more need new compound and composition, as use the attractive substitute of composition so far as whipping agent in these application and other application.Therefore applicant recognizes needs the new compound based on fluorohydrocarbon and composition, and it can effectively replace CFC and HCFC, and they can be considered to CFC and HCFC to the safer substitute of environment.But, conventionally being considered to very desirable is, any possible substitute must also have certain character or give foam certain character, these character are at least comparable to the character relevant to the most widely used many whipping agents, for example gas phase thermal conductivity (the low K-factor), hypotoxicity or nontoxicity, etc.

In many application, another so potential critical nature is flammable.That is,, in many application, particularly including in whipping agent application, use low combustible or nonflammable composition to be considered to important or necessary (essential).As used herein, term " nonflammable " refers to that according to ASTM standard E-681 in 2002, measuring (merging to by reference in this literary composition) is confirmed as nonflammable compound or composition.Unfortunately, many HFC may be desirable in foam foaming agent composition for being used in other respects, but are not nonflammable.For example, fluoric ether (fluoroalkane) C2H4F2 C2H4F2 (HFC-152a) and fluoroolefins (fluoroalkene) 1,1,1-trifluoro propene (HFO-1243zf) is all respectively inflammable, therefore cannot be for many application.

The example of another relative inflammable material is fluorinated ether 1,1,22-tetrafluoro ethyl-methyl ether (its be called as HFE-254pc or sometimes also referred to as HFE-254cb), has measured it and has had approximately 5.4% to approximately 24.4% combustion limits (flammability limit) (volume %).This medium-sized fluorinated ether is disclosed as whipping agent in authorizing No. the 5th, 137,932, the United States Patent (USP) of Beheme etc., is merged to by reference in this literary composition.

Authorizing the United States Patent (USP) the 5th of Tapscott, in 900, No. 185, built view is used brominated halocarbon additive to reduce some material combustibility of (comprising foam foaming agent).It is said that the feature of the additive in this patent is efficient and short atmospheric lifetime, that is, low-ozone consumes potential (ODP) and low global warming potential (GWP).

Although the brominated olefins of describing in the patent of Tapscott may have and the suitable efficiency of level of some material as fireproofing agent, does not disclose this material as the use of whipping agent.And, believe that such compound also may have some defect.For example, applicant has recognized that, many compounds of confirming in the patent of Tapscott will have relatively low efficiency as whipping agent, because this compound has relatively high molecular weight.In addition, believe many compounds that disclose in the patent of Tapscott, when it is used as whipping agent, will encounter problems, because this compound has relatively high boiling point.For example, and according to applicant's understanding, many compounds with high level replacement may have undesirable toxicity character and/or other undesirable character, undesirable biological accumulation on potential environment.

Although Tapscott points out the brominated alkene with 2 to 6 carbon atoms and also may contain fluoro substituents, but this patent propose " due to the reacting of tropospheric hydroxyl radical free radical; non-fluorine-containing bromoalkane will have very short atmospheric lifetime " (the 8th hurdle, 34-39 is capable), hint is from the position of environmental safety, and fluorochemicals not caters to the need completely.

And, be conventionally considered to desirable, in the situation that do not need the conventional equipment for foam preparation and formation and system to make the whipping agent substitute that very large design change can play a role.

Therefore applicant recognizes, needs such composition (particularly whipping agent, foamable composite), foam article and is used to form the method and system of foam, and it provides useful character and/or has eliminated above-mentioned one or more defects.Therefore applicant has recognized the need to such composition, particularly whipping agent, and it has still eliminated above-mentioned one or more defects likely for many application.

The present invention relates to composition useful in many application, method and system, particularly including the composition, method, system and the reagent that relate to foam of polymers.

General introduction

Applicant finds, above-mentioned needs need with other, can meet by foaming agent composotion, foamable composite, foam and/or the foam article that comprises one or more C2 to C6 fluoroolefins, more preferably comprise one or more C3 to C5 fluoroolefins, also more preferably comprise one or more and there is the compound as shown in the formula I:

XCF _zR _3-z(I)

Wherein X is C ₁, C ₂, C ₃, C ₄or C ₅undersaturated, that replace or unsubstituted group, each R is Cl, F, Br, I or H independently, and z is 1 to 3, and preferred fluoroolefins of the present invention has at least four (4) individual halogenic substituents conventionally, at least wherein three is F, and more preferably neither one is Br.

For there is the substituent embodiment of at least one Br, preferred compound is not hydrogeneous.In such embodiment, also preferably Br substituting group is positioned on unsaturated carbon conventionally, and also more preferably Br substituting group is positioned on non-terminal unsaturation carbon.A particularly preferred compound in this kind is CF ₃cBr=CF ₂, comprise its all isomer.

In some embodiments, it is most preferred that, the compound of formula I is propylene, butylene, amylene and the hexene (having or do not exist other substituting groups) with 3 to 5 fluoro substituents.Some preferred embodiment in, neither one R is Br, and preferably, unsaturated group is containing Br substituting group.In propylene, tetrafluoeopropene (HFO-1234) and fluorine propenyl chloride (for example trifluoro, a propenyl chloride (HFCO-1233)) are particularly preferred in some embodiments, more preferably CF ₃cCl=CH ₂and CF (HFO-1233xf) ₃cH=CHCl (HFO-1233zd)).

In some embodiments, preferably five fluorine propylene, have substituent five fluorine propylene, for example CF of hydrogen on unsaturated carbon endways particularly including those ₃cF=CFH (HFO-1225yez), particularly applicant find at least and Compound C F ₃cH=CF ₂(HFO-1225zc) compare, this compound has the toxicity of relative low degree.

In butylene, fluorine chlorobutylene is particularly preferred in some embodiments.

Term used herein " HFO-1234 " refers to all tetrafluoeopropenes.These tetrafluoeopropenes comprise 1,1,1,2-tetrafluoeopropene (HFO-1234yf) and cis-and anti-form-1,1,1,3-tetrafluoeopropene (HFO-1234ze).Term HFO-1234ze used herein is often referred to 1,1,1,3-tetrafluoeopropene, no matter and whether it is cis form or trans forms.Term used herein " cis HFO-1234ze " and " trans HFO-1234ze " cis form described respectively with 1,1,1 of trans forms, 3-tetrafluoeopropene.Therefore term " HFO-1234ze " comprises cis HFO-1234ze, trans HFO-1234ze and these all combinations and mixture within the scope of it.

Term used herein " HFO-1233 " refers to all trifluoros, a propenyl chloride.These trifluoros, a propenyl chloride comprises 1,1,1, three is fluoro-2, chloro-propylene (HFCO-1233xf) and cis-and anti-form-1,1,1-tri-is fluoro-3, propenyl chloride (HFCO-1233zd).It is fluoro-3 that term HFCO-1233zd used herein is often referred to 1,1,1-tri-, and chloro-propylene, no matter and whether it is cis form or trans forms.Term used herein " cis HFCO-1233zd " and " trans HFCO-1233zd " describe respectively 1,1 of cis form and trans forms, 1-trifluoro, chlorallylene.Therefore term " HFCO-1233zd " comprises cis HFCO-1233zd, trans HFCO-1233zd and these all combinations and mixture within the scope of it.

Term used herein " HFO-1225 " refers to five all fluorine propylene.Such molecule comprises 1,1,1,2,3 five fluorine propylene (HFO-1225yez), and cis form and trans forms.Therefore term used herein " HFO-1225yez " typically refers to 1,1,1,2, and 3 five fluorine propylene, no matter and whether it is cis form or trans forms.Therefore term " HFO-1225yez " comprises cis HFO-1225yez, trans HFO-1225yez and these all combinations and mixture within the scope of it.

Some preferred embodiment in, the invention provides the foaming agent composotion, foamable composite, foam and/or the foam article that comprise one or more C2 to C6 fluorinated olefin and one or more fluorinated ethers, described fluorinated olefin is C3 to C4 fluorinated olefin more preferably, comprise any or multiple preferred group and/or the preferred single fluorinated olefin compound of planting mentioned herein, described fluorinated ether is one or more hydrofluorination ethers (hydro-fluorinated ether) more preferably, also more preferably one or more C3 to C5 hydrofluorination ethers.In some highly preferred embodiment, the fluorinated ether using in this respect according to the present invention meets following formula (III):

C _aH _bF _c---O---C _dH _eF _f (III)

Wherein

A=1-6, more preferably 2-5, more preferably 3-5 also,

B=1-12, more preferably 1-6, more preferably 3-6 also,

C=1-12, more preferably 1-6, more preferably 2-6 also,

d＝1-2，

E=0-5, more preferably 1-3,

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

And C described in one of them _acan be bonded to a described C _dto form ring fluoroether.

The present invention also provides the method and system that utilizes the present composition, comprises the method and system for frostproof froth n..

Accompanying drawing explanation

Fig. 1 is the sketch of embodiment 1A container used.

Detailed description of the preferred embodiment

Composition

Composition of the present invention can be foaming agent composotion form or foamable composite form conventionally.In each case, the present invention needs at least one so civilian described fluoroolefin compounds, and optionally needs other compositions, and some other composition will be described in detail below.

A. fluoroolefins

The preferred embodiment of the present invention relates to and comprises at least one fluoroolefins composition, wherein said fluoroolefins contains 2 to 6, preferred 3-5 carbon atom, more preferably contain 3 to 4 carbon atoms, and most preferably contain in some embodiments 3 carbon atoms, and contain at least one carbon-to-carbon double bond.Sometimes for easy, if fluoroolefin compounds of the present invention contains at least one hydrogen, they are called as HF hydrocarbon or " HFO " in this literary composition.Although expect that HFO of the present invention can contain two carbon-to-carbon double bonds, now such compound is not thought preferably.For the HFO that also contains at least one chlorine atom, sometimes in this literary composition, use title HFCO.

As mentioned above, composition of the present invention comprises one or more according to the compound of formula I.In a preferred embodiment, described composition comprises the compound of one or more Formula Il:

Wherein each R is Cl, F, Br, I or H independently,

R ' is (CR ₂) _ny,

Y is CRF ₂

And n is 0,1,2 or 3, preferably 0 or 1, but conventionally preferably Br be not present in compound, or when Br is present in compound, in compound, there is no hydrogen.

In highly preferred embodiment, Y is CF ₃, n is that 0 or 1 (most preferably being 0) and at least one remaining R are F, and preferably neither one R is Br, or when there is Br, there is no hydrogen in compound.In some cases, in preferred formula II, neither one R is Br.

Applicant believes, conventionally, according to the instruction being included in herein, the compound of above definite formula I and II normally effectively and show the practicality in foaming agent composotion.But applicant finds surprisingly and unexpectedly, some has according to the compound of the structure of above-mentioned molecular formula, with other such Compound Phase ratios, shows very desirable low-level toxicity.Can recognize easily, this finds to have potential great advantages and benefit for preparation foaming agent composotion.More particularly, applicant thinks that relatively low toxic level and at least one R on unsaturated ends carbon atom are wherein H, and at least one remaining R is that (preferably Y is CF for the formula I of F or Cl or formula II ₃, n is 0 or 1) and compound is relevant.Applicant also thinks that all constitutional isomers, geometrical isomer and the steric isomer of such compound are all effectively and have useful hypotoxicity.

Some preferred embodiment in, compound of the present invention comprises C ₃or C ₄hFO or HFCO, preferably C ₃hFO, and more preferably according to the compound of formula I, wherein X is halo C ₃alkylene (C ₃alkylene) and z be 3.In some such embodiment, X is the C that fluorine and/or chlorine replace ₃alkylene, in some embodiments preferred following C ₃alkenes group:

-CH＝CF-CH ₃

-CF＝CH-CH ₃

-CH ₂-CF＝CH ₂

-CH ₂-CH＝CFH

Therefore such embodiment comprises following preferred compound: CF ₃-CH=CF-CH ₃; CF ₃-CF=CH-CH ₃; CF ₃-CH ₂-CF=CH ₂; CF ₃-CH ₂-CH=CFH; With these combinations each other and/or these and according to the combination of other compounds of formula I or formula II.

Some preferred embodiment in, compound of the present invention comprises C3 or C4HFCO, is preferably C3HFCO, and more preferably according to the compound of formula II, wherein Y is CF ₃, n is 0, at least one R on unsaturated ends carbon is H, and at least one remaining R is Cl.HFCO-1233 is the example of such preferred compound.

In highly preferred embodiment, particularly, in comprising the embodiment of above-mentioned low toxicity compounds, n is zero.In some highly preferred embodiment, composition of the present invention comprises one or more tetrafluoeopropenes, comprise HFO-1234yf, (cis) HFO-1234ze and (trans) HFO-1234ze, conventionally preferred HFO-1234ze, in some embodiments very preferably trans HFO-1234ze.Although the character of (cis) HFO-1234ze and (trans) HFO-1234ze is different at least in some aspects, expect that every kind in these compounds is all applicable to separately or is used from every kind of application described herein, method and system with other compounds one that comprise its steric isomer.For example, (trans) HFO-1234ze may be preferred in some system due to its relatively low boiling point (19 ℃), and (cis) HFO-1234ze has+boiling point of 9 ℃ may be preferred in other application.Certainly, in many embodiments, probably the combination of cis and trans-isomer(ide) is acceptable and/or preferred.Therefore, it being understood that term " HFO-1234ze " and 1,3,3,3-tetrafluoeopropene refer to two kinds of steric isomers, and except as otherwise noted, use this term to be intended to illustrate that cis form and trans forms are all suitable for, and/or can be used for described object.

HFO-1234 compound is known material and has been put into Chemical Abstracts (chemical abstracts) database.By various saturated and the undersaturated C that contain halogen ₃the catalyzed gas of compound fluoridizes to produce fluoropropenes, for example CF ₃cH=CH ₂, at United States Patent (USP) the 2nd, 889, No. 379, the 4th, 798, No. 818 and the 4th, describe in 465, No. 786, by reference they are merged so far in literary composition.EP974,571 (being also incorporated by reference into this literary composition) have disclosed passes through 1,1,1,3,3-pentafluoropropane (HFC-245fa) at high temperature contacts with the catalyzer based on chromium in gas phase, or pass through by 1,11,3,3-pentafluoropropane (HFC-245fa) in liquid phase with KOH, NaOH, Ca (OH) ₂or Mg (OH) ₂alcoholic solution contact, thereby prepare 1,1,1,3-tetrafluoeopropene.In addition, according to the production method of compound of the present invention, in name, be called synoptically in the U.S. Patent application co-pending of " Process for Producing Fluorpropenes the method for fluoropropenes (produce) ", lawyer's file number (H0003789 (26267)) and describe, also merged by reference so far in literary composition.

Other preferred compounds used according to the invention comprise that five fluorine propylene (comprise its all isomer (for example, HFO-1225)), tetrafluoro butylene and five fluorine butylene (comprising its all isomer (for example HFO-1354 and HFO-1345)).Certainly, composition of the present invention can be included in the combination of any two or more compounds in general range of the present invention (broad scope) or in any preferable range of the present invention.

Composition of the present invention, particularly those comprise the HFO-1234 composition of (comprising HFO-1234ze and HFO-1234yf), are considered to have for the favourable character of many major reasons.For example, at least partly based on mathematical modeling, applicant thinks that fluoroolefins of the present invention will can not produce substantial negative impact to atmospheric chemistry, compares with some other halogenation materials, and it can be ignored to the effect of ozone-depleting.Therefore preferred composition of the present invention does not have advantages of and can have substantive contribution to ozone-depleting.Compare with many hydro fluoroalkaness (hydrofluoroalkanes) of current use, preferred composition can not have substantial contribution to Global warming yet.

In some preferred form, composition of the present invention has not higher than approximately 1000, more preferably no higher than approximately 500, also more preferably no higher than approximately 150 global warming potential (GWP).In some embodiments, the GWP of the present composition is higher than approximately 100, more preferably, and not higher than approximately 75.As used herein, as (being incorporated by reference in this literary composition) in " The Scientific Assessment of Ozone Depletion; 2002; a report of the World Meteorological Association ' s Global Ozone Research and Monitoring Project (Scientific evaluation of ozone-depleting; 2002; the global ozone research of world meteorology association and the report of Supervisory Surveillance Program) " middle detailed description, " GWP " that measure is with respect to carbonic acid gas, through the GWP of 100 years.

In some preferred form, composition of the present invention also preferably has not higher than approximately 0.05, more preferably no higher than approximately 0.02, is also more preferably zero ozone depletion potential (ODP).As used herein, " ODP " is as described in detail in " The Scientific Assessment of Ozone Depletion; 2002; a report of the World Meteorological Association ' s Global Ozone Research and Monitoring Project (Scientific evaluation of ozone-depleting; 2002; the global ozone research of world meteorology association and the report of Supervisory Surveillance Program) ", merged by reference so far in literary composition.

The formula I compound containing in the present invention combination (HFO-1234 particularly, and HFO-1234ze more preferably) amount can great changes have taken place, determined specific application, and contained more than composition trace and that be less than 100% compound and all belong to general range of the present invention.And the present composition can be (azeotrope-like) azeotropic, class azeotropic or non-azeotropic.In a preferred embodiment, composition of the present invention, foaming agent composotion particularly, comprise formula I and/or formula II compound, preferred HFO-1234, and more preferably HFO-1234ze and/or HFO-1234yf, content is approximately 1% to approximately 99% by weight, more preferably being approximately 5% to approximately 95% by weight, is more preferably also 40% to approximately 90% by weight.

A. fluoroether

Some preferred embodiment relates to the composition that comprises the described fluoroolefins of at least one this literary composition and at least one fluoroether the present invention, wherein said at least one fluoroether is at least one hydrogen fluoroether more preferably, contain 2 to 8, preferably 2 to 7, more preferably 2 to 6 carbon atoms also, and in some embodiments most preferably containing three carbon atoms.If hydrogen fluoroether compound of the present invention contains at least one hydrogen, sometimes for easy, in this literary composition, they are called as hydrogen fluoroether or " HFE ".

Applicant thinks, conventionally, according to the instruction being included in this literary composition, according to the fluoroether of the disclosure of invention, particularly normally effective according to the fluoroether of above definite formula (III), and reveals practicality with fluoroolefin compounds associative list.But, applicant finds, preferably in some embodiments, particularly relate in the embodiment of foaming agent composotion and foam and foaming method, use fluoroether, in fluoroether, preferably utilize at least difluorizated, more preferably at least trifluorinated, more preferably at least tetrafluorizated hydrogen fluoroether also.Particularly preferably be in some embodiments there are 3 to 5 carbon atoms, more preferably 3 to 4 carbon atoms, the more preferably tetrafluoride fluoroether of 3 carbon atoms also.

Some preferred embodiment in, compound of the present invention comprises 1,1, and 2,2-tetrafluoro ethyl-methyl ether (tetrafluoroethylmethylether) (it is called as HFE-245pc or HFE-245cb2 in this literary composition sometimes), comprises its any and all isomeric forms.

The formula III compound containing in composition of the present invention (particularly 1,1,2,2-tetrafluoro ethyl-methyl ether) amount can great changes have taken place, determined specific application, and contained more than composition trace and that be less than 100% compound and all belong to general range of the present invention.In a preferred embodiment, the present composition, particularly foaming agent composotion, comprise formula III compound, comprise preferred compound colony, content is approximately 1% to approximately 99% by weight, more preferably being approximately 5% to approximately 95% by weight, is more preferably also 40% to approximately 90% by weight.

According to some of the preferred embodiment of the invention, preferably use one or more following compounds:

CHF ₂OCH ₂F(HFE-143E)

CH ₂FOCH ₂F(HFE-152E)

CH ₂FOCH ₃(HFE-161E)

Ring-CF ₂cH ₂oCF ₂o (HFE-c234fE α β)

Ring-CF ₂cF ₂cH ₂o (HFE-c234fE β Y)

CHF ₂OCF ₂CHF ₂(HFE-236caE)

CF ₃CF ₂OCH ₂F(HFE-236cbEβY)

CF ₃OCHFCHF ₂(HFE-236eaEαβ)

CHF ₂OCHFCF ₃(HFE-236eaEβY)

CHF ₂OCF ₂CH ₂F(HFE-245caEαβ)

CH ₂FOCF ₂CHF ₂(HFE-245caEβY)

CF ₃OCF ₂CH ₃(HFE-245cbEβY)

CHF ₂CHFOCHF ₂(HFE-245eaE)

CF ₃OCHFCH ₂F(HFE-245ebEαβ)

CF ₃CHFOCH ₂F(HFE-245ebEβY)

CF ₃OCH ₂CF ₂H(HFE-245faEαβ)

CHF ₂OCH ₂CF ₃(HFE-245faEβY)

CH ₂FCF ₂OCH ₂F(HFE-254caE)

CHF ₂OCF ₂CH ₃(HFE-254cbEαβ)

CHF ₂CF ₂OCH ₃(HFE-254caEβY)

CH ₂FOCHFCH ₂F(HFE-254eaEαβ)

CF ₃OCHFCH ₃(HFE-254ebEαβ)

CF ₃CHFOCH ₃(HFE-254ebEβY)

CHF ₂OCH ₂CHF ₂(HFE-254faE)

CF ₃OCH ₂CH ₂F(HFE-254fbEαβ)

CF ₃CH ₂OCH ₂F(HFE-254fbEβY)

CH ₃OCF ₂CH ₂F(HFE-263caEβY)

CF ₃CH ₂OCH ₃(HFE-263fbEβY)

CH ₃OCH ₂CHF ₂(HFE-272fbEβY)

CHF ₂OCHFCF ₂CF ₃(HFE-338mceEYδ)

CHF ₂OCF ₂CHFCF ₃(HFE-338mceEYδ)_

CF ₃CF ₂OCH ₂CF ₃(HFE-338mfEβY)

(CF ₃) ₂CHOCHF ₂(HFE-338mmzEβY)

CF ₃CF ₂CF ₂OCH ₃(HFE-347sEYδ)

CHF ₂OCH ₂CF ₂CF ₃(HFE-347mfcEYδ)

CF ₃OCH ₂CF ₂CHF ₂(HFE-347mfcEαβ)

CH ₃OCF ₂CHFCF ₃(HFE-356mecEYδ)

CH ₃OCH(CF ₃) ₂(HFE-356mmzEβY)

CF ₃CF ₂OCH ₂CH ₃(HFE-365mcEβY)

CF ₃CF ₂CH ₂OCH ₃(HFE-365mcEYδ)

CF ₃CF ₂CF ₂OCHFCF ₃(HFE-42-11meEYδ)

CF ₃CFCF ₃CF ₂OCH ₃

CF ₃CF ₂CF ₂CF ₂OCH ₃

CF ₃CFCF ₃CF ₂OCH ₂CH ₃

CF ₃CF ₂CF ₂CF ₂OCH ₂CH ₃

CF ₃CF ₂CF ₂OCH ₃.

It should be understood that present inventor expects, according to a preferred aspect of the present invention, any two or more above-mentioned HFE can combinedly be used.For example, according to some of the preferred embodiment of the invention, expection can be used the material of the commodity sold by 3M HFE-7100 by name to produce good result (to advantage), and this material is understood to be the mixture of the methyl nine fluoro butyl ethers of approximately 20% to approximately 80% methyl nine fluoro isobutyl ethers (methyl nonafluoroisobutyl ether) and approximately 20% to approximately 80%.By more embodiment, according to some of the preferred embodiment of the invention, expection can be used the material of the commodity sold by 3M HFE-7200 by name to produce good result, and this material is understood to be the mixture of the ethyl nine fluoro butyl ethers of approximately 20% to approximately 80% ethyl nine fluoro isobutyl ethers and approximately 20% to approximately 80%.

Also expection, any or multiple HFE listed above also can be combined with other compounds, comprises that other (designated) fluoroethers the HFE clearly listing in this literary composition and/or known and appointment form other compound of azeotropic mixture.For example, known following every kind of compound forms azeotropic mixture together with trans-dichloroethylene, and expection, is object of the present invention, and the use of such azeotropic mixture should be considered to belong to general range of the present invention:

CF ₃CFCF ₃CF ₂OCH ₃

CF ₃CF ₂CF ₂CF ₂OCH ₃

CF ₃CFCF ₃CF ₂OCH ₂CH ₃

CF ₃CF ₂CF ₂CF ₂OCH ₂CH ₃

CF ₃CF ₂CF ₂OCH ₃.

C. other composition-foaming agent composotions

Expection In some embodiments of the present invention, foaming agent composotion by or basic (essentially) by forming according to one or more compounds of this paper Chinese style I.Therefore, the present invention includes such method and system, it comprises one or more compounds of the present invention as whipping agent, and does not have any a large amount of extra composition.But one or more compounds or the composition that do not belong to formula I or formula II scope are optional, but preferably, they are included in foaming agent composotion of the present invention.Optional added compound like this comprises, but be not limited to, other are also as whipping agent (below for easy but be not intended to restriction and be called co-foaming agent (co-blowing agent)), tensio-active agent, polymer modifiers, toughner, tinting material, dyestuff, solubilizing agent, rheology modifier, softening agent, flammable inhibitor (flammability suppressants), antiseptic-germicide, visbreaking properties-correcting agent (viscosity reduction modifiers), weighting material, vapour pressure properties-correcting agent (vapor pressure modifiers), nucleator, the compound of catalyzer etc.Some preferred embodiment in, dispersion agent, hole stablizer (cell stabilizers), tensio-active agent and other additives also can be added in foaming agent composotion of the present invention.Some tensio-active agent is optional, but be preferably added into, usings as hole stablizer.Some representational materials are sold with commodity DC-193, B-8404 by name and L-5340, conventionally they are polysiloxane polyoxyalkylene block multipolymers, for example those are at United States Patent (USP) the 2nd, 834, No. 748, the 2nd, 917, No. 480 and the 2nd, the material disclosing in 846, No. 458, merges them so far in literary composition by reference.Other optional additives for blowing agent blends can comprise fire retardant, for example tris(2-chloroethyl)phosphate, tricresyl phosphate (2-chlorine propyl ester), tricresyl phosphate (2,3-dibromo propyl ester), tricresyl phosphate (1,3-dichloro propyl ester), Secondary ammonium phosphate, the aromatic substance of various halogenations, weisspiessglanz, aluminum trihydrate (aluminum trihydrate), polyvinyl chloride, etc.

For nucleator, all known compounds with kernel function and material all can be used in the present invention, particularly including talcum.

Certainly, other regulate compound and/or the composition of the special properties (for example cost) of described composition also can be included in composition of the present invention, and the existence of all such compounds and composition belongs to general range of the present invention.

Therefore, the preferred implementation of the present composition, the compound (particularly including HFO-1234ze and/or HFO-1234yf) except formula I, also comprises one or more co-foaming agents.According to co-foaming agent of the present invention, can comprise pneumatogen, chemical foaming agent (preferably comprising in some embodiments water) or there is the whipping agent of pneumatogen character and chemical foaming agent properties of combination.Also will recognize, be included in the whipping agent (compound and the described co-foaming agent that comprise formula I) in the present composition, can show except those are as the character the essential characteristic of whipping agent.For example, expect that foaming agent composotion of the present invention can comprise the composition of the compound that comprises above-mentioned formula I, it is also given foaming agent composotion or is added with its some useful character of foamable composite.For example, the compound of formula I or co-foaming agent also can be used as polymer modifiers or as visbreaking properties-correcting agent, this all belongs to scope of the present invention.

Although expection can be used a variety of co-foaming agents according to the present invention, in some embodiments, preferably, foaming agent composotion of the present invention comprises that one or more HFC are as co-foaming agent, more preferably one or more C1-C4HFC, and/or one or more hydrocarbon, more preferably C4-C6 hydrocarbon.For example, about HFC, foaming agent composotion of the present invention can comprise following one or more: all isomer of methylene fluoride (HFC-32), fluoroethane (HFC-161), C2H4F2 C2H4F2 (HFC-152), Halothane (HFC-143), Tetrafluoroethane (HFC-134), pentafluoride ethane (HFC-125), pentafluoropropane (HFC-245), HFC-236fa (HFC-236), heptafluoro-propane (HFC-227ea), 3-pentafluorobutane (HFC-365), hexafluoro butane (HFC-356) and all such HFC.About hydrocarbon, in some preferred implementation, foaming agent composotion of the present invention can comprise, for example, and for iso-pentane, Skellysolve A and/or the pentamethylene of thermosetting foams, and for butane or the Trimethylmethane of thermoplastic foam.Certainly, also can comprise other materials, for example water, CO ₂, CFC (for example trichlorofluoromethane (CFC-11) and Refrigerant 12 (CFC-12)), hydrogen chlorocarbon (hydrochlorocarbons) (HCC, Ethylene Dichloride (preferably trans-dichloroethylene) for example, ethyl chloride and chloropropane), HCFC, C1-C5 alcohol (for example, ethanol and/or propyl alcohol and/or butanols), C1-C4 aldehyde, C1-C4 ketone, C1-C4 ether (comprises ether (for example dme and diethyl ether), diether (for example Methylal(dimethoxymethane) and methylene diethyl ether)) and the combination of methyl-formiate and any these materials, it is not preferred that the composition of even now is expected in many embodiments because of its negative environmental influence.

In some embodiments, one or more following HFC isomer are preferably used as the co-foaming agent in composition of the present invention:

1,1,1,2,2-pentafluoride ethane (HFC-125)

1,1,2,2-Tetrafluoroethane (HFC-134)

HFA 134a (HFC-134a)

1,1-C2H4F2 C2H4F2 (HFC-152a)

HFC-227ea (HFC-227ea)

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

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

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

Any above-mentioned extra co-foaming agent, and any relative quantity that is included in the extra composition in the present composition, can in total general range of the present invention, do according to the application-specific of composition very large change, and all such relative quantities are all considered to belong to scope of the present invention.But applicant notices, at least some for example, is that such compound has relatively low combustibility according to a special advantage of the compound of formula I of the present invention (HFO-1234ze).Therefore, in some embodiments, preferably, foaming agent composotion of the present invention comprises at least one co-foaming agent and a certain amount of according to the compound of formula I, is enough to produce nonflammable foaming agent composotion generally.Therefore,, in this embodiment, co-foaming agent will depend on the combustibility of co-foaming agent at least in part than the relative quantity of the compound of formula I.

Foaming agent composotion of the present invention can comprise the compound of the present invention of various content ranges.But, conventionally preferably, for be used as the preferred composition of whipping agent according to the present invention, according to the compound of formula I, more preferably according to the compound of formula II, its amount account for by weight described composition at least about 1%, more preferably at least about 5%, also more preferably at least about 15%.Some preferred embodiment in, whipping agent comprises the whipping agent compound of the present invention at least about 50% (by weight), and in some embodiments, whipping agent is comprised of compound according to the present invention substantially.In this, the use that is noted that one or more co-foaming agents is with novelty of the present invention consistent with basic feature.For example, be expected in many embodiments, water will be used as co-foaming agent or for example, be combined with other co-foaming agents (pentane, particularly pentamethylene).

Expect that foaming agent composotion of the present invention can comprise two or more combination of HFO-1234yf, cis HFO-1234ze, trans HFO-1234ze or these, their amount be preferably by weight described composition at least about 15%.In many preferred implementations, the co-foaming agent that comprises water is included in composition, is most preferably included in the composition for thermosetting foams.Some preferred embodiment in, the combination that foaming agent composotion of the present invention comprises cis HFO-1234ze and trans HFO-1234ze, wherein cis: trans weight ratio is approximately 1: 99 to approximately 50: 50, more preferably approximately 10: 90 to approximately 30: 70.In some embodiments, may preferably use the combination of cis HFO-1234ze and trans HFO-1234ze, wherein cis: trans weight ratio is approximately 1: 99 to approximately 10: 90, and is preferably approximately 1: 99 to approximately 5: 95.Certainly, in some embodiments, using wherein cis-isomeride may be desirable with the combination existing than trans-isomer(ide) greater concn, for example, and for the foamable composite that is applicable to using together with liquid blowing agent.

In some preferred implementation, foaming agent composotion comprises by weight for approximately 30% to approximately 95%, more preferably from about 30% to approximately 96%, more preferably from about 30% to approximately 97%, also more preferably from about 30% to approximately 98%, the compound of 30% to approximately 99% formula I more preferably from about also, the compound of formula II more preferably, one or more HFO-1234 compounds more preferably also, and be approximately 5% to approximately 90%, more preferably from about 5% to approximately 65% co-foaming agent by weight, comprise one or more fluoroethers.In some such embodiment, co-foaming agent comprises and is selected from following compound, and preferably substantially by being selected from following compound, forms: H ₂o, HFC, HFE, hydrocarbon, alcohol (preferably C2, C3 and/or C4 alcohol), CO ₂with these any two or more combination.

Lower Table A confirmed according to some preferred embodiment, and HFO particularly some of HFO-1234 (being more specifically HFO-1234ze) and HFE combines (all percentage ratio is all weight percentage).

Table A

At co-foaming agent, contain H ₂in the preferred implementation of O, composition comprises H ₂the amount of O accounts for approximately 5% to approximately 50% of total foaming agent composotion by weight, more preferably accounts for by weight approximately 10% to approximately 40%, also more preferably accounts for by weight approximately 10% to approximately 20% of total whipping agent.

At co-foaming agent, contain CO ₂preferred implementation in, composition comprises CO ₂amount account for by weight approximately 5% to approximately 60% of total foaming agent composotion, more preferably account for by weight approximately 20% to approximately 50%, also more preferably account for by weight approximately 40% to approximately 50% of total whipping agent.

In the preferred implementation that contains alcohol (preferably C2, C3 and/or C4 alcohol) at co-foaming agent, the amount that composition comprises alcohol accounts for approximately 5% to approximately 40% of total foaming agent composotion by weight, more preferably account for by weight approximately 10% to approximately 40%, also more preferably account for by weight approximately 15% to approximately 25% of total whipping agent.

For the composition that contains HFC co-foaming agent, HFC co-foaming agent (preferably C2, C3, C4 and/or C5HFC), more preferably methylene fluoride (HFC-152a) (thermoplastics that HFC-152a is particularly preferred for extruding) and/or the amount of pentafluoropropane (HFC-245) in composition preferably account for approximately 5% to approximately 80% of total foaming agent composotion by weight, more preferably be approximately 10% to approximately 75% by weight, also more preferably account for by weight approximately 25% to approximately 75% of total whipping agent.And in such embodiment, HFC is preferably C2-C4HFC, more preferably C3HFC, in some embodiments very preferably pentafluorated C3HFC, for example HFC-245fa.

For the composition that contains HFE co-foaming agent, HFE co-foaming agent (preferably C2, C3, C4 and/or C5HFE), more preferably the amount of HFE-254 (particularly including HFE-254pc) in composition preferably accounts for approximately 5% to approximately 80% of total foaming agent composotion by weight, more preferably be approximately 10% to approximately 75% by weight, also more preferably account for by weight approximately 25% to approximately 75% of total whipping agent.And in such embodiment, HFE is preferably C2-C4HFE, more preferably C3HFE, in some embodiments very preferably tetrafluorizated C3HFE.

For the composition that contains HC co-foaming agent, the amount of HC co-foaming agent (preferably C3, C4 and/or C5HC) in composition preferably accounts for approximately 5% to approximately 80% of total foaming agent composotion by weight, more preferably accounts for by weight approximately 20% to approximately 60% of total whipping agent.

C. other composition-foamable composites

One aspect of the present invention provides foamable composite.As known to those skilled, foamable composite contains one or more compositions that can form foam conventionally.As used herein, term " formation of foam agent (foam foaming agent) " is used to refer to and can forms the composition of foamy structure (preferred general is vesicular foamy structure) or the combination of composition.According to the present invention, foamable composite of the present invention comprises such composition and whipping agent compound, is preferably the compound of formula I.One or more compositions that in some embodiments, can form foam comprise thermoset composition and/or the foamable composite that can form foam.The example of thermoset composition comprises urethane and polyisocyanurate foam composition, and phenolic foams composition.This reaction and foaming process can be by being used various additives to strengthen, and described additive is catalyzer and surfactant material for example, and it is used for controlling and adjusting hole size stable foam structure during forming.And the above any or multiple extra composition described about foaming agent composotion of the present invention of expection can be added in foamable composite of the present invention.In such thermosetting foams embodiment, one or more present compositions are included in foamable composite as whipping agent or partial foaming agent, or as a part for two portions or many parts foamable composite, it preferably includes one or more can react and/or foam to form the composition of foamy structure or vesicular structure under conditions suitable.

In some other embodiment of the present invention, the described composition that one or more can foam comprises thermoplastic material, particularly thermoplastic polymer and/or resin.The example of thermoplastic foam composition comprises polyolefine, for example formula Ar-CHCH ₂mono-vinyl (monovinyl) aromatic substance, wherein Ar is the aromatic hydrocarbon group of benzene series, for example polystyrene (PS).According to the present invention, the example of the polyolefin resin that other are suitable comprises various ethenoid resins (comprising Alathon, for example polyethylene, and ethylene copolymer), polypropylene (PP) and polyethylene terephthalate (PET).In some embodiments, thermoplastic foamable composition is extrudable (extrudable) composition.

Method and system

Expect and be allly at present knownly all easy to be applicable to the present invention with method and system available, that be used to form foam.For example, method of the present invention need to add according to whipping agent of the present invention conventionally in foamable composite or formation of foam composition, preferably by a step or series of steps, described composition is foamed subsequently, described step comprises to be made according to whipping agent volumetric expansion of the present invention.Conventionally, expection use at present for adding system and the device of whipping agent and foaming to be easy to be applicable to the present invention.In fact, think that an advantage of the present invention is the supply of the whipping agent of improvement, it adapts with existing foaming method and system conventionally.

Therefore, those skilled in the art will recognize, the present invention includes the method and system that makes all types frostproof froth n., comprise thermosetting foams, thermoplastic foam and original position shaping (formed-in-place) foam.Therefore, one aspect of the present invention is under conventional processing condition, and whipping agent of the present invention is combined with the conventional foaming machine of for example polyurethane foaming equipment.Therefore present method comprises that the operation of masterbatch (masterbatch) type, mixed type operation, the 3rd fluid foaming agent add (third stream blowing agent addition), and add whipping agent at foam head (foam head).

For thermoplastic foam, preferred method for example generally includes, to thermoplastic material (preferred thermoplastic polymkeric substance, polyolefine) to be introduced according to whipping agent of the present invention, then makes thermoplastic material stand effectively to cause the condition of foaming.For example, step from whipping agent to thermoplastic material that introduce can comprise in the screw extrusion press that contains thermoplastic material introduces whipping agent, and cause the step of foaming can comprise the pressure being reduced on thermoplastic material, thereby cause the expansion of whipping agent and facilitate the foaming of material.

Those skilled in the art, while particularly considering content disclosed herein, will recognize, order and the mode that whipping agent of the present invention forms and/or order and the mode joining in foamable composite do not affect operability of the present invention conventionally.For example, if extrudable foam, the various compositions of whipping agent, the composition of foamable composite even, can be not mixed before being incorporated into extrusion equipment, or even described composition can not be added into the same position of extrusion equipment.And whipping agent can directly be introduced into or be introduced into as premix (premix) part, this premix is further joined other parts of foamable composite subsequently.

Therefore, in some embodiments, may desirablely be, in first position of forcing machine, introduce one or more compositions of whipping agent, this position is positioned at the upstream of the position of adding one or more other compositions of whipping agent, expect that these compositions will pool together in forcing machine, and/or expection operates by this way more effective.Yet, in some embodiments, be pre-mixed two or more compositions of whipping agent and directly or as the part of premix be incorporated into together in foamable composite, described premix is further joined other parts of foamable composite subsequently.

An embodiment of the invention relate to the method that forms foam (optimization polyurethane and polyisocyanurate foam).As known in the art, the method generally includes provides foaming agent composotion of the present invention, foaming agent composotion (directly or indirectly) is joined in foamable composite, under the condition that effectively forms foamy structure or vesicular structure, make foamable composite reaction.Any well-known method in any this area, for example those are at " Polyurethanes Chemistry and Technology (polyurethane chemistry and technology) " I and II volume, Saunders and Frisch, 1962, John Wiley and Sons, New York, the method for describing in NY (being incorporated by reference in this literary composition), can be used or make it to be applicable to foam embodiment of the present invention by foam embodiment according to the present invention.Conventionally, such preferred method for example comprises, by mixing mixture, the whipping agent of isocyanic ester, polyol or polyol or the blowing agent blends that comprises one or more present compositions and other materials (catalyzer, tensio-active agent) and optional fire retardant, tinting material or other additives and prepares urethane or polyisocyanurate foam.

In many application, the composition that is provided for urethane or polyisocyanurate foam with the form of pre-mixed formulation is easily.The most representative ground, foam formulations is pre-blended into two kinds of compositions.Isocyanic ester and optional some tensio-active agent and whipping agent form the first composition, are commonly called " A " composition.Polyol or polyol mixture, tensio-active agent, catalyzer, whipping agent, fire retardant and other isocyanate-reactive compositions (reactive components) form the second composition, are commonly called " B " composition.Therefore, by manual mixing (while preparing on a small quantity), preferably, by machine mix set A composition and B composition, to form (spray applied) foam, blister (froth) of blocks (blocks), blob of viscose (slabs), laminating material, original position casting (pour-in-place) plate and other products, spray application etc., be easy to prepare urethane or polyisocyanurate foam.Optionally, other compositions, for example fireproofing agent, tinting material, auxiliary blowing agent, even other polyvalent alcohols, can be used as one or more extra fluids and are injected towards mixing head (mix head) or response location (reaction site).But most preferably, they are all added in an above-mentioned B-composition.

Present method and system also comprise the single composition foam of formation, preferably contain the polyurethane foam of with good grounds whipping agent of the present invention.In some preferred implementation, a part of whipping agent is preferably comprised in formation of foam agent by being dissolved in formation of foam agent, under the pressure of described formation of foam agent in container, is liquid, and the whipping agent of another part exists with independent gas phase.In such system, involved/whipping agent dissolving mainly causes the expansion of foam, and independent gas phase is given formation of foam agent with propulsive force.Like this single becomes sub-system conventionally and to be preferably packaged in the container of aerosol-type tank for example, therefore whipping agent of the present invention preferably provides for foam being expanded and/or being provided for the energy of foam/can foam material transport from packing, and preferably possesses two kinds of effects simultaneously.In some embodiments, such system and method comprises (fully formulated) system (preferred isocyanate/polyol system) preparing completely to packing loading and adds according to gaseous foaming agent of the present invention in packing (preferably aerosol-type tank).

Any well-known method in this area, for example those are at " Polyurethanes Chemistry and Technology (polyurethane chemistry and technology) " I and II volume, Saunders and Frisch, 1962, John Wiley and Sons, New York, the method for describing in NY (being incorporated by reference in this literary composition), can be used or make it to be applicable to formation of foam embodiment of the present invention by formation of foam embodiment according to the present invention.

Also expection, in some embodiments, when in supercritical state or nearly supercritical state, using composition of the present invention may be desirable as whipping agent.

Foam

The invention still further relates to foam (including but not limited to closed-cell foam, open celled foam, rigid foam, flexible foam, integral skin foam (integeral skin) etc.) prepared by all foam of polymers formulas (formulation) by containing the whipping agent that comprises the present composition.Applicant finds, foam (thermosetting foams particularly, for example, according to polyurethane foam of the present invention) an advantage be, preferably in thermosetting foams embodiment, can under cold condition particularly and preferably, at cold condition, be issued to abnormal superior thermal characteristics (thermal performance), described thermal characteristics for example can be measured by the K-factor or lambda factor.Although expect foam of the present invention, thermosetting foams of the present invention particularly, can be used in multiple application, but some preferred embodiment in, the present invention includes according to apparatus foam of the present invention, comprise refrigerator foam, refrigerator foam, refrigerator/refrigerator foam, slab foam (panel foams) and other colds or deep cooling Application in manufacture.

According to foam of the present invention, in some preferred implementation, except the low-ozone relevant to the many preferred whipping agents of the present invention consumes potential and low global warming potential, one or more uncommon features, characteristic and/or character are also provided, comprise: heat insulating ability (particularly for thermosetting foams), dimensional stability, compressive strength, thermal insulating properties aging.In some highly preferred embodiment, the invention provides thermosetting foams, comprise this foam of making foam article, with respect to use same amount but containing the foam of manufacturing according to the identical whipping agent of the compound of formula I of the present invention (or normally used blowing agent H FC-245fa), it shows the thermal conductivity of improvement.In some highly preferred embodiment, thermosetting foams of the present invention, optimization polyurethane foam shows not the K-factor (the BTU in/hr ft higher than approximately 0.14 in the time of 40 °F ²°F), more preferably no higher than 0.135, also more preferably no higher than 0.13.And, in some embodiments, preferably, thermosetting foams of the present invention, optimization polyurethane foam shows not the K-factor (the BTU in/hr ft higher than approximately 0.16 in the time of 75 °F ²°F), more preferably no higher than 0.15, also more preferably no higher than 0.145.

In other preferred implementations, the foam of producing with respect to the whipping agent using outside the scope of the invention, bubble of the present invention goes out the mechanical property of improvement.For example, the foam that some of the preferred embodiment of the invention provides and foam article, the foam that the whipping agent being comprised of pentamethylene with respect to utilization is produced under essentially identical condition, has better compressive strength, preferably relatively exceed at least about 10%, more preferably relatively exceed at least about 15%.And, in some embodiments, the compressive strength that preferably foam produced according to the invention has, the compressive strength that can be comparable in commercialization scale under essentially identical condition, the foam of manufacture has when just whipping agent is comprised of HFC-245fa.In some preferred implementation, bubble of the present invention goes out at least about the compressive strength of 12.5% yield rate (yield) (in parallel direction and vertical direction), and more preferably described in each, direction is at least about the compressive strength of 13% yield rate.

Embodiment

Following examples are provided for the present invention is described, not limit the scope of the invention.

Embodiment 1A-polystyrene foam

This embodiment has illustrated the use of the whipping agent of two preferred implementations according to the present invention, the i.e. production of the use of HFO-1234ze and HFO-1234yf, and polystyrene foam.As auxiliary, set up testing tool and formulated testing scheme, with the quality of determining whether specific whipping agent and polymkeric substance can produce foam and foam.In container, mix the polymkeric substance (Dow Polystyrene685D) grinding and the whipping agent substantially being formed by HFO-1234ze.The sketch of container as shown in Figure 1.Container volume is 200cm ³, it is that 2 inches, the stainless steel tube of long 4 inches, No. 40 (schedule40) are made by two pipe flanges (pipe flange) and one section of diameter.Container is placed on temperature and is arranged on approximately 190 °F to the baking oven of 285 °F (preferably for polystyrene, temperature is arranged on 265 °F), and container is continued to be placed on that, until reach temperature equilibrium.

Discharge subsequently the pressure in container, generate fast the polymkeric substance of foaming.Along with dissolving, whipping agent enters in polymkeric substance polymkeric substance described in its plasticising.Utilize the final densities of the such two kinds of foams producing of present method to provide in table 1, for using the density of the foam of trans HFO-1234ze and HFO-1234yf production.Data presentation, can obtain polystyrene foam according to the present invention.In this respect, be noted that under about room temperature, the bulk density of polystyrene is 1050kg/m ³or 65.625Ib/ft ³.

Table 1

embodiment 1B-polystyrene foam

This embodiment has confirmed the performance of the whipping agent of the HFO-1234ze polystyrene foam that conduct is shaped in double-screw type extruding machine separately.The instrument using is in this embodiment the Leistritz twin screw extruder machine with following characteristic:

30mm corotation screw rod

L: D ratio=40: 1

Extruding machine is divided into 10 parts, and each represents the L of 4: 1: D.Polystyrene resin is introduced in first part, and whipping agent is introduced in the 6th part, and extrudate departs from the tenth part.Extruding machine is mainly as the operation of fusing/mixing extruding machine.The cooling extruding machine of follow-up series winding, its design feature is:

Leistritz twin screw extruder machine

40mm corotation screw rod

L: D ratio=40: 1

Mould (die): 5.0mm is circular

Polystyrene resin, the common extrusion grade polystyrene of Nova Chemical-, is labeled as Nova1600, under condition described above, is added in extruding machine.Resin has the recommendation temperature of fusion of 375 °F to 525 °F.Extruding machine is approximately 1320 pounds (psi) per square inch at the pressure at mould place, and temperature at mould place is approximately 115 ℃.

The basic whipping agent being comprised of trans HFO-1234ze is added in extruding machine in position described above, wherein comprise account for by weight total whipping agent approximately 0.5% talcum as nucleator.According to the present invention, working concentration is that the whipping agent of 10% (by weight), 12% (by weight) and 14% (by weight) is produced foam.The density of the foam of producing is the scope of every cubic centimetre approximately 0.1 gram to 0.07 gram every cubic centimetre, and hole dimension is approximately 49 to approximately 68 microns.The foam that diameter is 30 millimeters seems to have good quality, very meticulous hole dimension, there is no visible or significantly pore or space.

embodiment 1C-polystyrene foam

Repeat the program of embodiment 1B, the HFC-245fa of the trans HFO-1234ze and 50% (by weight) that just whipping agent comprises approximately 50% (by weight), and the nucleator of concentration described in embodiment 1B.The polystyrene of the density of foaming agent preparation foaming with approximately 10% and 12%.The density of the foam producing is approximately 0.09 gram every cubic centimetre, and hole dimension is approximately 200 microns.The foam that diameter is 30 millimeters seems to have good quality, meticulous pore structure, there is no visible or obvious space.

embodiment 1D-polystyrene foam

Repeat the program of embodiment 1B, the HFC-245fa of the HFO-1234ze and 20% (by weight) that just whipping agent comprises approximately 80% (by weight), and the nucleator of concentration described in embodiment 1B.The polystyrene of the density of foaming agent preparation foaming with approximately 10% and 12%.The density of the foam producing is approximately 0.08 gram every cubic centimetre, and hole dimension is approximately 120 microns.The foam that diameter is 30 millimeters seems to have good quality, meticulous pore structure, there is no visible or obvious space.

embodiment 1E-polystyrene foam

Repeat the program of embodiment 1B, the HFC-245fa of the HFO-124ze and 20% (by weight) that just whipping agent comprises approximately 80% (by weight), and the nucleator of concentration described in embodiment 1B.The polystyrene of the density of foaming agent preparation foaming with approximately 10% and 12%.The density of foam is the scope of 0.1 gram at every cubic centimetre.The foam that diameter is 30 millimeters seems to have good quality, meticulous pore structure, there is no visible or obvious space.

embodiment 1F-polystyrene foam

Repeat the program of embodiment 1E, just omitted nucleator.The density of foam is the scope of 0.1 gram at every cubic centimetre, and hole dimension diameter is approximately 400.The foam that diameter is 30 millimeters seems to have good quality, meticulous pore structure, there is no visible or obvious space.

embodiment 2-polyurethane foam compressive strength

This embodiment has confirmed the HFO-1234ze that is combined with hydrocarbon co-foaming agent and the performance of isomer thereof, and the composition that has confirmed especially to comprise HFO-1234ze and pentamethylene co-foaming agent is in the practicality of the compressive strength aspect of performance of polyurethane foam.

This embodiment provides commercially available, freezing apparatus polyurethane foam formula (formation of foam agent).Polyol mixture is comprised of business polyol, catalyzer and tensio-active agent.This formula is applicable to being combined with gaseous foaming agent.Normal business urethane treatment facility is used to formation of foam process.Form gaseous foaming agent mixture (combination), its HFO-1234ze (comprising its isomer) and concentration that comprises that concentration accounts for approximately 60 % by mole of total whipping agents is the pentamethylene that accounts for approximately 40 % by mole of total whipping agents.This embodiment has illustrated the physicals of the mixture of HFO-1234ze (comprising its isomer) coupling collar pentane co-foaming agent.Following table 2 has been recorded, and the foam that the whipping agent being comprised of HFC-245fa with use is made with the whipping agent being comprised of pentamethylene is compared, the compressive strength of similar machine-made polyurethane foam (using whipping agent of the present invention).

table 2

A unexpected result of this embodiment explanation is in conventional foam treatment facility, particularly, in urethane treatment facility, to process HFO-1234ze and HFC-1234ze/HFC mixture.This has potential huge advantage, to such an extent as to can process foam by various types of systems and equipment, comprising: the 3rd fluid of masterbatch type mixing equipment, gas foaming agent mixing equipment, whipping agent adds, or adds at the whipping agent of foam head.

embodiment 3---the polyurethane foam K-factor

Preparation polyurethane foam also makes it be suitable as business " applied " polyurethane formulations.In formation of foam process, the same foam formula of describing in embodiment 2 is used for to identical normal business urethane treatment facility.Prepared several systems, each system is used identical composition, system and equipment, but uses different whipping agents.Except whipping agent according to the present invention, HFC-134a, HFC-245fa and pentamethylene are also tested as whipping agent respectively.In each system, with substantially the same volumetric molar concentration, in polyol mixture, add whipping agent.Described polyol mixture is comprised of business polyol, catalyzer and tensio-active agent.According to the business manufacturing operation process of standard, prepare foam, for example, for the preparation of the commercial operation process of the foam for freeze applications.Evaluate the K-factor of prepared foam, and by this information recording in following table 3.For determining benchmark and making comparisons, use HFC-134a to prepare foam, can consult the business data of HFC-134a.The K-factor data of these foams is presented in table 3.

table 3

This embodiment confirmed, when HFO-1234ze whipping agent is replaced while entering in (substituted into) polyurethane formulations, and the K-factor performance of HFO-1234ze and isomer thereof.To replace to HFO-1234ze with the volumetric molar concentration equating in benchmark foam.Table 3 data declaration, the HFO-1234ze foam K-factor is more much better than HFC-134a or pentamethylene foam.

the embodiment 4-polyurethane foam K-factor

This embodiment has confirmed the performance of the HFC co-foaming agent whipping agent that be combined, that comprise HFO-1234ze (comprising its isomer) that uses in the various preparations in polyurethane foam.Same foam formula, equipment and program that use is used in embodiment 2 and 3, but use different whipping agents.Prepare such whipping agent, it comprises the HFO-1234ze that concentration is approximately 80% (weight) of total whipping agent (comprising its isomer), and concentration be total whipping agent the HFC-245fa of approximately 20% (weight).Except whipping agent according to the present invention, HFC-134a and pentamethylene are also tested as whipping agent respectively.In each system, with essentially identical volumetric molar concentration, whipping agent is added in polyol mixture.Then use this whipping agent to form foam and measure the K-factor of foam.Following table 4 illustrated, when jointly using with HFC co-foaming agent, and the K-factor performance of HFO-1234ze (comprising its isomer) mixture.

table 4

A unexpected result of this embodiment explanation is in conventional urethane treatment facility, to process HFO-1234ze and HFC-1234ze/HFC mixture.This has potential huge advantage, to such an extent as to can process foam by various types of systems and equipment, comprising: the 3rd fluid of masterbatch type mixing equipment, gas foaming agent mixing equipment, whipping agent adds, or adds at the whipping agent of foam head.

the embodiment 5-polyurethane foam K-factor

This embodiment has further confirmed, when being used to the production of polyurethane foam, according to the unforeseeable performance of whipping agent of the present invention.Manufacture three kinds of apparatus polyurethane foams, with essentially identical material, program and equipment, form respectively, but use different whipping agents.Polyol system is commercially available, applied formula (formulation), and it is applicable to using together with liquid blowing agent.With foaming machine, form foam.With substantially equal volumetric molar concentration, use whipping agent.After formation, each foam is cut into the sample that is applicable to measuring the K-factor, and the K-factor is as shown in following table 5B.The weight percentage that blowing agent component accounts for total whipping agent is disclosed in following table 5A.

Table 5A

Whipping agent	A	B	C
				HFO-1234ze*	85	0	60
HFC-245fa	15	100	11

[0223]

Pentamethylene

0

29

* 100% cis

Table 5B

The presentation of results of recording in table 8C, with these levels, using the compounds of this invention (HFO-1234ze) and as the pentamethylene of co-foaming agent and HFC-245fa in conjunction with for thermosetting foams, can not produce injurious effects to the K-factor performance of independent use or the HFO-1234ze using together with HFC-245fa.This is unforeseeable result, because up to now, in blowing agent preparations, a large amount of pentamethylene that use produce harmful effect to K-factor performance.

the embodiment 6-polyurethane foam K-factor

Use polyol formula in the same manner as in Example 5 and isocyanic ester to carry out another experiment.Manual mixing is prepared foam.Whipping agent is by according to the compound of formula II, i.e. HFCO-1233zd (CF ₃cH=CHCl) * forms, and its molecular fraction that accounts for foamable composite is approximately identical with the whipping agent in embodiment 5.The K-factor is as shown in table 6 below.

table 6

The present invention relates to embodiment:

1. a whipping agent, it comprises:

(a) fluoroolefins of at least one formula I:

XCF _zR _3-z(I)

Wherein X is C ₁, C ₂, C ₃, C ₄or C ₅undersaturated, substituted or unsubstituted group, each R is Cl, F, Br, I or H independently, and z is 1 to 3, and

(b) at least one fluorinated ether.

2. the composition of embodiment 1, it further comprises at least one auxiliary, and described auxiliary is selected from any two or more combination of other co-foaming agent, tensio-active agent, polymeric modifier, toughner, tinting material, dyestuff, solubilizing agent, rheology modifier, softening agent, flammable inhibitor, antiseptic-germicide, visbreaking properties-correcting agent, weighting material, vapour pressure properties-correcting agent, nucleator, catalyzer and these.

3. the whipping agent of embodiment 1, wherein said at least one fluoroolefins comprise have 3 to 5 fluoro substituents at least one three carbon and/(or) at least one four carbon olefin.

4. the whipping agent of embodiment 1, wherein said at least one fluoroolefins comprises cis HFO-1234ze, or trans HFO-1234ze or these combination.

5. the whipping agent of embodiment 1, wherein said at least one fluoroolefins comprises at least one butylene with 3 to 5 fluoro substituents.

6. the whipping agent of embodiment 1, wherein said at least one fluoroolefins is the compound of formula II:

Wherein each R is Cl, F, Br, I or H independently,

R ' is (CR ₂) _ny,

Y is CRF ₂

And n is 0 or 1.

7. the whipping agent of embodiment 6, wherein Y is CF ₃.

8. the whipping agent of embodiment 6, wherein at least one R on unsaturated ends carbon is not F.

9. the whipping agent of embodiment 6, wherein at least one R on unsaturated ends carbon is H.

10. the whipping agent of embodiment 1, it has not the global warming potential (GWP) higher than approximately 150.

The whipping agent of 11. embodiments 1, it has not the ozone depletion potential (ODP) higher than approximately 0.05.

The whipping agent of 12. embodiments 1, wherein said fluoroolefins comprises and has the substituent unsaturated ends carbon of a no more than F.

The whipping agent of 13. embodiments 1, wherein said fluoroolefins comprises unsaturated ends carbon and at least one substituting group on unsaturated ends carbon is H.

The whipping agent of 14. embodiments 1, the compound of wherein said formula I is not containing Br.

The whipping agent of 15. embodiments 1, wherein said compound comprises at least one chlorine substituent.

The whipping agent of 16. embodiments 15, wherein said compound comprises HFCO-1233.

The whipping agent of 17. embodiments 15, wherein said HFCO-1233 comprises HFCO-1233xf.

The whipping agent of 18. embodiments 15, wherein said HFCO-1233 comprises HFCO-1233zd.

The whipping agent of 19. embodiments 1, the amount of the compound of wherein said at least one formula I in composition is approximately 5% to approximately 95% of whipping agent by weight.

The whipping agent of 20. embodiments 1, wherein said auxiliary comprises the co-foaming agent that at least one is other.

The whipping agent of 21. embodiments 20, wherein said at least one other co-foaming agent comprises one or more C1-C4HFC.

The whipping agent of 22. embodiments 21, wherein said one or more HFC are selected from two or more combination of methylene fluoride (HFC-32), fluoroethane (HFC-161), C2H4F2 C2H4F2 (HFC-152), Halothane (HFC-143), Tetrafluoroethane (HFC-134), pentafluoride ethane (HFC-125), pentafluoropropane (HFC-245), HFC-236fa (HFC-236), heptafluoro-propane (HFC-227ea), 3-pentafluorobutane (HFC-365), hexafluoro butane (HFC-356), all isomer of all these and these.

The whipping agent of 23. embodiments 20, wherein said at least one other co-foaming agent comprises one or more C4-C6 hydrocarbon.

The whipping agent of 24. embodiments 23, wherein said one or more hydrocarbon are selected from iso-pentane, Skellysolve A, pentamethylene, butane and Trimethylmethane, and these two or more combination.

25. 1 kinds of foamable composites that comprise formation of foam agent and whipping agent, described whipping agent comprises the fluoroolefins of at least one formula I:

XCF _zR _3-z(I)

Wherein X is C ₁, C ₂, C ₃, C ₄or C ₅undersaturated, substituted group, each R is Cl, F, Br, I or H independently, and z is 1 to 3; With at least one fluorinated ether.

The foamable composite of 26. embodiments 25, wherein said formation of foam agent comprises at least one thermosetting foams composition.

The foamable composite of 27. embodiments 26, wherein said at least one thermoset composition comprises the composition that can form polyurethane foam.

The foamable composite of 28. embodiments 26, wherein said at least one thermoset composition comprises the composition that can form polyisocyanurate foam.

The foamable composite of 29. embodiments 26, wherein said at least one thermoset composition comprises the composition that can form phenolic foams.

The foamable composite of 30. embodiments 25, wherein said formation of foam agent comprises at least one thermoplastic foam composition.

The foamable composite of 31. embodiments 30, wherein said at least one thermoplastic foam composition comprises thermoplastic polymer.

The foamable composite of 32. embodiments 30, wherein said at least one thermoplasticity composition comprises polyolefine.

The foamable composite of 33. embodiments 32, wherein said polyolefine is selected from monovinyl aromatic compounds, the compound based on ethene, the polymkeric substance based on propylene and these combination.

34. 1 kinds of foam premix compositions, it comprises polyol and whipping agent, and described whipping agent comprises the fluoroolefins of at least one formula I:

XCF _zR _3-z(I)

35. 1 kinds of methods that form foam, it comprise to can foam and/or foaming composition in add whipping agent, described whipping agent comprises the fluoroolefins of at least one formula I:

XCF _zR _3-z (I)

36. 1 kinds of foams, it comprises a plurality of polymkeric substance hole and is included in the composition in hole described at least one, described composition comprises: (a) at least one whipping agent, described whipping agent comprises the fluoroolefins of at least one formula I:

XCF _zR _3-z (I)

The foam of 37. embodiments 36, its form is one or more in blocks, blob of viscose, laminating material, rigid foam, open celled foam, closed-cell foam, flexible foam, integral skin foam, refrigerator foam and refrigerator foam.

The foam of 38. embodiments 36, it has not the K-factor (the BTU in/hr ft higher than approximately 0.14 in the time of 40 °F ²°F).

The foam of 39. embodiments 36, it has not the K-factor (the BTU in/hr ft higher than approximately 0.16 in the time of 75 °F ²°F).

The foam of 40. embodiments 36, it has the compressive strength at least about 12.5% yield rate in parallel direction.

The foam of 41. embodiments 36, it has the compressive strength at least about 12.5% yield rate in vertical direction.

The whipping agent of 42. embodiments 1, wherein said auxiliary comprises at least one co-foaming agent, described co-foaming agent is selected from water, CO ₂, CFC, HCC, HCFC, C1-C5 alcohol, C1-C4 aldehyde, C1-C4 ketone, C1-C4 ether and these two or more combination.

The foamable composite of 43. embodiments 25, wherein said formation of foam agent is thermoplastic, and described whipping agent further comprises the compound that is selected from C1-C5 alcohol.

The foamable composite of 44. embodiments 25, wherein said formation of foam agent is thermoplastic, and described whipping agent further comprises ethanol.

The foamable composite of 45. embodiments 25, wherein said formation of foam agent is thermoplastic, and described whipping agent further comprises the compound that is selected from dme, diethyl ether and these combination.

The foamable composite of 46. embodiments 25, wherein said formation of foam agent is heat cured, and described whipping agent further comprises methyl-formiate.

The whipping agent of 47. embodiments 1, the compound of wherein said formula I has at least four (4) individual halogenic substituents.

The whipping agent of 48. embodiments 47, wherein said at least four (4) individual halogenic substituents comprise at least three F substituting groups.

The whipping agent of 49. embodiments 1, wherein said fluorinated ether comprises at least one hydrofluorination ether.

The whipping agent of 50. embodiments 1, wherein said fluorinated ether comprises at least one C3 to C5 hydrofluorination ether.

The whipping agent of 51. embodiments 1, wherein said fluorinated ether is according to the fluorinated ether of following formula (III):

C _aH _bF _c-O-C _dH _eF _f (III)

Wherein

a＝1-6，

b＝1-12，

c＝1-12，

d＝1-2，

e＝0-5，

f＝0-5，

The whipping agent of 52. embodiments 1, wherein said fluorinated ether is selected from

CHF ₂oCH ₂f (HFE-143E), CH ₂fOCH ₂f (HFE-152E), CH ₂fOCH ₃(HFE-161E), ring-CF ₂cH ₂oCF ₂o (HFE-c234fE α β), ring-CF ₂cF ₂cH ₂o (HFE-c234fE β Y), CHF ₂oCF ₂cHF ₂(HFE-236caE), CF ₃cF ₂oCH ₂f (HFE-236cbE β Y), CF ₃oCHFCHF ₂(HFE-236eaE α β), CHF ₂oCHFCF ₃(HFE-236eaE β Y), CHF ₂oCF ₂cH ₂f (HFE-245caE α β), CH ₂fOCF ₂cHF ₂(HFE-245caE β Y), CF ₃oCF ₂cH ₃(HFE-245cbE β Y), CHF ₂cHFOCHF ₂(HFE-245eaE), CF ₃oCHFCH ₂f (HFE-245ebE α β), CF ₃cHFOCH ₂f (HFE-245ebE β Y), CF ₃oCH ₂cF ₂h (HFE-245faE α β), CHF ₂oCH ₂cF ₃(HFE-245faE β Y), CH ₂fCF ₂oCH ₂f (HFE-254caE), CHF ₂oCF ₂cH ₃(HFE-254cbE α β), CHF ₂cF ₂oCH ₃(HFE-254caE β Y), CH ₂fOCHFCH ₂f (HFE-254eaE α β), CF ₃oCHFCH ₃(HFE-254ebE α β), CF ₃cHFOCH ₃(HFE-254ebE β Y), CHF ₂oCH ₂cHF ₂(HFE-254faE), CF ₃oCH ₂cH ₂f (HFE-254fbE α β), CF ₃cH ₂oCH ₂f (HFE-254fbE β Y), CH ₃oCF ₂cH ₂f (HFE-263caE β Y), CF ₃cH ₂oCH ₃(HFE-263fbE β Y), CH ₃oCH ₂cHF ₂(HFE-272fbE β Y), CHF ₂oCHFCF ₂cF ₃(HFE-338mceEY δ), CHF ₂oCF ₂cHFCF ₃(HFE-338mceEY δ), CF ₃cF ₂oCH ₂cF ₃(HFE-338mfE β Y), (CF ₃) ₂cHOCHF ₂(HFE-338mmzE β Y), CF ₃cF ₂cF ₂oCH ₃(HFE-347sEY δ), CHF ₂oCH ₂cF ₂cF ₃(HFE-347mfcEY δ), CF ₃oCH ₂cF ₂cHF ₂(HFE-347mfcE α β), CH ₃oCF ₂cHFCF ₃(HFE-356mecEY δ), CH ₃oCH (CF ₃) ₂(HFE-356mmzE β Y), CF ₃cF ₂oCH ₂cH ₃(HFE-365mcE β Y), CF ₃cF ₂cH ₂oCH ₃(HFE-365mcEY δ), CF ₃cF ₂cF ₂oCHFCF ₃(HFE-42-11meEY δ), CF ₃cFCF ₃cF ₂oCH ₃, CF ₃cF ₂cF ₂cF ₂oCH ₃, CF ₃cFCF ₃cF ₂oCH ₂cH ₃, CF ₃cF ₂cF ₂cF ₂oCH ₂cH ₃, CF ₃cF ₂cF ₂oCH ₃, and this this any two or more combination.

Claims

1. a whipping agent, it comprises:

(a) fluoroolefins of at least one formula I:

XCF _zR _3-z(I)

(b) at least one fluorinated ether.

2. the composition of claim 1, it further comprises at least one auxiliary, and described auxiliary is selected from any two or more combination of other co-foaming agent, tensio-active agent, polymeric modifier, toughner, tinting material, dyestuff, solubilizing agent, rheology modifier, softening agent, flammable inhibitor, antiseptic-germicide, visbreaking properties-correcting agent, weighting material, vapour pressure properties-correcting agent, nucleator, catalyzer and these.

3. the whipping agent of claim 1, wherein said at least one fluoroolefins comprise have 3 to 5 fluoro substituents at least one three carbon and/(or) at least one four carbon olefin.

4. the whipping agent of claim 1, wherein said at least one fluoroolefins comprises cis HFO-1234ze, or trans HFO-1234ze or these combination.

5. the whipping agent of claim 1, wherein said at least one fluoroolefins comprises at least one butylene with 3 to 5 fluoro substituents.

6. the whipping agent of claim 1, wherein said at least one fluoroolefins is the compound of formula II:

Wherein each R is Cl, F, Br, I or H independently,

R ' is (CR ₂) _ny,

Y is CRF ₂

And n is 0 or 1.

7. the whipping agent of claim 6, wherein Y is CF ₃.

8. the whipping agent of claim 6, wherein at least one R on unsaturated ends carbon is not F.

9. the whipping agent of claim 6, wherein at least one R on unsaturated ends carbon is H.

10. the whipping agent of claim 1, it has not the global warming potential (GWP) higher than approximately 150.