CN101448913A - Compositions containing flourine substituted olefins - Google Patents

Abstract

The present invention provides 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

Invention field

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

Background

Find, in many commercial and industrials are used, be commonly used, comprise as aerosol propellant (aerosol propellants) with as whipping agent based on the fluid of fluorohydrocarbon.Because some shady (suspected) environmental problem, comprise high relatively global warming potential (use that has been used composition so far with some in these are used is relevant), use has fluid low even zero ozone depletion potential (ozone depletion potential) and has become and more and more cater to the need, hydrogen fluorohydrocarbon (hydrofluorocarbons, " HFC ") for example.Therefore, it is desirable using the fluid that does not contain a large amount of Chlorofluorocarbons (CFCs) (＂ CFC ＂) or Hydrochlorofluorocarbons (hydrochlorofluorocarbons, ＂ HCFC ＂).And some HFC fluid may have relative high relatively global warming potential, has hydrogen fluorohydrocarbon or other fluorinated fluids of alap global warming potential and use, keep simultaneously and use the performance of wanting in the character, and be desirable.As indicated in above, recent years, more and more about the potential destructive of earth atmosphere and weather is paid close attention to, in this, it is the problem especially severe that some chlorine-containing compound has been determined.The use of chlorine-containing component (for example Chlorofluorocarbons (CFCs) (CFC), Hydrochlorofluorocarbons (HCF) or the like) in many application become and has not been popular, because many such compounds have ozone-depleting character.So, more and more need new fluorohydrocarbon and hydrogen fluorocarbon compound and composition, as the attractive substitute that in these application and other application, is used composition so far.For example, by with non-chlorine-containing compound that can not depletion, for example hydrogen fluorohydrocarbon (HFC) replaces chlorine-containing compound, thereby having become caters to the need in (retrofit) the chloride system of improvement (for example foaming agent system or refrigeration system).Generally speaking, industrially just constantly seek new mixture based on fluorohydrocarbon, but its substitute CFC and HCFC, and be considered to safer CFC of environment and the substitute of HCFC.But, be considered in many cases importantly, any possible substitute must also have those and be present in 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 do not have combustibility, or the like.

In addition, it has been generally acknowledged that desirable is not need that the foam generating system of routine is done very big design and change the CFC whipping agent substitute that can play a role.

The method and composition that is used to make conventional foam materials (for example thermoplastic material and thermosetting material) is well known for a long time.These method and compositions use chemical foaming agent and/or pneumatogen to form foamy structure in polymeric matrix usually.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 usually, comprises and the material generation chemical reaction that forms polymeric matrix (carrying out under predetermined temperature/pressure usually) that this causes discharging gas, for example nitrogen, carbonic acid gas or carbon monoxide.One of the most frequently used chemical foaming agent is a water.Pneumatogen is dissolved in polymkeric substance or the polymer precursor material usually, and volumetric expansion subsequently (still carrying out under predetermined temperature/pressure) is to help to form foamy structure.Pneumatogen usually is used for thermoplastic foam, although chemical foaming agent also fungible things haircut infusion be used in or be used in thermoplastic foam with pneumatogen.For example, the known chemical foaming agent that when the foam that forms based on polyvinyl chloride, uses.Chemical foaming agent and/or pneumatogen generally are 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 generally is used as the standard whipping agent in the preparation of the foam (for example hard and flexible PU foam and polyisocyanurate foam) based on isocyanic ester.For example, CCl ₃F (CFC-11) has become the standard whipping agent.But the use of this material is forbidden by international treaties that meeting destroys the ozonosphere in the stratosphere because it is discharged into the atmosphere.Thereby, use pure CFC-11 no longer general as the standard whipping agent that is used to form the thermosetting foams foam and the phenolic foams of isocyanic ester (for example based on).

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

The whipping agent of another kind of known kind is non-chlorating, partially hydrogenated fluorohydrocarbon (being called as " HFC ").Current some HFC that just is being used as whipping agent has at least one potential serious problems, and promptly they have high relatively inherence (intrinsic) thermal conductivity (promptly poor heat insulating ability) usually.On the other hand, with some more recently HFC whipping agent (CF for example ₃CH ₂CF ₂H (＂ HFC-245fa ＂)) foam of Zhi Zaoing, partly because the low heat conductivity of HFC-245fa steam, and partly because HFC-245fa gives the meticulous cell structure of foamy (cell structure), thereby the heat insulating ability of improvement is provided.HFC-245fa in thermal insulation is used, particularly in refrigerator, refrigerator, refrigerator/refrigerator and spraying foam (spray foam) are used, is widely used.Yet many HFC fluids all have the shortcoming of the high relatively global warming potential of tool, and desirable is that use has hydrogen fluorohydrocarbon or other fluorizated fluids of alap global warming potential, keeps the performance of using in the character of wanting 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 the foam insulation body, particularly in the rigid foam thermal insulator as the use of whipping agent, cause HFC to become more unfavorable whipping agent in the commercial foam thermal insulator.

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

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

In many application, another so potential critical nature is flammable.That is, in many application,, use low combustible or nonflammable composition to be considered to important or necessary (essential) particularly including in whipping agent is used.As used herein, term " nonflammable " is meant that measuring (merging to by reference in this literary composition) according to ASTM standard E-681 in 2002 is confirmed as nonflammable compound or composition.Unfortunately, many HFC may be desirable in the 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) all are respectively inflammable, therefore cannot be used for many application.

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

In No. the 5th, 900,185, the United States Patent (USP) of authorizing Tapscott, advised using bromated halocarbon additive to reduce some material combustibility of (comprising foam foaming agent).It is said that the characteristics of the additive in this patent are efficient and short atmospheric lifetimes, that is, low-ozone consumes potential (ODP) and low global warming potential (GWP).

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

Though Tapscott points out the brominated alkene with 2 to 6 carbon atoms and also may contain fluoro substituents, but this patent propose " since with the reaction 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 is not to cater to the need fully.

And, be considered to desirable usually and be, in the whipping agent substitute that does not need the conventional equipment that is used for foam preparation and formation and system done can play a role under the situation that very big design changes.

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

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

General introduction

The applicant finds, above-mentioned needs and other need, can satisfy 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 have 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 be Cl, F, Br, I or H independently, and z is 1 to 3, and common preferred fluoroolefins of the present invention has at least four (4) individual halogenic substituents, and at least wherein three is F, and more preferably none is Br.

For there being the substituent embodiment of at least one Br, preferred compound is not hydrogeneous.In such embodiment, also preferred usually Br substituting group is positioned on the unsaturated carbon, and also more preferably the Br substituting group is positioned on the 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, none R is Br, and preferably, unsaturated group does not contain the 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 ₂(HFO-1233xf) and CF ₃CH=CHCl (HFO-1233zd)).

In some embodiments, preferred five fluorine propylene have substituent five fluorine propylene, for example CF of hydrogen on the 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, the fluorine chlorobutylene is particularly preferred in some embodiments.

The term of Shi Yonging " HFO-1234 " is meant all tetrafluoeopropenes herein.These tetrafluoeopropenes comprise 1,1,1,2-tetrafluoeopropene (HFO-1234yf) and cis-and anti-form-1,1,1,3-tetrafluoeopropene (HFO-1234ze).The term HFO-1234ze of Shi Yonging is often referred to 1,1,1 herein, and the 3-tetrafluoeopropene is no matter and whether it is cis form or trans forms.Herein the term of Shi Yonging " cis HFO-1234ze " and " trans HFO-1234ze " the 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 in its scope.

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

The term of Shi Yonging " HFO-1225 " is meant five all fluorine propylene herein.Such molecule comprises 1,1,1,2,3 five fluorine propylene (HFO-1225yez), and cis form and trans forms.Therefore the term " HFO-1225yez " that herein uses typically refers to 1,1,1,2, and 3 five fluorine propylene are 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 in its scope.

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 that uses 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 one of them described C _aCan be bonded to a described C _dTo form the ring fluoroether.

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

Detailed description of the preferred embodiment

Composition

Composition of the present invention can be foaming agent composotion form or foamable composite form usually.In each case, the present invention needs the described fluoroolefin compounds of at least a literary composition like this, and randomly needs other compositions, and some other composition will be described in detail following.

A. fluoroolefins

Preferred implementation of the present invention relates to and comprises at least a 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 3 carbon atoms in some embodiments, 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, then 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, this moment, such compound was not thought preferably.For the HFO that also contains at least one chlorine atom, use title HFCO sometimes in this literary composition.

As mentioned above, composition of the present invention comprises one or more compounds according to formula I.In 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, preferred 0 or 1, but usually preferred Br is not present in the compound, perhaps when Br is present in the compound, does not have hydrogen in the compound.

In highly preferred embodiment, Y is CF ₃, n is that the remaining R of 0 or 1 (most preferably being 0) and at least one is F, and preferred none R is Br, perhaps when having Br, does not have hydrogen in the compound.In some cases, none R is Br among the preferred formula II.

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

Some preferred embodiment in, compound of the present invention comprises C ₃Or C ₄HFO or HFCO, preferred 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, preferred in some embodiments following C ₃The alkenes 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 ₃CF ₃-CF=CH-CH ₃CF ₃-CH ₂-CF=CH ₂CF ₃-CH ₂-CH=CFH; With these each other combination and/or these and according to other combination of compounds of formula I or formula II.

Some preferred embodiment in, compound of the present invention comprises C3 or C4 HFCO, is preferably C3 HFCO, 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 promptly 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, usually preferred HFO-1234ze, very preferably trans in some embodiments HFO-1234ze.Though (cis) HFO-1234ze is different at least in some aspects with the character of (trans) HFO-1234ze, expects that in these compounds every kind all is fit to separately or be used from every kind of application describing herein, the method and system with other compounds one that comprise its steric isomer.For example, (trans) HFO-1234ze is because its low relatively boiling point (19 ℃) and may being preferred in some system, and (cis) HFO-1234ze has+9 ℃ boiling point may be preferred in other are used.Certainly, in many embodiments, the combination of cis and trans-isomer(ide) is acceptable and/or preferred probably.Therefore, it being understood that term " HFO-1234ze " and 1,3,3, the 3-tetrafluoeopropene is meant two kinds of steric isomers, and except as otherwise noted, uses this term to be intended to illustrate that cis form and trans forms all are suitable for, and/or can be used for described purpose.

The 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 is fluoridized and is produced 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, 465, describe in No. 786, by reference they are merged so far in the literary composition.EP 974,571 (also being incorporated by reference into this literary composition) have disclosed passes through 1,1,1,3,3-pentafluoropropane (HFC-245fa) at high temperature contacts with catalyzer based on chromium in gas phase, perhaps pass through with 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, the 3-tetrafluoeopropene.In addition, production method according to compound of the present invention is called in name in the U.S. Patent application co-pending of " Processfor Producing Fluorpropenes the method for fluoropropenes (produce) ", lawyer's file number (H0003789 (26267)) synoptically to be described, and also by reference it is merged so far in the 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 general range of the present invention (broad scope) or any two or more combination of compounds 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 many major reason favorable properties.For example, to small part based on mathematical modeling, the applicant thinks that fluoroolefins of the present invention will can not produce substantial negative impact to atmospheric chemistry, compares with some other halogenation materials, its effect to ozone-depleting can be ignored.Therefore preferred composition of the present invention does not have and can have the advantage of substantive contribution to ozone-depleting.Compare with many hydro fluoroalkaness (hydrofluoroalkanes) of present use, preferred compositions can not have substantial contribution to Global warming yet.

In some preferred form, composition of the present invention have be not higher than about 1000, more preferably no higher than about 500, also more preferably no higher than about 150 global warming potential (GWP).In some embodiments, it is about 100 that the GWP of the present composition is not higher than, and more preferably, is not higher than about 75.As used herein, as (being incorporated by reference in this literary composition) that in " The Scientific Assessment of OzoneDepletion; 2002; a report of the World Meteorological Association ' sGlobal Ozone Research and Monitoring Project (the science assessment of ozone-depleting; 2002; the global ozone research of world's meteorology association and the report of Supervisory Surveillance Program) ", describes in detail, " 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 and is not higher than approximately 0.05, more preferably no higher than about 0.02, also is more preferably zero ozone depletion potential (ODP).As used herein, " ODP " is as describing in detail in " The Scientific Assessment of OzoneDepletion; 2002; a report of the World Meteorological Association ' sGlobal Ozone Research and Monitoring Project (science of ozone-depleting assessment; 2002; the global ozone research of world's meteorology association and the report of Supervisory Surveillance Program) ", by reference it merged so far in the literary composition.

The formula I compound that contains in the present invention combination (HFO-1234 particularly, and HFO-1234ze more preferably) amount can great changes have taken place, determined specific application, and the compound compositions with being less than 100% that contains more than trace all belongs to general range of the present invention.And the present composition can be azeotropic, class azeotropic (azeotrope-like) or non-azeotropic.In 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 about 1% to about 99% by weight, more preferably being about 5% to about 95% by weight, also more preferably is 40% to about 90% by weight.

A. fluoroether

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

The applicant thinks, and is particularly normally effective according to the fluoroether of above definite formula (III) according to the fluoroether of the disclosure of invention according to the instruction that is included in this literary composition usually, and reveals practicality with the fluoroolefin compounds associative list.But, the applicant finds, preferably in some embodiments, particularly relate in the embodiment of foaming agent composotion and foam and foaming method, use fluoroether, preferably in fluoroether utilize difluorizated at least, more preferably trifluorinated at least, more preferably tetrafluorizated at least hydrogen fluoroether also.Particularly preferably be in some embodiments have 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 that contains in the 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 the compound compositions with being less than 100% that contains more than trace all belongs to general range of the present invention.In preferred embodiment, the present composition, particularly foaming agent composotion, comprise the formula III compound, comprise preferred compound colony, content is about 1% to about 99% by weight, more preferably being about 5% to about 95% by weight, also more preferably is 40% to about 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 γ)

CHF ₂OCF ₂CHF ₂(HFE-236caE)

CF ₃CF ₂OCH ₂F(HFE-236cbEβγ)

CF ₃OCHFCHF ₂(HFE-236eaEaβ)

CHF ₂OCHFCF ₃(HFE-236eaEβγ)

CHF ₂OCF ₂CH ₂F(HFE-245caEaβ)

CH ₂FOCF ₂CHF ₂(HFE-245caEβγ)

CF ₃OCF ₂CH ₃(HFE-245cbEβγ)

CHF ₂CHFOCHF ₂(HFE-245eaE)

CF ₃OCHFCH ₂F(HFE-245ebEaβ)

CF ₃CHFOCH ₂F(HFE-245ebEβγ)

CF ₃OCH ₂CF ₂H(HFE-245faEaβ)

CHF ₂OCH ₂CF ₃(HFE-245faEβγ)

CH ₂FCF ₂OCH ₂F(HFE-254caE)

CHF ₂OCF ₂CH ₃(HFE-254cbEαβ)

CHF ₂CF ₂OCH ₃(HFE-254caEβγ)

CH ₂FOCHFCH ₂F(HFE-254eaEαβ)

CF ₃OCHFCH ₃(HFE-254ebEαβ)

CF ₃CHFOCH ₃(HFE-254ebEβγ)

CHF ₂OCH ₂CHF ₂(HFE-254faE)

CF ₃OCH ₂CH ₂F(HFE-254fbEαβ)

CF ₃CH ₂OCH ₂F(HFE-254fbEβγ)

CH ₃OCF ₂CH ₂F(HFE-263caEβγ)

CF ₃CH ₂OCH ₃(HFE-263fbEβγ)

CH ₃OCH ₂CHF ₂(HFE-272fbEβγ)

CHF ₂OCHFCF ₂CF ₃(HFE-338mceEγδ)

CHF ₂OCF ₂CHFCF ₃(HFE-338mceEγδ)_

CF ₃CF ₂OCH ₂CF ₃(HFE-338mfEβγ)

(CF ₃) ₂CHOCHF ₂(HFE-338mmzEβγ)

CF ₃CF ₂CF ₂OCH ₃(HFE-347sEγδ)

CHF ₂OCH ₂CF ₂CF ₃(HFE-347mfcEγδ)

CF ₃OCH ₂CF ₂CHF ₂(HFE-347mfcEaβ)

CH ₃OCF ₂CHFCF ₃(HFE-356mecEγδ)

CH ₃OCH(CF ₃) ₂(HFE-356mmzEβγ)

CF ₃CF ₂OCH ₂CH ₃(HFE-365mcEβγ)

CF ₃CF ₂CH ₂OCH ₃(HFE-365mcEγδ)

CF ₃CF ₂CF ₂OCHFCF ₃(HFE-42-11meEγδ)

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

Also expection, any or multiple HFE listed above also can be used in combination with other compounds, comprises that other form other compound of azeotropic mixture the HFE that clearly lists and/or known and specified (designated) fluoroether in this literary composition.For example, known following every kind of compound forms azeotropic mixture with trans-dichloroethylene, and expection, is purpose 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 chosen wantonly, but preferably, they are included in the foaming agent composotion of the present invention.Optional added compound like this comprises, but be not limited to, other are also as whipping agent (following for easy but be not to be called co-foaming agent (co-blowing agent) for restriction), tensio-active agent, polymer modifiers, toughner, tinting material, dyestuff, solubilizing agent, rheology modifier, softening agent, flammable inhibitor (flammabilitysuppressants), 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 the foaming agent composotion of the present invention.Some tensio-active agent is chosen wantonly, but preferably is added into as the hole stablizer.Some representational materials are sold with commodity DC-193, B-8404 by name and L-5340, usually 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 that discloses in 846, No. 458 merges them so far in the literary composition by reference.Other optional additives that are used 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, various halogenated aromatic substance, weisspiessglanz, aluminum trihydrate (aluminum trihydrate), polyvinyl chloride, or the like.

For nucleator, all known compound and materials with kernel function all can be used among the present invention, particularly including talcum.

Certainly, other compound and/or compositions of regulating the special properties (for example cost) of described composition also can be included in the composition of the present invention, and the compound that all are such and the existence of composition belong 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.Can comprise pneumatogen, chemical foaming agent (preferred package is moisture in some embodiments) or have pneumatogen character and the whipping agent of chemical foaming agent properties of combination according to co-foaming agent of the present invention.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 that those 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.

Though 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 the HFC that all are such.About hydrocarbon, in some preferred implementation, foaming agent composotion of the present invention can comprise, for example, is used for iso-pentane, Skellysolve A and/or the pentamethylene of thermosetting foams and is used for the butane or the Trimethylmethane of thermoplastic foam.Certainly, also can comprise other materials, for example water, CO ₂CFC (for example trichlorofluoromethane (CFC-11) and Refrigerant 12 (CFC-12)), hydrogen chlorocarbon (hydrochlorocarbons) (HCC, Ethylene Dichloride (preferred 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 of these material, 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 the composition of the present invention:

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

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

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

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

1,1,1,2,3,3,3-heptafluoro-propane (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 very big change according to the application-specific of composition, and all such relative quantities all are considered to belong to scope of the present invention.But the applicant notices that a special advantage of some compound according to formula I of the present invention (for example HFO-1234ze) is that such compound has relatively low combustibility at least.Therefore, in some embodiments, preferably, foaming agent composotion of the present invention comprises at least a co-foaming agent and a certain amount of compound according to formula I, is enough to produce nonflammable generally foaming agent composotion.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, usually preferably, for the preferred composition that is used as 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 made up of compound according to the present invention substantially.In this, be noted that the use of one or more co-foaming agents is with novelty of the present invention consistent with basic characteristics.For example, be expected in many embodiments, water will be used as co-foaming agent or be used in combination with other co-foaming agents (for example 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, wrap aqueous co-foaming agent and be included in the composition, most preferably be included in the composition that is used for thermosetting foams.Some preferred embodiment in, foaming agent composotion of the present invention comprises the combination of cis HFO-1234ze and trans HFO-1234ze, wherein cis: trans weight ratio for about 1:99 to about 50:50, more preferably about 10:90 is about 30:70 extremely.In some embodiments, may preferably use the combination of cis HFO-1234ze and trans HFO-1234ze, wherein cis: trans weight ratio is extremely about 10:90 of about 1:99, and is preferably about 1:99 to about 5:95.Certainly, in some embodiments, use wherein that cis-isomeride may be desirable with the combination that exists than trans-isomer(ide) greater concn, for example, be used for being fit to the foamable composite that uses with liquid blowing agent.

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

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

Table A

HFO	HFE	HFO% scope 1	HFE% scope 1	HFO% scope 2	HFE% scope 2
						1234ze	CHF 2OCH 2F(HFE-143E)	5-99	1-95	30-99	1-70
1234ze	CH 2FOCH 2F(HFE-152E)	5-99	1-95	30-99	1-70
						1234ze	CH 2FOCH 3(HFE-161E)	5-99	1-95	30-99	1-70
1234ze	Ring-CF 2CH 2OCF 2O(HFE-c234fEαβ)	5-99	1-95	30-99	1-70
						1234ze	Ring-CF 2CF 2CH 2O(HFE-c234fEβγ)	5-99	1-95	30-99	1-70
1234ze	CHF 2OCF 2CHF 2(HFE-236caE)	5-99	1-95	30-99	1-70
						1234ze	CF 3CF 2OCH 2F(HFE-236cbEβγ)	5-99	1-95	30-99	1-70
1234Ze	CF 3OCHFCHF 2(HFE-236eaEαβ)	5-99	1-95	30-99	1-70
						1234ze	CHF 2OCHFCF 3(HFE-236eaEβγ)	5-99	1-95	30-99	1-70
1234ze	CHF 2OCF 2CH 2F(HFE-245caEαβ)	5-99	1-95	30-99	1-70
						1234ze	CH 2FOCF 2CHF 2(HFE-245caEβγ)	5-99	1-95	30-99	1-70
1234ze	CF 3OCF 2CH 3(HFE-245cbEβγ)	5-99	1-95	30-99	1-70
						1234ze	CHF 2CHFOCHF 2(HFE-245eaE)	5-99	1-95	30-99	1-70
1234ze	CF 3OCHFCH 2F(HFE-245ebEαβ)	5-99	1-95	30-99	1-70

HFO	HFE	HFO% scope 1	HFE% scope 1	HFO% scope 2	HFE% scope 2
						1234ze	CF 3CHFOCH 2F(HFE-245ebEβγ)	5-99	1-95	30-99	1-70
1234ze	CF3OCH 2CF 2H(HFE-245faEαβ)	5-99	1-95	30-99	1-70
						1234ze	CHF 2OCH 2CF 3(HFE-245faEβγ)	5-99	1-95	30-99	1-70
1234ze	CH 2FCF 2OCH 2F(HFE-254caE)	5-99	1-95	30-99	1-70
						1234ze	CHF 2OCF 2CH 3(HFE-254cbEαβ)	5-99	1-95	30-99	1-70
1234ze	CHF 2CF 2OCH 3(HFE-254caEβγ)	5-99	1-95	30-99	1-70
						1234ze	CH 2FOCHFCH 2F(HFE-254eaEαβ)	5-99	1-95	30-99	1-70
1234ze	CF 3OCHFCH 3(HFE-254ebEαβ)	5-99	1-95	30-99	1-70
						1234ze	CF 3CHFOCH 3(HFE-254ebEβγ)	5-99	1-95	30-99	1-70
1234ze	CHF 2OCH 2CHF 2(HFE-254faE)	5-99	1-95	30-99	1-70
						1234ze	CF 3OCH 2CH 2F(HFE-254fbEαβ)	5-99	1-95	30-99	1-70
1234ze	CF 3CH 2OCH 2F(HFE-254fbEβγ)	5-99	1-95	30-99	1-70
						1234ze	CH 3OCF 2CH 2F(HFE-263caEβγ)	5-99	1-95	30-99	1-70
1234ze	CF 3CH 2OCH 3(HFE-263fbEβγ)	5-99	1-95	30-99	1-70

HFO	HFE	HFO% scope 1	HFE% scope 1	HFO% scope 2	HFE% scope 2
						1234ze	CH 3OCH 2CHF 2(HFE-272fbEβγ)	5-99	1-95	30-99	1-70
1234ze	CHF 2OCHFCF 2CF 3(HFE-338mceEγδ)	5-99	1-95	30-99	1-70
						1234ze	CHF 2OCF 2CHFCF 3(HFE-338mceEγδ)_	5-99	1-95	30-99	1-70
1234ze	CF 3CF 2OCH 2CF 3(HFE-338mfEβγ)	5-99	1-95	30-99	1-70
						1234ze	(CF 3) 2CHOCHF 2(HFE-338mmzEβγ)	5-99	1-95	30-99	1-70
1234ze	CF 3CF 2CF 2OCH 3(HFE-347sEγδ)	5-99	1-95	30-99	1-70
						1234ze	CHF 2OCH 2CF 2CF 3(HFE-347mfcEγδ)	5-99	1-95	30-99	1-70
1234ze	CF 3OCH 2CF 2CHF 2(HFE-347mfcEαβ)	5-99	1-95	30-99	1-70
						1234ze	CH 3OCF 2CHFCF 3(HFE-356mecEγδ)	5-99	1-95	30-99	1-70
1234ze	CH 3OCH(CF 3) 2(HFE-356mmzEβγ)	5-99	1-95	30-99	1-70
						1234ze	CF 3CF 2OCH 2CH 3(HFE-365mcEβγ)	5-99	1-95	30-99	1-70
1234ze	CF 3CF 2CF 2OCHFCF 3(HFE-42-11meEγδ)	5-99	1-95	30-99	1-70
						1234ze	CF 3CFCF 3CF 2OCH 3	5-99	1-95	30-99	1-70
1234ze	CF 3CF 2CF 2CF 2OCH 3	5-99	1-95	30-99	1-70
						1234ze	CF 3CFCF 3CF 2OCH 2CH 3	5-99	1-95	30-99	1-70
1234ze	CF 3CF 2CF 2CF 2OCH 2CH 3	5-99	1-95	30-99	1-70

HFO	HFE	HFO% scope 1	HFE% scope 1	HFO% scope 2	HFE% scope 2
						1234ze	CF 3CF 2CF 2OCH 3.	5-99	1-95	30-99	1-70

Contain H at co-foaming agent ₂In the preferred implementation of O, composition comprises H ₂The amount of O account for by weight total foaming agent composotion about 5% to about 50%, more preferably account for about 10% by weight to about 40%, also more preferably account for about 10% to about 20% of total whipping agent by weight.

Contain CO at co-foaming agent ₂Preferred implementation in, composition comprises CO ₂Amount account for by weight total foaming agent composotion about 5% to about 60%, more preferably account for about 20% by weight to about 50%, also more preferably account for about 40% to about 50% of total whipping agent by weight.

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

For the composition that contains the HFC co-foaming agent, HFC co-foaming agent (preferred C2, C3, C4 and/or C5 HFC), 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 about 5% to about 80% of total foaming agent composotion by weight, more preferably be about 10% to about 75% by weight, also more preferably account for about 25% to about 75% of total whipping agent by weight.And in such embodiment, HFC is preferably C2-C4 HFC, C3 HFC more preferably, very preferably pentafluorated in some embodiments C3 HFC, for example HFC-245fa.

For the composition that contains the HFE co-foaming agent, HFE co-foaming agent (preferred C2, C3, C4 and/or C5 HFE), more preferably the amount of HFE-254 (particularly including HFE-254pc) in composition preferably accounts for about 5% to about 80% of total foaming agent composotion by weight, more preferably be about 10% to about 75% by weight, also more preferably account for about 25% to about 75% of total whipping agent by weight.And in such embodiment, HFE is preferably C2-C4 HFE, C3 HFE more preferably, very preferably tetrafluorizated in some embodiments C3 HFE.

For the composition that contains the HC co-foaming agent, the amount of HC co-foaming agent (preferred C3, C4 and/or C5 HC) in composition preferably account for by weight total foaming agent composotion about 5% to about 80%, more preferably account for about 20% to about 60% of total whipping agent by weight.

C. other composition-foamable composites

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

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

Expecting that all are at present known and available, be used to form the foamy method and system all is easy to be applicable to the present invention.For example, method of the present invention need add according to whipping agent of the present invention in foamable composite or foam formation composition usually, preferably make described composition foaming by a step or series of steps subsequently, described step comprises to be made according to whipping agent volumetric expansion of the present invention.Usually, system and device that expection is used at present is used to add whipping agent and foaming are 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 improved, it adapts with existing foaming method and system usually.

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 the conventional processing condition, and the conventional foaming machine of whipping agent of the present invention with for example polyurethane foam equipment is used in combination.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, preferable methods generally includes to thermoplastic material (preferred thermoplastic polymkeric substance, for example polyolefine) and introduces according to whipping agent of the present invention, makes thermoplastic material stand effectively to cause the condition that foams then.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 the step that causes foaming can comprise the pressure that is reduced on the thermoplastic material, thereby causes the expansion of whipping agent and facilitate the foaming of material.

Those skilled in the art when particularly considering content disclosed herein, will recognize that order and mode that whipping agent of the present invention forms and/or order and the mode that joins in the foamable composite do not influence operability of the present invention usually.For example, if extrudable foam, the various compositions of whipping agent, even the composition of foamable composite can be not mixed before being incorporated into extrusion equipment, perhaps in addition 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, and this premix is further joined other parts of foamable composite subsequently.

Therefore, in some embodiments, may desirablely be, introduce one or more compositions of whipping agent in first position of forcing machine, 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 is operated by this way more effective.Yet, in some embodiments, being pre-mixed two or more compositions of whipping agent and directly or as the part of premix being incorporated into together in the 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, this method generally includes provides foaming agent composotion of the present invention, foaming agent composotion (directly or indirectly) is joined in the foamable composite, under the condition that effectively forms foamy structure or vesicular structure, make the foamable composite reaction.Any well-known method in any this area, for example those are at " PolyurethanesChemistry and Technology (polyurethane chemistry and technology) " I and II volume, Saunders and Frisch, 1962, John Wiley and Sons, the method of describing among the New York, 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.Usually, such preferred method comprises by mixture, the whipping agent that mixes isocyanic ester, polyol or polyol or the blowing agent blends that comprises one or more present compositions and other materials (for example 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 constitute first kind of composition, are commonly called " A " composition.Polyol or polyol mixture, tensio-active agent, catalyzer, whipping agent, fire retardant and other isocyanate-reactive compositions (reactivecomponents) constitute second kind of composition, are commonly called " B " composition.Therefore, by manual mixing (when preparing on a small quantity), preferably, by machine mix set A composition and B composition, with (spray applied) foam of forming blocks (blocks), blob of viscose (slabs), laminating material, original position casting (pour-in-place) plate and other products, spray application, blister (froth) or the like, be easy to prepare urethane or polyisocyanurate foam.Randomly, 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 all are added in the 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 preferably is comprised in the foam formation agent by being dissolved in the foam formation agent, and it is liquid that described foam forms under the pressure of agent in container, and the whipping agent of another part exists with independent gas phase.In such system, involved/dissolved whipping agent mainly causes foamy to expand, and independent gas phase is given foam formation agent with propulsive force.Like this single becomes sub-system to be packaged in usually and preferably in the container of aerosol-type jar for example, therefore whipping agent of the present invention preferably provides the energy that is used for making foam expansion and/or is provided for but foam/foam material is transported from packing, and preferably possesses two kinds of effects simultaneously.In some embodiments, such system and method comprise to packing load (fully formulated) system (preferred isocyanate/polyol system) of preparing fully and in packing (preferred aerosol-type jar) adding according to gaseous foaming agent of the present invention.

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

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 all foams (including but not limited to closed-cell foam, open celled foam, rigid foam, flexible foam, integral skin foam (integeral skin) or the like) by foam of polymers prescription (formulation) preparation that contains the whipping agent that comprises the present composition.The applicant finds, foam (thermosetting foams particularly, for example according to polyurethane foam of the present invention) an advantage be, preferably in the thermosetting foams embodiment, can be issued to unusual superior thermal characteristics (thermal performance) at cold condition under cold condition particularly and preferably, described thermal characteristics for example can be measured by the K-factor or lambda factor.Though expect foam of the present invention, thermosetting foams particularly of the present invention, can be used in the 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 manufacturing application.

According to foam of the present invention, in some preferred implementation, except that the low-ozone relevant with the many preferred whipping agents of the present invention consumes potential and low global warming potential, one or more uncommon characteristics, characteristic and/or character also are 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 do not contain the foam that the identical whipping agent (or normally used blowing agent H FC-245fa) according to the compound of formula I of the present invention is made, it shows the thermal conductivity of improvement.In some highly preferred embodiment, thermosetting foams of the present invention, optimization polyurethane foam show when 40 ℉ and are not higher than about 0.14 the K-factor (BTUin/hr ft ²℉), 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 show when 75 ℉ and are not higher than about 0.16 the K-factor (BTU in/hr ft ²℉), more preferably no higher than 0.15, also more preferably no higher than 0.145.

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

Embodiment

Following examples are provided and are used for illustrating the present invention, are not to 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, whether can produce foam and foamy quality to determine specific whipping agent and polymkeric substance.The whipping agent that in container, mixes ground polymkeric substance (Dow Polystyrene 685D) and form by HFO-1234ze substantially.The sketch drafting of container is as follows.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 diameter.Container is placed on temperature and is arranged in the baking oven of about 190 ℉ to 285 ℉ (preferably for polystyrene, temperature is arranged on 265 ℉), and container is continued to be placed on that, up to reaching temperature equilibrium.

Discharge the pressure in the container subsequently, generate the polymkeric substance of foaming fast.Along with the whipping agent dissolving enters in the polymkeric substance the described polymkeric substance of its plasticising.Two kinds of foamy final densities utilizing present method to produce like this provide in table 1, are the foamy density of using trans HFO-1234ze and HFO-1234yf to produce.Data presentation can obtain polystyrene foam according to the present invention.In this respect, be noted that under about room temperature that 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 polystyrene foam that the independent conduct of HFO-1234ze is shaped in the double-screw type extruding machine.The instrument of Shi Yonging is the Leistritz twin screw extruder machine with following characteristic in this embodiment:

30mm corotation screw rod

L:D ratio=40:1

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

The Leistritz twin screw extruder machine

40mm corotation screw rod

L:D ratio=40:1

Mould (die): 5.0mm circle

Polystyrene resin, promptly the common extrusion grade polystyrene of Nova Chemical-is labeled as Nova 1600, is added in the extruding machine under the condition of above explanation.Resin has the recommendation temperature of fusion of 375 ℉ to 525 ℉.Extruding machine is about 1320 pounds (psi) per square inch at the pressure at mould place, and the temperature at the mould place is about 115 ℃.

The basic whipping agent of being made up of trans HFO-1234ze is added in the extruding machine in the position of above explanation, wherein comprise account for total whipping agent by weight about 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 foamy density of being produced is in the scope of every cubic centimetre of about 0.1 gram to every cubic centimetre 0.07 gram, and hole dimension is about 49 to about 68 microns.The about 30 millimeters foam of diameter seems to have good quality, very meticulous hole dimension, do not have visible or significantly pore or space.

Embodiment 1C-polystyrene foam

Repeat the program of embodiment 1B, just whipping agent comprises the nucleator of concentration described in the HFC-245fa of trans HFO-1234ze and 50% (by weight) of about 50% (by weight) and the embodiment 1B.The polystyrene of density of foaming agent preparation foaming with about 10% and 12%.The foamy density that is produced is every cubic centimetre of about 0.09 gram, and hole dimension is about 200 microns.The about 30 millimeters foam of diameter seems to have good quality, meticulous pore structure, do not have visible or tangible space.

Repeat the program of embodiment 1B, just whipping agent comprises the nucleator of concentration described in the HFC-245fa of HFO-1234ze and 20% (by weight) of about 80% (by weight) and the embodiment 1B.The polystyrene of density of foaming agent preparation foaming with about 10% and 12%.The foamy density that is produced is every cubic centimetre of about 0.08 gram, and hole dimension is about 120 microns.The about 30 millimeters foam of diameter seems to have good quality, meticulous pore structure, do not have visible or tangible space.

Embodiment 1E-polystyrene foam

Repeat the program of embodiment 1B, just whipping agent comprises the nucleator of concentration described in the HFC-245fa of HFO-124ze and 20% (by weight) of about 80% (by weight) and the embodiment 1B.The polystyrene of density of foaming agent preparation foaming with about 10% and 12%.Foamy density is the scope of 0.1 gram at every cubic centimetre.The about 30 millimeters foam of diameter seems to have good quality, meticulous pore structure, do not have visible or tangible space.

Embodiment 1F-polystyrene foam

Repeat the program of embodiment 1E, just omitted nucleator.Foamy density is the scope of 0.1 gram at every cubic centimetre, and the hole dimension diameter is about 400.The about 30 millimeters foam of diameter seems to have good quality, meticulous pore structure, do not have visible or tangible space.

Embodiment 2-polyurethane foam compressive strength

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

This embodiment provides commercially available, freezing apparatus type polyurethane foam formulation (foam formation agent).The polyol mixture is made up of commercial polyol, catalyzer and tensio-active agent.This prescription is fit to be used in combination with gaseous foaming agent.Normal business urethane treatment facility is used to the foam forming process.Form gaseous foaming agent mixture (combination), its HFO-1234ze (comprising its isomer) and concentration that comprises that concentration accounts for the about 60 moles of % of total whipping agent is the pentamethylene that accounts for the about 40 moles of % of total whipping agent.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 put down in writing, and compares the compressive strength of similar machine-made polyurethane foam (using whipping agent of the present invention) with using the foam of being made by HFC-245fa whipping agent of forming and the whipping agent of being made up of pentamethylene.

Table 2

The whipping agent compressive strength
	Parallel vertical
% yield rate % yield rate
	HFO1234ze/ pentamethylene 13.513 14.672
HFC-245fa 13.881 14.994
	Pentamethylene 11.462 10.559

A unexpected result of this embodiment explanation is particularly in the urethane treatment facility, to handle HFO-1234ze and HFC-1234ze/HFC mixture in the foam treatment facility of routine.This has the potential huge advantage, to such an extent as to can use various types of systems and equipment to handle foam, 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

The preparation polyurethane foam also makes it be suitable as commerce " applied " polyurethane formulations.In the foam forming process, the same foam prescription of describing among the embodiment 2 is used for identical normal business urethane treatment facility.Prepared several systems, each system uses 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, in the polyol mixture, add whipping agent with substantially the same volumetric molar concentration.Described polyol mixture is made up of commercial polyol, catalyzer and tensio-active agent.Commercial manufacturing operation process according to standard prepares foam, for example is used to prepare the foamy commercial operation process that is used for freeze applications.Estimate the prepared foamy K-factor, and this information is recorded in the following table 3.For determining benchmark and making comparisons, use HFC-134a to prepare foam, can consult the business data of HFC-134a.These foamy K-factor data is presented in the table 3.

Table 3

Medial temperature (℉) the K-factor (BTU in/hr ft 2℉)
	HFO-1234ze HFC-134a pentamethylene
40 0.127 0.146 0.143
	75 0.142 0.163 0.153

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

Embodiment 4-polyurethane foam K-factor

This embodiment has confirmed with the various HFC co-foaming agent bonded that use in the preparation of polyurethane foam, has comprised the performance of the whipping agent of HFO-1234ze (comprising its isomer).Same foam prescription, 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 about 80% (weight) of total whipping agent (comprising its isomer) and concentration is the HFC-245fa of about 20% (weight) of total whipping agent.Except whipping agent according to the present invention, HFC-134a and pentamethylene are also tested as whipping agent respectively.In each system, whipping agent is added in the polyol mixture with essentially identical volumetric molar concentration.Use this whipping agent formation foam then and measure the foamy K-factor.Following table 4 illustrated, when using jointly with the HFC co-foaming agent, and the K-factor performance of HFO-1234ze (comprising its isomer) mixture.

Medial temperature (℉) the K-factor (BTU in/hr ft 2℉)
	HFC-1234ze/HFC-245fa HFC-134a pentamethylene
40 0.129 0.146 0.143
	75 0.144 0.163 0.153

A unexpected result of this embodiment explanation is to handle HFO-1234ze and HFC-1234ze/HFC mixture in the urethane treatment facility of routine.This has the potential huge advantage, to such an extent as to can use various types of systems and equipment to handle foam, 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 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.Make three kinds of apparatus polyurethane foams, use essentially identical material, program and equipment to form respectively, but use different whipping agents.The polyol system is commercially available, an applied prescription (formulation), and it is fit to use with liquid blowing agent.Use foaming machine to form foam.Use whipping agent with the volumetric molar concentration that equates basically.After the formation, each foam is cut into the sample that is fit to measure the K-factor, and the K-factor is shown in following table 5B.The weight percentage that blowing agent component accounts for total whipping agent is disclosed among the following table 5A.

Table 5A

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

Pentamethylene

0

0

29

^*100% cis

Table 5B

Medial temperature (℉) the K-factor (BTU in/hr ft 2℉)
	A B C
40 0.116 0.119 0.116
	75 0.131 0.134 0.132
110 0.146 0.149 0.148

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

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

Medial temperature (℉) the K-factor (BTUin/hr ft2 ℉)
	40 0.127
75 0.143
	110 0.159

Claims (52)

1. whipping agent, it comprises:

(a) fluoroolefins of at least a 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 are Cl, F, Br, I or H independently, and z be 1 to 3 and

(b) at least a fluorinated ether.

2. the composition of claim 1, it further comprises at least a 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 a fluoroolefins comprise at least a three carbon with 3 to 5 fluoro substituents and/(or) at least a four carbon olefins.

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

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

6. the whipping agent of claim 1, wherein said at least a 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 and is not higher than about 150 global warming potential (GWP).

11. the whipping agent of claim 1, it has and is not higher than about 0.05 ozone depletion potential (ODP).

12. comprising, the whipping agent of claim 1, wherein said fluoroolefins have the substituent unsaturated ends carbon of a no more than F.

13. the whipping agent of claim 1, wherein said fluoroolefins comprise unsaturated ends carbon and at least one substituting group on unsaturated ends carbon is H.

14. the whipping agent of claim 1, the compound of wherein said formula I does not contain Br.

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

16. the whipping agent of claim 15, wherein said compound comprises HFCO-1233.

17. the whipping agent of claim 15, wherein said HFCO-1233 comprises HFCO-1233xf.

18. the whipping agent of claim 15, wherein said HFCO-1233 comprises HFCO-1233zd.

19. the whipping agent of claim 1, the amount of the compound of wherein said at least a formula I in composition are about 5% to about 95% of whipping agent by weight.

20. the whipping agent of claim 1, wherein said auxiliary comprise at least a other co-foaming agent.

21. the whipping agent of claim 20, wherein said at least a other co-foaming agent comprises one or more C1-C4 HFC.

22. the whipping agent of claim 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.

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

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

25. one kind comprises the foamable composite that foam forms agent and whipping agent, described whipping agent comprises the fluoroolefins of at least a formula I:

XCF _zR _3-z(I)

Wherein X is C ₁, C ₂, C ₃, C ₄Or C ₅Undersaturated, substituted group, each R are C1, F, Br, I or H independently, and z is 1 to 3; With at least a fluorinated ether.

26. the foamable composite of claim 25, wherein said foam form agent and comprise at least a thermosetting foams composition.

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

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

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

30. the foamable composite of claim 25, wherein said foam form agent and comprise at least a thermoplastic foam composition.

31. the foamable composite of claim 30, wherein said at least a thermoplastic foam composition comprises thermoplastic polymer.

32. the foamable composite of claim 30, wherein said at least a thermoplasticity composition comprises polyolefine.

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

34. a foam premix composition, it comprises polyol and whipping agent, and described whipping agent comprises the fluoroolefins of at least a formula I:

XCF _zR _3-z(I)

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

35. one kind forms the foamy method, it comprise to can foam and/or foaming composition in add whipping agent, described whipping agent comprises the fluoroolefins of at least a formula I:

XCF _zR _3-z(I)

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

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

XCF _zR _3-z(I)

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

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

38. the foam of claim 36, it has when 40 ℉ and is not higher than about 0.14 the K-factor (BTU in/hr ft ²℉).

39. the foam of claim 36, it has when 75 ℉ and is not higher than about 0.16 the K-factor (BTU in/hr ft ²F)。

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

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

42. the whipping agent of claim 1, wherein said auxiliary comprises at least a co-foaming agent, and 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.

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

44. the foamable composite of claim 25, it is thermoplastic that wherein said foam forms agent, and described whipping agent further comprises ethanol.

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

46. the foamable composite of claim 25, it is heat cured that wherein said foam forms agent, and described whipping agent further comprises methyl-formiate.

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

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

49. the whipping agent of claim 1, wherein said fluorinated ether comprise at least a hydrofluorination ether.

50. the whipping agent of claim 1, wherein said fluorinated ether comprise at least a C3 to C5 hydrofluorination ether.

51. the whipping agent of claim 1, wherein said fluorinated ether are the fluorinated ethers according to 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，

And one of them described C _aCan be bonded to a described C _dTo form the ring fluoroether.

52. the whipping agent of claim 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 γ), CHF ₂OCF ₂CHF ₂(HFE-236caE), CF ₃CF ₂OCH ₂F (HFE-236cbE β γ), CF ₃OCHFCHF ₂(HFE-236eaE α β), CHF ₂OCHFCF ₃(HFE-236eaE β γ), CHF ₂OCF ₂CH ₂F (HFE-245caE α β), CH ₂FOCF ₂CHF ₂(HFE-245caE β γ), CF ₃OCF ₂CH ₃(HFE-245cbE β γ), CHF ₂CHFOCHF ₂(HFE-245eaE), CF ₃OCHFCH ₂F (HFE-245ebE α β), CF ₃CHFOCH ₂F (HFE-245ebE β γ), CF ₃OCH ₂CF ₂H (HFE-245faE α β), CHF ₂OCH ₂CF ₃(HFE-245faE β γ), CH ₂FCF ₂OCH ₂F (HFE-254caE), CHF ₂OCF ₂CH ₃(HFE-254cbE α β), CHF ₂CF ₂OCH ₃(HFE-254caE β γ), CH ₂FOCHFCH ₂F (HFE-254eaE α β), CF ₃OCHFCH ₃(HFE-254ebE α β), CF ₃CHFOCH ₃(HFE-254ebE β γ), CHF ₂OCH ₂CHF ₂(HFE-254faE), CF ₃OCH ₂CH ₂F (HFE-254fbE α β), CF ₃CH ₂OCH ₂F (HFE-254fbE β γ), CH ₃OCF ₂CH ₂F (HFE-263caE β γ), CF ₃CH ₂OCH ₃(HFE-263fbE β γ), CH ₃OCH ₂CHF ₂(HFE-272fbE β γ), CHF ₂OCHFCF ₂CF ₃(HFE-338mceE γ δ), CHF ₂OCF ₂CHFCF ₃(HFE-338mceE γ δ), CF ₃CF ₂OCH ₂CF ₃(HFE-338mfE β γ), (CF ₃) ₂CHOCHF ₂(HFE-338mmzE β γ), CF ₃CF ₂CF ₂OCH ₃(HFE-347sE γ δ), CHF ₂OCH ₂CF ₂CF ₃(HFE-347mfcE γ δ), CF ₃OCH ₂CF ₂CHF ₂(HFE-347mfcE α β), CH ₃OCF ₂CHFCF ₃(HFE-356mecE γ δ), CH ₃OCH (CF ₃) ₂(HFE-356mmzE β γ), CF ₃CF ₂OCH ₂CH ₃(HFE-365mcE β γ), CF ₃CF ₂CH ₂OCH ₃(HFE-365mcE γ δ), CF ₃CF ₂CF ₂OCHFCF ₃(HFE-42-11meE γ 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 ₃And these any two or more combination.