(19)
(11)EP 2 718 253 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
09.09.2020 Bulletin 2020/37

(21)Application number: 12726957.9

(22)Date of filing:  22.05.2012
(51)International Patent Classification (IPC): 
C07C 49/175(2006.01)
C07D 295/084(2006.01)
B29C 44/00(2006.01)
C07D 307/12(2006.01)
C09K 5/00(2006.01)
B23K 35/00(2006.01)
(86)International application number:
PCT/US2012/038960
(87)International publication number:
WO 2012/170196 (13.12.2012 Gazette  2012/50)

(54)

PARTIALLY FLUORINATED KETONES AND METHODS OF MAKING AND USING THE SAME

TEILWEISE FLUORIERTE KETONE UND VERFAHREN ZU IHRER HERSTELLUNG UND VERWENDUNG

CÉTONES PARTIELLEMENT FLUORÉES ET LEURS PROCÉDÉS DE FABRICATION ET D'UTILISATION


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 10.06.2011 US 201161495633 P

(43)Date of publication of application:
16.04.2014 Bulletin 2014/16

(73)Proprietor: 3M Innovative Properties Company
St. Paul, MN 55133-3427 (US)

(72)Inventors:
  • COSTELLO, Michael G.
    Saint Paul, Minnesota 55133-3427 (US)
  • BULINSKI, Michael J.
    Saint Paul, Minnesota 55133-3427 (US)
  • FLYNN, Richard M.
    Saint Paul, Minnesota 55133-3427 (US)

(74)Representative: Mathys & Squire 
Mathys & Squire Europe LLP Theatinerstraße 7
80333 München
80333 München (DE)


(56)References cited: : 
WO-A1-2007/075804
WO-A1-2008/070606
  
     
    Remarks:
    The file contains technical information submitted after the application was filed and not included in this specification
     
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Field



    [0001] This invention relates to partially fluorinated ketone compounds and processes for using the same.

    Background



    [0002] Presently various fluids are used for heat transfer, cleaning solvents, deposition solvents and other purposes in the electronics industry. The suitability of a fluid depends upon the application process. For example, some electronic applications require fluids which are inert, have a high dielectric strength, have low toxicity, have good environmental properties, and have good heat transfer properties over a wide temperature range. Other applications require precise temperature control and thus the heat-transfer fluid is required to be a single phase over the entire process temperature range and the heat-transfer fluid properties are required to be predictable, i.e., the composition remains relatively constant so that the viscosity, boiling point, etc. can be predicted so that a precise temperature can be maintained and so that the equipment can be appropriately designed.

    [0003] Perfluorocarbons, perfluoropolyethers, and some hydrofluoroethers have been used for heat transfer and other purposes in the electronic industry. Perfluorocarbons (PFCs) can have high dielectric strength and high resistivity. PFCs can be non-flammable and are generally mechanically compatible with materials of construction, exhibiting limited solvency. Additionally, PFCs generally exhibit low toxicity and good operator friendliness. PFCs can be manufactured in such a way as to yield a product that has a narrow molecular weight distribution. They can exhibit one important disadvantage, however, and that is a long atmospheric lifetime which can give rise to a high global warming potential (GWP).

    [0004] Perfluoropolyethers (PFPEs) exhibit many of the same advantageous attributes described for PFCs. They also have the same major disadvantage, i.e., a long atmospheric lifetime which can give rise to a high global warming potential (GWP). In addition, the methods developed for manufacturing these materials can yield products that are not of consistent molecular weight and thus can be subject to performance variability.

    [0005] Hydrofluoropolyethers (HFPEs), a class of hydrofluoroethers (HFEs), can exhibit some of the same advantageous attributes of PFCs, but differ greatly in two areas. They can exhibit markedly lower environmental persistence, yielding atmospheric lifetimes on the order of decades rather than millennia which can give rise to a lower, though still relatively high, global warming potential. However, some of the HFPEs taught as heat-transfer fluids can be a mixture of components of widely disparate molecular weight. Thus, their physical properties may change over time which makes it difficult to predict performance.

    [0006] WO 2008/070606 relates to a hydrofluoroether compound comprising two terminal, independently fluoroalkyl or perfluoroalkyl groups and an intervening oxytetrafluoroethylidene moiety (-OCF(CF3)-) bonded through its central carbon atom to an alkoxy- or fluoroalkoxy-substituted fluoromethylene moiety (-CF(OR)-), each of said terminal groups optionally comprising at least one catenated heteroatom.

    [0007] WO 2007/075804 relates to a fluorochemical ketone compound consisting of two terminal, branched, independently fluoroalkylcarbonyl or perfluoroalkylcarbonyl groups and an intervening linear perfluoropolyether segment, each of said terminal groups optionally comprising at least one catenated heteroatom, and said perfluoropolyether segment consisting essentially of at least one tetrafluoroethyleneoxy moiety and, optionally, at least one difluoromethyleneoxy moiety, said moieties being randomly or non-randomly distributed within said perfluoropolyether segment.

    Summary



    [0008] The need exists for electronic fluids that are inert, have high dielectric strength, low electrical conductivity, chemical inertness, thermal stability and effective heat transfer, are liquid over a wide temperature range, have good heat-transfer properties over a wide range of temperatures and also have an acceptable environmental profile including a relatively short atmospheric lifetime and relatively low global warming potential (GWP). The need exists for electronic fluids that can be low GWP alternatives to many applications where perfluorocarbons, perfluoropolyethers, and hydrofluoroethers are currently used. The provided partially fluorinated ketones are a new and unique class of compounds which can find utility in the electronics industry as low GWP alternatives to currently used materials.

    [0009] The invention is defined by the appended claims 1-9.

    [0010] In one aspect, a partially fluorinated ketone is provided having the formula:

            RHC(=O)CF2CFHORf,

    or

            RH1C(=O)CF2CFHORfOCFHCF2C(=O)RH2

    wherein each RH, RH1, and RH2 is, independently, an alkyl group having from 1 to 4 carbon atoms, and wherein Rf is a fluorinated alkyl or alkylene moiety having from 1 to 6 carbon. Each RH, RH1, and RH2 is, independently, linear, branched, cyclic, or a combination thereof. In some embodiments, Rf can be perfluorinated.

    [0011] In another aspect, a process is provided for removing a contaminant from an article that includes contacting the article with at least one provided partially fluorinated ketone compound.

    [0012] In another aspect, a process is provided for preparing a foamed plastic that includes vaporizing a blowing agent mixture in the presence of at least one foamable polymer or the precursors of at least one foamable polymer, said blowing agent mixture comprising at least one provided partially fluorinated ketone compound.

    [0013] In another aspect, a process for transferring heat is provided that includes transferring heat between a heat source and a heat sink through the use of a heat transfer agent that comprises at least provided one partially fluorinated ketone compound.

    [0014] In another aspect, a process for depositing a coating on a substrate is provided that includes applying to at least a portion of at least one surface of said substrate a composition comprising (a) a solvent composition comprising at least one provided partially fluorinated ketone compound and (b) at least one coating material that is soluble or dispersible in said solvent composition.

    [0015] Disclosed herein is also a polymerization process that includes polymerizing at least one monomer in the presence of at least one polymerization initiator in the presence of at least one provided partially fluorinated ketone compound.

    [0016] Disclosed herein is also a method of preparing partially fluorinated ketones that includes reacting an alkyl aldehyde having from 2 to 6 carbon atoms with a perfluorinated vinyl ether using a free-radical initiator to form at least one partially fluorinated ketone,
    wherein the partially fluorinated ketone comprises a partially fluorinated hydrocarbon moiety, having from 2 to 4 carbon atoms, containing at least one hydrogen substituent, bonded to the carbonyl group with a carbon-carbon bond, and an ether oxygen that is distal to the carbonyl group; and a fluorinated alkyl group, having from 1 to 6 carbon atoms, bonded to the ether oxygen of the partially fluorinated hydrocarbon moiety, and wherein the fluorinated alkyl group may contain at least one catenated oxygen or nitrogen atom.

    [0017] In the present disclosure,

    "catenated heteroatom" refers to an atom other than carbon (for example, oxygen or nitrogen) that is bonded to carbon atoms in a carbon chain so as to form a carbon-heteroatom-carbon chain;

    "ether oxygen bonded to a carbon atom that is at least two carbons removed from the carbonyl group" refers to a structure that has a partially fluorinated alkylene moiety that includes a carbon chain of at least two carbon atoms between the ether oxygen and the carbonyl group;

    "fluoro-" (for example, in reference to a group or moiety, such as in the case of "fluoroalkylene" or "fluoroalkyl" or "fluorocarbon") or "fluorinated" refers to only partially fluorinated such that there is at least one carbon-bonded hydrogen atom;

    "fluorochemical" refers to "fluorinated" or "perfluorinated"; and

    "perfluoro-" (for example, in reference to a group or moiety, such as in the case of "perfluoroalkylene" or "perfluoroalkyl" or "perfluorocarbon") or "perfluorinated" refers to completely fluorinated such that, except as may be otherwise indicated, there are no carbon-bonded hydrogen atoms replaceable with fluorine.



    [0018] The provided partially fluorinated ketones can be used in a number of different applications including, for example, use as a solvent in coating deposition, as a cleaning or drying fluid, as a dry cleaning fluid, as a polymerization medium, as a document preservation medium, as a heat transfer agent, as a cell size regulator for use in foam blowing and as a metal working agent in the cutting or forming of metals. At least some of the partially fluorinated ketones boil above 100°C yet also exhibit surprisingly good low temperature viscosity characteristics. Thus, at least some embodiments of the invention meet the above-described, ongoing need for partially fluorinated ketones that can meet the performance requirements of a variety of different applications (as well as the need for efficient and cost-effective processes for their preparation).

    [0019] The above summary is not intended to describe each disclosed embodiment of every implementation of the present invention. The detailed description which follows more particularly exemplifies illustrative embodiments.

    Detailed Description



    [0020] In the following description, reference is made to several specific embodiments. It is to be understood that other embodiments are contemplated and may be made. The following detailed description, therefore, is not to be taken in a limiting sense.

    [0021] Unless otherwise indicated, all numbers expressing feature sizes, amounts, and physical properties used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5) and any range within that range.

    [0022] Partially fluorinated ketones are disclosed that include a terminal alkyl group having between 1 to 6 carbon atoms bonded to a carbonyl group to which is bonded a partially fluorinated hydrocarbon moiety having from 2 to 4 carbon atoms and containing at least one hydrogen substituent. The partially fluorinated ketones also include an ether oxygen bonded to a carbon atom that is at least two carbons removed from the carbonyl group. The partially fluorinated ketones also include a fluorinated alkyl group, having from 1 to 10 carbon atoms, bonded to the ether oxygen of the partially fluorinated hydrocarbon moiety. The fluorinated alkyl group may contain at least one catenated oxygen or nitrogen atom.

    [0023] The terminal alkyl group can be linear, branched, cyclic, or a combination thereofThe terminal alkyl group can be ethyl or methyl. The partially fluorinated hydrocarbon moiety can comprise (-CF2-CFH-) with the (-CF2-) bonded to the carbonyl group. The fluorinated alkyl group can be perfluorinated and can comprise a terminal group.

    [0024] Exemplary partially fluorinated ketone compounds include C3F7OCFHCF2C(O)CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH3, CF3OCFHCF2C(O)CH3, C4F9OCFHCF2C(O)CH3, CF3OC3F6OCFHCF2C(O)CH3, C2F5OCFHCF2C(O)CH3, (CF3)2CFCF2OCFHCF2C(O)CH3, C5F11OCFHCF2C(O)CH3, HCF2CF2CF2OCFHCF2C(O)CH3, CH3OCF2CF2CF2OCFHCF2C(O)CH3,

    CH3C(O)CF2CFHOC4F8OCFHCF2C(O)CH3, C3F7OCFHCF2C(O)CH2CH3, C3F7OCFHCF2C(O)CH2CH2CH3, C3F7OCFHCF2C(O)CH(CH3)2, C4F9OCFHCF2C(O)CH2CH3, C4F9OCFHCF2C(O)CH2CH2CH3, C4F9OCFHCF2C(O)CH(CH3)2, CF3OC3F6OCFHCF2C(O)CH2CH3, CF3OC3F6OCFHCF2C(O)CH2CH2CH3, CF3OC3F6OCFHCF2C(O)CH(CH3)2, CF3OCFHCF2C(O)CH2CH3, CF3OCFHCF2C(O)CH2CH2CH3, CF3OCFHCF2C(O)CH(CH3)2, C3F7OCF(CF3)CF2OCFHCF2C(O)CH2CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH2CH2CH3, C3F7OCF(CF3)OCF2OCFHCF2C(O)CH(CH3)2, CH3CH2(O)CCF2CFHOC4F8OCFHCF2C(O)CH2CH3, CH3CH2CH2C(O)CF2CFHOC4F8OCFHCF2C(O)CH2CH2CH3, (CH3)2CH(O)CCF2CFHOC4F8OCFHCF2C(O)CH(CH3)2,



    and mixtures thereof.

    [0025] The partially fluorinated ketone compounds can be prepared by the free-radical addition of an alkyl aldehyde with fluoro- or perfluorovinyl ethers. The aldehydes can have an alkyl group that contains from 1 to 6 carbon atoms. The aldehydes have the structure, R-C(O)-H, where R is the alkyl group. Typically, the alkyl group is a straight chained or branched alkyl group such as, for example, methyl, ethyl, propyl or iso-propyl. The alkyl group can have at least one catenated oxygen or nitrogen atom.

    [0026] Typically, the alkyl aldehyde and the fluoro-or perfluorovinyl ethers are placed in a pressure reactor such as a Parr reactor along with a free-radical initiator that works at the appropriate reaction temperature for the desired reaction. Typical free-radical initiators include peroxides and azo compounds. Typical peroxides include diacyl peroxides, dialkyl peroxydicarbonates, t-alkyl peroxyesters, di-(t-alkyl)peroxyketals, and di-t-alkyl peroxides. Particularly useful are initiators that have initiating temperatures between about 65°C and 135°C. These include peroxides under the trade designation LUPEROX (available from Arkema, Inc, Philadelphia, PA) or under the trade designations CUROAT, CUROX (available from United Initiators, Pullach Germany). Exemplary organic peroxides include 1,1-di(t-amylperoxy)cyclohexane, 1,1-di(t-butylperoxy)3,3,5-trimethyl cyclohexane, t-amyl peroxy-2-ethyl hexanoate, benzoyl peroxide, t-amyl peroxybenzoate, t-butyl peroxyacetate, t-butyl peroxybenzoate ethyl 3,3-di-(t-amylperoxy)butyrate, ethyl 3,3-di(t-butylperoxy)butyrate, and dicumyl peroxide. Azo initiators include compounds available under the trade designation PERCARBAMID (United Initiators) and include materials such as carbamide peroxide. Additional azo initiators include azobisisobutyronitrile (AIBN) and 2,2'-azodi(2-methylbutyronitrile).

    [0027] Fluoro- and perfluorovinyl ethers that are useful in carrying out the process of preparation of the partially fluorinated ketones include those that possess a terminal perfluorovinyl group. Such fluoro- and perfluorovinyl ethers, which optionally, can further contain one or more catenated heteroatoms (in addition to the ether oxygen of the fluoro- and perfluorovinyl ethers), can be prepared by the reaction of a fluorochemical acid fluoride or a fluorochemical ketone with hexafluoropropylene oxide (HFPO) to form an intermediate branched acid fluoride adduct. This adduct can then be reacted with a base to form an intermediate carboxylic acid salt, which can then be decarboxylated at elevated temperature (optionally, in the presence of an inert solvent). Some perfluorovinyl ethers (for example, perfluorovinyl ethers such as C3F7OCF=CF2, C3F7OCF(CF3)CF2OCF=CF2, and CF3OCF=CF2) are also commercially available (for example, from Synquest Laboratories, Alachua, FL or from Apollo Scientific, Ltd., Chershire, UK).

    [0028] The fluorochemical acid fluorides (used for preparing the fluoro- and perfluorovinyl ethers) can be prepared from, for example, the corresponding hydrocarbon acid fluorides or acid chlorides (the latter of which are commercially available) or certain lactones, anhydrides, or esters by electrochemical fluorination in anhydrous hydrogen fluoride or by direct fluorination using elemental fluorine. Suitable fluorochemical acid fluorides include those having no hydrogen atoms bonded to the carbon atom adjacent to the carbonyl moiety. Representative examples of such fluorochemical acid fluorides include
    CF3C(O)F, CF3CF2C(O)F, CF3CF2CF2C(O)F, (CF3)2CFC(O)F, C4F9C(O)F, CF3OCF2CF2C(O)F, HCF2CF2C(O)F, CH3OCF2CF2C(O)F, FC(O)C2F4C(O)F, FC(O)C3F6C(O)F,





    and mixtures thereof. Perfluorinated acid fluorides are typically employed from a cost and availability perspective.

    [0029] Representative examples of fluoro- and perfluorovinyl ethers that are useful in preparing the partially fluorinated ketone compounds include C3F7OCF=CF2, C3F7OCF(CF3)CF2OCF=CF2, CF3OCF=CF2, C4F9OCF=CF2, CF3OC3F6OCF=CF2, C2F5OCF=CF2, (CF3)2CFCF2OCF=CF2, C5F11OCF=CF2, HCF2CF2CF2OCF=CF2, CH3OCF2CF2CF2OCF=CF2,

    CF2=CFOC4F8OCF=CF2, and mixtures thereof. Preferred vinyl ethers include C3F7OCF=CF2, C4F9OCF=CF2, CF3OC3F6OCF=CF2, CF3OCF=CF2 , C3F7OCF(CF3)CF2OCF=CF2, CF2=CFOC4F8OCF=CF2 and mixtures thereof. C3F7OCF=CF2, C4F9OCF=CF2, and mixtures thereof are more preferred. (Mixtures of starting compounds can be used, if desired, but mixtures are generally less preferred due to the resulting production of product mixtures that can require purification.)

    [0030] Suitable solvents include anhydrous, polar, aprotic solvents such as glycol ether solvents (for example, glyme, diglyme, triglyme, tetraglyme, and mixtures thereof), tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, sulfolane, acetonitrile, and mixtures thereof. Typical solvents include glyme, diglyme, triglyme, tetraglyme, dimethylformamide, and mixtures thereof; with glyme, diglyme, dimethylformamide, and mixtures thereof being especially preferred.

    [0031] In preparing the partially fluorinated ketone compounds, an alkyl aldehyde, a perfluorinated vinyl ether, and, optionally, a solvent can be combined in any order in any suitable reactor (for example, a metal reactor; typically, a pressure reactor such as a Parr reactor). The reactor can then be sealed and heated to a desired reaction temperature (for example, about 70-80°C, or even 100-150°C) under autogenous pressure for a period sufficient to achieve a desired level of conversion (for example, for about 16-72 hours), generally with stirring or agitation of the reactor contents and, preferably, with temperature control.

    [0032] After the reaction has run to completion, the reactor can be cooled and vented and the contents purified by any suitable separation method. For example, the resulting reaction mixture can be filtered, phase separated (for example, to remove the solvent and catalyst), washed with a washing solvent (for example, washed with acetone to remove residual solvent and catalyst), phase separated (for example, to remove the washing solvent), and subjected to rotary evaporation and/or distillation (for example, to remove any residual volatile materials and to purify the resulting partially fluorinated ketone product). In some embodiments, the product can be fractionally distilled directly from the reaction mixture.

    [0033] The provided partially fluorinated ketone compounds (or a normally liquid composition comprising, consisting, or consisting essentially thereof) can be used in various applications. For example, the compounds can be used as solvents for precision or metal cleaning of electronic articles such as disks or circuit boards; as heat transfer agents (for example, for hybrid vehicle cooling and for the cooling or heating of integrated circuit tools in the semiconductor industry, including tools such as dry etchers, integrated circuit testers, photolithography exposure tools (steppers), ashers, chemical vapor deposition equipment, automated test equipment (probers), and physical vapor deposition equipment (sputterers); as cell size regulators in making foam insulation (for example, polyurethane, phenolic, and thermoplastic foams); as carrier fluids or solvents for document preservation materials and for lubricants; as power cycle working fluids such as for heat pumps; as heat recovery fluids in Rankine cycle engines; as inert media for polymerization reactions; as buffing abrasive agents to remove buffing abrasive compounds from polished surfaces such as metal; as displacement drying agents for removing water, such as from jewelry or metal parts; as resist developers in conventional circuit manufacturing techniques including chlorine-type developing agents; and as strippers for photoresists when used with, for example, a chlorohydrocarbon such as 1,1,1-trichloroethane or trichloroethylene.

    [0034] The provided partially fluorinated ketone compounds can exhibit high dielectric strengths (for example, greater than about 108 ohm-cm), which can make them well-suited for use in the semiconductor industry. Partially fluorinated ketone compounds can exhibit unexpectedly high thermal stabilities and can be particularly useful in high temperature applications such as in heat transfer applications in the semiconductor industry and in flat screen panel manufacture, and the partially fluorinated ketone compounds that have boiling points above 100°C, as well as good low temperature viscosity characteristics, are particularly useful in applications that require cycling between high temperature and low temperature heat sinks.

    [0035] The provided partially fluorinated ketone compounds can be used alone or in admixture with each other or with other commonly-used solvents (for example, alcohols, ethers, alkanes, alkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, siloxanes, hydrochlorocarbons, chlorinated alkenes, hydrochlorofluorocarbons, hydrofluorocarbons, and mixtures thereof). Such co-solvents can be chosen to modify or enhance the properties of a composition for a particular use and can be utilized in ratios (of co-solvent(s) to partially fluorinated ketone(s)) such that the resulting composition preferably has no flash point. If desired, the partially fluorinated ketone compounds can be used alone or in combination with other provided partially fluorinated ketone compounds.

    [0036] Minor amounts of optional components can be added to the compounds to impart particular desired properties for particular uses. Useful compositions can comprise conventional additives such as, for example, surfactants, coloring agents, stabilizers, anti-oxidants, flame retardants, and mixtures thereof.

    [0037] The partially fluorinated ketone compounds are useful as solvents for cleaning and drying applications such as, for example, those described in U. S. Pat. Nos. 5,125,089 (Flynn et al.), 3,903,012 (Brandreth), 4,169,807 (Zuber), and 5,925,611 (Flynn et al.) Both organic and inorganic substrates can be cleaned by contacting them with a composition comprising at least one partially fluorinated ketone of the invention. Most contaminants can be removed, including hydrocarbon contaminants, fluorocarbon contaminants, particulates, and water.

    [0038] In using partially fluorinated ketone compounds for the drying of or displacing water from the surface of articles (such as circuit boards), the process of drying or water displacement described in, for example, U. S. Pat. No. 5,125,978 (Flynn et al.) can be used. Broadly, such process comprises contacting the surface of an article with a liquid composition comprising at least one partially fluorinated ketone compound of the invention, typically in admixture with a nonionic fluoroaliphatic surface active agent. The wet article is immersed in the liquid composition and agitated therein, the displaced water is separated from the liquid composition, and the resulting water-free article is removed from the liquid composition. Further description of the process and the articles that can be treated can be found in said U. S. Pat. No. 5,125,978.

    [0039] In using the provided partially fluorinated ketones as cell size regulators in making plastic foam (such as foamed polyurethane), the process reactants and reaction conditions described in, for example, U. S. Pat. Nos. 5,210,106 (Dams et al.) and 5,539,008 (Dams et al.) can be used. One such process comprises vaporizing a blowing agent mixture in the presence of at least one foamable polymer or the precursors of at least one foamable polymer, the blowing agent mixture comprising at least one provided partially fluorinated ketone.

    [0040] In using the provided partially fluorinated ketones as heat transfer agents, the processes described in, for example, U. S. Reissue Pat. No. 37,119 E (Sherwood) and U. S. Pat. No. 6,374,907 (Tousignant et al.) can be used. In carrying out such processes, heat is transferred between a heat source (for example, a silicon wafer or a component of a flat panel display) and a heat sink through the use of a heat transfer agent comprising at least one provided partially fluorinated ketone compound. The provided partially fluorinated ketones are not mixtures of components of widely disparate molecular weights. Rather, the partially fluorinated ketones are generally monodisperse (that is, of a single molecular weight). This means that their physical properties remain relatively constant over time, thereby avoiding significant heat transfer performance deterioration. In addition, the provided partially fluorinated ketones generally exhibit a wide liquid range, useful viscosity over that range, and relatively high thermal stability at end use temperatures, making them well-suited for use as heat transfer fluids.

    [0041] In using the provided partially fluorinated ketone compounds as deposition solvents in coating applications or in document preservation applications, the processes described in, for example, U. S. Pat. Nos. 5,925,611 (Flynn et al.) and 6,080,448 (Leiner et al.) can be used. Such processes for depositing a coating on a substrate (for example, magnetic recording media or cellulose-based materials) comprises applying, to at least a portion of at least one surface of the substrate, a composition comprising (a) a solvent composition comprising at least one provided partially fluorinated ketone compound; and (b) at least one coating material that is soluble or dispersible in the solvent composition. Coating materials that can be deposited by the process include pigments, lubricants, stabilizers, adhesives, anti-oxidants, dyes, polymers, pharmaceuticals, release agents, inorganic oxides, document preservation materials (for example, alkaline materials used in the deacidification of paper), and combinations thereof. Typical materials include perfluoropolyether, hydrocarbon, and silicone lubricants; amorphous copolymers of tetrafluoroethylene; polytetrafluoroethylene; document preservation materials; and combinations thereof. In some other useful embodiments, the material is a perfluoropolyether lubricant or a document preservation material.

    [0042] In using the provided partially fluorinated ketone compounds in cutting or abrasive working operations, the processes described in, for example, U.S. Patent No. 6,759,374 (Milbrath et al.) can be used. Such a process for metal, cermet, or composite working comprises applying a working fluid to a metal, cermet, or composite workpiece and tool, the working fluid comprising at least one provided partially fluorinated ketone compound and at least one lubricious additive. The working fluid can further comprise one or more conventional additives (for example, corrosion inhibitors, antioxidants, defoamers, dyes, bactericides, freezing point depressants, metal deactivators, co-solvents, and mixtures thereof).

    [0043] In using the provided partially fluorinated ketone compounds as polymerization media, the processes described in, for example, Research Disclosures, Number 40576, page 81 (January 1998) and in U. S. Pat. Nos. 5,182,342 (Feiring et al.) and 6,399,729 (Farnham et al.) can be used. Such processes comprise polymerizing at least one monomer (preferably, at least one fluorine-containing monomer) in the presence of at least one polymerization initiator and at least one provided partially fluorinated ketone compound.

    [0044] Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.

    Examples


    Example 1



    [0045] Preparation of 3,3,4-trifluoro-4-(1,1,2,2,3,3,4,4,4-nonafluorobutoxy)butan-2-one CH3C(O)CF2CFHOC4F9

    [0046] 1,1,1,2,2,3,3,4,4-nonafluoro-4-(1,2,2-trifluorovinyloxy)butane (180 g, 0.57 mol) which can be prepared by the methods described in U. S. Pat. App. Publ. No. 2008/0139683 (Flynn et al.) was combined with acetaldehyde (50.17 g, 1.14 mol, Sigma-Aldrich, St. Louis, MO) and t-amylperoxy-2-ethylhexanoate (4 g, 0.017 mol, United Initiators, Pullach, Germany) in a 600 mL Parr pressure reactor. The mix was heated to 75°C for 18 hours. The reaction mix was then analyzed by GC-FID which indicated a reaction conversion of at least 64% to the product. GC/MS analysis of the crude product confirmed the desired product mass was present as the major component. The product was purified by fractional distillation to a purity of 99.4%. The boiling point of the product was 130°C at atmospheric pressure.

    Example 2 (comparative)


    Preparation of 3,3,4-trifluoro-4-[1,1,2,2,3,3-hexafluoro-3-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)propoxy]butan-2-one.



    [0047] 



    [0048] The Michael addition reaction of methyl acrylate and morpholine was performed to generate the methyl 3-morpholinopropanoate. This organic ester was converted to the perfluorinated acyl fluoride by electrochemical fluorination (ECF) in a Simons ECF cell of essentially the type described in U.S. Patent No. 2,713,593 (Brice et al.) and in R.E. Banks, Preparation, Properties and Industrial Applications of Organofluorine Compounds, pages 19-43, Halsted Press, New York (1982) to produce 2,2,3,3-tetrafluoro-3-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)propanoyl fluoride.

    [0049] Hexafluoropropene oxide (HFPO) (89.6 g, 0.54 mol, 3M Company) was added to the acyl fluoride (205 g, 0.54 mol) in a solution of diglyme solvent (56 g) and potassium fluoride (4 g 0.069 mol, Aldrich) in a 600mL Parr pressure reactor. The reactor temperature was kept below 16°C and the pressure of the HFPO was kept at or below 69 kPa during the addition. Once the HFPO addition was complete the reactor contents were emptied. Analysis by GC-FID revealed that 76% of this recovered amount was the mono-addition product and 8.8% was the di-adduct. The mono adduct was then separated from the di-adduct by fractional distillation. 2,3,3,3-tetrafluoro-2-[1,1,2,2,3,3-hexafluoro-3-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)propoxy]propanoyl fluoride (270 g, 0.49 mol) was combined with oven dried sodium carbonate (103 g, 0.98 mol, Aldrich) and anhydrous diglyme (400 g, Aldrich) via an addition funnel at 75°C in a 2L round bottom flask equipped with overhead stirring, heating mantle, thermocouple and a cold water condenser. The mix was kept dry with a nitrogen bubbler. The mixture was stirred for 18 hours at 75°C. A one-plate distillation column was put in place of the reflux line and the product was distilled from the mixture by gradually heating to 150°C. Approximately 123g of the vinyl ether 2,2,3,3,5,5,6,6-octafluoro-4-[1,1,2,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propyl]morpholine was recovered from this distillation.

    [0050] 2,2,3,3,5,5,6,6-octafluoro-4-[1,1,2,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propyl]morpholine (123 g 0.26 mol) was combined with acetaldehyde (23 g, 0.52 mol, Aldrich) and t-amylperoxy-2-ethyl hexanoate (5 g, United Initiators) in a 600 mL Parr pressure reactor. The reactor was sealed and heated to 75°C for 18 hours. The reaction mixture was then emptied and analyzed by GC/MS which confirmed that the major component was 3,3,4-trifluoro-4-[1,1,2,2,3,3-hexafluoro-3-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)propoxy]butan-2-one.

    Example 3


    Preparation of 3,3,4-trifluoro-4-[1,1,2,2,3,3,4,4-octafluoro-4-(1,2,2-trifluoro-3-oxo-butoxy)butoxy]butan-2-one



    [0051] 


    Preparation of 1,1,2,2,3,3,4,4-octafluoro-1,4-bis(1,2,2-trifluorovinyloxy)butane



    [0052] Unless otherwise noted, all solvents and reagents were obtained from Aldrich Chemical Co. of Milwaukee, WI.

    Preparation of tetrafluorosuccinyl fluoride



    [0053] Tetrafluorosuccinyl fluoride was prepared by electrochemical fluorination of butyrolactone in a Simons ECF cell of the type described in U.S. Pat. No. 2,713,593 (Brice et al.) and in R. E. Banks, Preparation and Industrial Applications of Organofluorine Compounds, 19-43 (1982). The gaseous products from the cell were further purified by fractional distillation to yield 83 % tetrafluorosuccinyl fluoride, 2 % tetrafluoromethylmalonyl fluoride, 7% 3-trifluoromethoxytetrafluoropropionyl fluoride and the remainder being perfluorinated inert materials. This mixture could be used in subsequent reactions without further purification. As used herein, the term "perfluorosuccinyl fluoride" will refer to the mixture of tetrafluorosuccinyl fluoride, tetrafluoromethylmalonyl fluoride and 3-trifluoromethoxytetrafluoropropionyl fluoride just described.

    Preparation of HFPO Adducts of perfluorosuccinyl fluoride, FOC(CF3)CF[OCF2(CF3)CF]mOCF2CF2CF2CF2O[CF(CF3)CF2O]nCF(CF3)COF



    [0054] A 600 ml stainless steel jacketed Parr pressure reactor was charged with spray-dried potassium fluoride (1.6 grams, 0.027 moles) and anhydrous diglyme (27.0 grams). The vessel was sealed, cooled to -25 °C, charge with perfluorosuccinyl fluoride (200 grams, 0.934 moles) and warmed to and controlled at 13 °C. Hexafluoropropene oxide (570 grams, 3.43 moles) was added over a 27 hour period with a fairly constant addition rate. The mixture was allowed to react for an additional hour and 790 grams of lower product phase was collected with the following composition.
    Table 1
    Composition of HFPO Adducts of Perfluorosuccinyl Fluoride
    m+nGC Area %
    0 11
    1 45
    2 26

    Preparation of di-vinyl ether, CF2=CF[OCF2(CF3)CF]mOCF2CF2CF2CF2O[CF(CF3)CF2O]nCF=CF2 m+n= 0-2



    [0055] A lL round bottom flask equipped with agitation, heating mantle, thermocouple temperature control, 100 ml barret trap and condenser connected to a nitrogen bubbler was charged with anhydrous sodium carbonate (85 grams, 0.80 moles) and anhydrous diglyme (236 grams). The vessel was heated to distill out 95 grams of wet diglyme. The reactor was cooled to 75°C and 230 gram of HFPO adduct was charged over a 15 minute period. Following a 1 hour hold at 110°C, distillate was collected when the batch was heated to 158°C. A water wash yielded 105 grams of product containing the following components.
    CF2=CF[OCF2(CF3)CF]mOCF2CF2CF2CF2O[CF(CF3)CF2O]nCF=CF2 m+n= 0-2
    Table 2
    Composition of Divinyl Ether
    m+nGC Area %
    0 6
    1 26
    2 15


    [0056] In a 600mL Parr pressure reactor, 1,1,2,2,3,3,4,4-octafluoro-1,4-bis(1,2,2-trifluorovinyloxy)butane (18 g, m+n = 0) was combined with 119g of acetaldehyde and 6g of - amylperoxy-2-ethyl hexanoate. The mixture was heated to 75 °C for 18 hours after which the reactor contents were emptied and analyzed by GC/MS. This analysis confirmed that the major component was the desired 3,3,4-trifluoro-4-[1,1,2,2,3,3,4,4-octafluoro-4-(1,2,2-trifluoro-3-oxo-butoxy)butoxy]butan-2-one.

    Example 4


    Preparation of 3,3,4-trifluoro-4-(1,1,2,3,3,3-hexafluoro-2-heptafluoropropyloxy-propoxy)-butan-2-one



    [0057] 



    [0058] 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoro-1-trifluoromethyl-2-trifluorovinyloxy-ethoxy)-propane, (208 grams, 0.481 moles), acetaldehyde (43.6 grams, 0.991 moles), benzoyl peroxide (1.0g, 0.004 moles) were charged to a 600ml Parr reactor. The reactor was cooled in dry ice and vacuum was pulled using a water aspirator. The reactor was heated to 80°C and stirred for 16 hours. The pressure rose to a maximum of 552 kPa (80 psig) and dropped to 172 kPa at the end of the 16 hours. The reactor was cooled to room temperature and excess pressure vented. The reactor contents were fractionated using a 10-plate Oldershaw column to obtain 143.6 grams of 3,3,4-trifluoro-4-(1,1,2,3,3,3-hexafluoro-2-heptafluoropropyloxy-propoxy)-butan-2-one with a purity of 99.4%. Structure was confirmed by g.c./m.s. Boiling Point is 156°C.


    Claims

    1. A partially fluorinated ketone having the formula:

            RHC(=O)CF2CFHORf,

    or

            RH1C(=O)CF2CFHORfOCFHCF2C(=O)RH2

    wherein each RH, RH', and RH2 is, independently, an alkyl group having from 1 to 4 carbon atoms,

    wherein Rf is a fluorinated alkyl moiety or alkylene moiety and wherein the alkyl or alkylene moiety has from 1 to 6 carbon atoms, and

    wherein each RH, RH', and RH2 is, independently, linear, branched, cyclic, or a combination thereof.


     
    2. A partially fluorinated ketone compound according to claim 1, wherein the partially fluorinated ketone compound is selected from the group consisting of C3F7OCFHCF2C(O)CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH3, CF3OCFHCF2C(O)CH3, C4F9OCFHCF2C(O)CH3, CF3OC3F6OCFHCF2C(O)CH3, C2F5OCFHCF2C(O)CH3, (CF3)2CFCF2OCFHCF2C(O)CH3, C5F11OCFHCF2C(O)CH3, HCF2CF2CF2OCFHCF2C(O)CH3, CH3OCF2CF2CF2OCFHCF2C(O)CH3, CH3C(O)CF2CFHOC4F8OCFHCF2C(O)CH3, C3F7OCFHCF2C(O)CH2CH3, C3F7OCFHCF2C(O)CH2CH2CH3, C3F7OCFHCF2C(O)CH(CH3)2, C4F9OCFHCF2C(O)CH2CH3, C4F9OCFHCF2C(O)CH2CH2CH3, C4F9OCFHCF2C(O)CH(CH3)2, CF3OC3F6OCFHCF2C(O)CH2CH3, CF3OC3F6OCFHCF2C(O)CH2CH2CH3, CF3OC3F6OCFHCF2C(O)CH(CH3)2 CF3OCFHCF2C(O)CH2CH3, CF3OCFHCF2C(O)CH2CH2CH3, CF3OCFHCF2C(O)CH(CH3)2, C3F7OCF(CF3)CF2OCFHCF2C(O)CH2CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH2CH2CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH(CH3)2, CH3CH2(O)CCF2CFHOC4F8OCFHCF2C(O)CH2CH3, CH3CH2CH2C(O)CF2CFHOC4F8OCFHCF2C(O)CH2CH2CH3, (CH3)2CH(O)CCF2CFHOC4F8OCFHCF2C(O)CH(CH3)2, and mixtures thereof.
     
    3. A partially fluorinated ketone according to claim 1, wherein each RH, RH1, and RH2 is, independently, linear.
     
    4. A partially fluorinated ketone according to claim 3, wherein RH is methyl and Rf is selected from:

            -CF2CF2CF2CF3, and -CF2CF2CF3.


     
    5. A partially fluorinated ketone according to claim 3, wherein RH1 and RH2 are each methyl and Rf is -CF2CF2CF2CF2-.
     
    6. A process for removing a contaminant from an article comprising contacting said article with a composition comprising at least one partially fluorinated ketone compound of claim 1.
     
    7. A process for preparing a foamed plastic comprising vaporizing a blowing agent mixture in the presence of at least one foamable polymer or the precursors of at least one foamable polymer, said blowing agent mixture comprising at least one partially fluorinated ketone compound of claim 1.
     
    8. A process for transferring heat comprising transferring heat between a heat source and a heat sink through the use of a heat transfer agent comprising at least one partially fluorinated ketone compound of claim 1.
     
    9. A process for depositing a coating on a substrate comprising:
    applying to at least a portion of at least one surface of said substrate a composition comprising (a) a solvent composition comprising at least partially fluorinated ketone compound of claim 1 and (b) at least one coating material that is soluble or dispersible in said solvent composition.
     


    Ansprüche

    1. Teilweise fluoriertes Keton der Formel:

            RHC(=O)CF2CFHORf,

    oder

            RH1C(=O)CF2CFHORfOCFHCF2C(=O)RH2,

    worin jedes RH, RH1 und RH2 unabhängig eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist,

    worin Rf ein fluorierter Alkylrest oder Alkylenrest ist und wobei der Alkyl- oder Alkylenrest 1 bis 6 Kohlenstoffatome aufweist, und

    worin jedes RH, RH1 und RH2 unabhängig linear, verzweigt, zyklisch oder eine Kombination davon ist.


     
    2. Teilweise fluorierte Ketonverbindung nach Anspruch 1, wobei die teilweise fluorierte Ketonverbindung ausgewählt ist aus der Gruppe, bestehend aus C3F7OCFHCF2C(O)CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH3, CF3OCFHCF2C(O)CH3, C4F9OCFHCF2C(O)CH3, CF3OC3F6OCFHCF2C(O)CH3, C2F5OCFHCF2C(O)CH3, (CF3)2CFCF2OCFHCF2C(O)CH3, C5F11OCFHCF2C(O)CH3, HCF2CF2CF2OCFHCF2C(O)CH3, CH3OCF2CF2CF2OCFHCF2C(O)CH3, CH3C(O)CF2CFHOC4F8OCFHCF2C(O)CH3, C3F7OCFHCF2C(O)CH2CH3, C3F7OCFHCF2C(O)CH2CH2CH3, C3F7OCFHCF2C(O)CH(CH3)2, C4F9OCFHCF2C(O)CH2CH3, C4F9OCFHCF2C(O)CH2CH2CH3, C4F9OCFHCF2C(O)CH(CH3)2, CF3OC3F6OCFHCF2C(O)CH2CH3, CF3OC3F6OCFHCF2C(O)CH2CH2CH3, CF3OC3F6OCFHCF2C(O)CH(CH3)2, CF3OCFHCF2C(O)CH2CH3, CF3OCFHCF2C(O)CH2C2CH3, CF3OCFHCF2C(O)CH(CH3)2, C3F7OCF(CF3)CF2OCFHCF2C(O)CH2CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH2CH2CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH(CH3)2, CH3CH2(O)CCF2CFHOC4F8OCFHCF2C(O)CH2CH3, CH3CH2CH2C(O)CF2CFHOC4F8OCFHCF2C(O)CH2CH2CH3, (CH3)2CH(O)CCF2CFHOC4F8OCFHCF2C(O)CH(CH3)2 und Mischungen davon.
     
    3. Teilweise fluoriertes Keton nach Anspruch 1, wobei jedes RH, RH1 und RH2 unabhängig linear ist.
     
    4. Teilweise fluoriertes Keton nach Anspruch 3, wobei RH Methyl ist und Rf ausgewählt ist aus:

            -CF2CF2CF2CF3, und -CF2CF2CF3.


     
    5. Teilweise fluoriertes Keton nach Anspruch 3, wobei RH1 und RH2 jeweils Methyl sind und Rf-CF2CF2CF2CF2- ist.
     
    6. Verfahren zum Entfernen eines Verunreinigungsstoffs von einem Artikel, das das Inkontaktbringen des Artikels mit einer Zusammensetzung umfasst, die mindestens eine teilweise fluorierte Ketonverbindung nach Anspruch 1 umfasst.
     
    7. Verfahren zum Herstellen eines geschäumten Kunststoffs, das das Verdampfen einer Treibmittelmischung in Gegenwart von mindestens einem schäum baren Polymer oder den Vorläufern von mindestens einem schäumbaren Polymer umfasst, wobei die Treibmittelmischung mindestens eine teilweise fluorierte Ketonverbindung nach Anspruch 1 umfasst.
     
    8. Verfahren zur Übertragung von Wärme, das die Übertragung von Wärme zwischen einer Wärmequelle und einem Kühlkörper durch die Verwendung eines Wärmeübertragungsmittels umfasst, das mindestens eine teilweise fluorierte Ketonverbindung nach Anspruch 1 umfasst.
     
    9. Verfahren zum Abscheiden einer Beschichtung auf einem Substrat, das Folgendes umfasst:
    Aufbringen, auf mindestens einen Teil mindestens einer Oberfläche des Substrats, einer Zusammensetzung, die (a) eine Lösungsmittelzusammensetzung, die die mindestens teilweise fluorierte Ketonverbindung nach Anspruch 1 umfasst, und (b) mindestens ein Beschichtungsmaterial, das in dem Lösungsmittel lösbar oder dispergierbar ist, umfasst.
     


    Revendications

    1. Cétone partiellement fluorée de formule :

            RHC(=O)CF2CFHORf,

    ou

            RH1C(=O)CF2CFHORfOCFHCF2C(=O)RH2

    dans laquelle chacun de RH, RH1 et RH2 est, indépendamment, un groupe alkyle ayant de 1 à 4 atomes de carbone,

    dans laquelle Rf est un fragment alkyle ou fragment alkylène fluoré et dans laquelle le fragment alkyle ou alkylène a de 1 à 6 atomes de carbone, et

    dans laquelle chacun de RH, RH1 et RH2 est, indépendamment, linéaire, ramifié, cyclique, ou une combinaison de ceux-ci.


     
    2. Composé de cétone partiellement fluorée selon la revendication 1, dans laquelle le composé de cétone partiellement fluorée est choisi dans le groupe constitué de C3F7OCFHCF2C(O)CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH3, CF3OCFHCF2C(O)CH3, C4F9OCFHCF2C(O)CH3, CF3OC3F6OCFHCF2C(O)CH3, C2F5OCFHCF2C(O)CH3, (CF3)2CFCF2OCFHCF2C(O)CH3, C5F11OCFHCF2C(O)CH3, HCF2CF2CF2OCFHCF2C(O)CH3, CH3OCF2CF2CF2OCFHCF2C(O)CH3, CH3C(O)CF2CFHOC4F8OCFHCF2C(O)CH3, C3F7OCFHCF2C(O)CH2CH3, C3F7OCFHCF2C(O)CH2CH2CH3, C3F7OCFHCF2C(O)CH(CH3)2, C4F9OCFHCF2C(O)CH2CH3, C4F9OCFHCF2C(O)CH2CH2CH3, C4F9OCFHCF2C(O)CH(CH3)2, CF3OC3F6OCFHCF2C(O)CH2CH3, CF3OC3F6OCFHCF2C(O)CH2CH2CH3, CF3OC3F6OCFHCF2C(O)CH(CH3)2, CF3OCFHCF2C(O)CH2CH3, CF3OCFHCF2C(O)CH2CH2CH3, CF3OCFHCF2C(O)CH(CH3)2, C3F7OCF(CF3)CF2OCFHCF2C(O)CH2CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH2CH2CH3, C3F7OCF(CF3)CF2OCFHCF2C(O)CH(CH3)2, CH3CH2(O)CCF2CFHOC4F8OCFHCF2C(O)CH2CH3, CH3CH2CH2C(O)CF2CFHOC4F8OCFHCF2C(O)CH2CH2CH3, (CH3)2CH(O)CCF2C FHOC4F8OCFHCF2C(O)CH(CH3)2, et des mélanges de ceux-ci.
     
    3. Cétone partiellement fluorée selon la revendication 1, dans laquelle chacun de RH, RH1 et RH2 est, indépendamment, linéaire.
     
    4. Cétone partiellement fluorée selon la revendication 3, dans laquelle RH est méthyle et Rf est choisi parmi :

            -CF2CF2CF2CF3 et -CF2CF2CF3.


     
    5. Cétone partiellement fluorée selon la revendication 3, dans laquelle RH1 et RH2 sont chacun méthyle et Rf est -CF2CF2CF2CF2-.
     
    6. Procédé d'élimination d'un contaminant d'un article comprenant la mise en contact dudit article avec une composition comprenant au moins un composé de cétone partiellement fluorée selon la revendication 1.
     
    7. Procédé de préparation d'un plastique alvéolaire comprenant la vaporisation d'un mélange d'agent d'expansion en présence d'au moins un polymère expansible ou des précurseurs d'au moins un polymère expansible, ledit mélange d'agent d'expansion comprenant au moins un composé de cétone partiellement fluorée selon la revendication 1.
     
    8. Procédé de transfert de chaleur comprenant le transfert de chaleur entre une source de chaleur et un dissipateur thermique par l'utilisation d'un agent de transfert de chaleur comprenant au moins un composé de cétone partiellement fluorée selon la revendication 1.
     
    9. Procédé de dépôt d'un revêtement sur un substrat comprenant :
    l'application sur au moins une partie d'au moins une surface dudit substrat d'une composition comprenant (a) une composition solvante comprenant au moins le composé de cétone partiellement fluorée selon la revendication 1 et (b) au moins un matériau de revêtement qui est soluble ou dispersible dans ladite composition solvante.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description




    Non-patent literature cited in the description