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    • 专利摘要:
    The invention relates to a composition comprising at least one polyol ester lubricant and a refrigerant F comprising 1-chloro-3,3,3-trifluoropropene. The invention also relates to various uses of this composition.
    公开号:FR3056222A1
    申请号:FR1658751
    申请日:2016-09-19
    公开日:2018-03-23
    发明作者:Wissam Rached
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    The present invention relates to a composition containing 1-chloro-3,3,3trifluoropropene and at least one lubricant, suitable for use in refrigeration, air conditioning and heat pump.
    TECHNICAL BACKGROUND
    The problems posed by substances that deplete the atmospheric ozone layer were dealt with in Montreal, where the protocol requiring a reduction in the production and use of chlorofluorocarbons (CFCs) was signed. This protocol has been the subject of amendments which have forced the abandonment of CFCs and extended the regulation to other products, including hydrochlorofluorocarbons (HCFCs).
    The refrigeration and air conditioning industry has invested heavily in the substitution of these refrigerants and this is how hydrofluorocarbons (HFCs) were marketed.
    In the automotive industry, the air conditioning systems of vehicles sold in many countries have gone from a chlorofluorocarbon (CFC-12) refrigerant to that of hydrofluorocarbon (1,1,1,2 tetrafluoroethane: HFC-134a ), less harmful to the ozone layer. However, with regard to the objectives set by the Kyoto protocol, HFC-134a (GWP = 1430) is considered to have a high warming power. The contribution to the greenhouse effect of a fluid is quantified by a criterion, the GWP (Global Warming Potential) which summarizes the warming power by taking a reference value of 1 for carbon dioxide.
    Hydrofluoroolefins (HFO) have a low heating power and therefore meet the objectives set by the Kyoto Protocol. Document JP 4-110388 discloses hydrofluoropropenes as a heat transfer agent.
    In the industrial field, the most widely used refrigeration machines are based on evaporative cooling of a liquid refrigerant. After vaporization, the fluid is compressed and then cooled in order to return to the liquid state and thus continue the cycle.
    The refrigeration compressors used are of the alternative, spiro-orbital, centrifugal or screw type. In general, the internal lubrication of compressors is essential to reduce wear and warming of moving parts, improve their sealing and protect them against corrosion.
    In addition to the good properties of heat transfer agent, for a refrigerant to be accepted commercially it must in particular have thermal stability and compatibility with lubricants. Indeed, it is highly desirable that the refrigerant is compatible with the lubricant used in the compressor, present in the majority of refrigeration systems. This combination of refrigerant and lubricant is important for the implementation and efficiency of the refrigeration system, in particular the lubricant must be sufficiently soluble or miscible in the refrigerant throughout the operating temperature range.
    There is therefore a need to find new pairs of refrigerant and lubricant, in particular thermally stable, suitable for use in refrigeration, air conditioning and heat pump.
    DESCRIPTION OF THE INVENTION
    The present application relates to a composition comprising a refrigerant F comprising 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), and at least one lubricant based on polyol esters (POE).
    In the context of the invention, "HCFO-1233zd" refers to 1-chloro-3,3,3trifluoropropene, regardless of whether it is the cis or trans form. The terms "HCFO-1233zdZ" and "trans-HCFO-1233zdE" refer to the cis- and trans- forms of 1-chloro-3,3,3-trifluoropropene, respectively. The term “HCFO-1233zd” therefore covers HCFO-1233zdZ, HCFO-1233zdE, and all mixtures of the two isomeric forms in all proportions.
    Unless otherwise stated, throughout the application, the proportions of compounds indicated are given in percentages by mass.
    The Applicant has discovered that the compositions according to the invention are advantageously thermally stable.
    Refrigerant
    According to one embodiment, the refrigerant F comprises at least one stabilizing compound.
    The stabilizing compound according to the invention can be any stabilizing compound known in the field of refrigerants.
    Among the stabilizers, mention may in particular be made of nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-ter-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated or alkenyl or aromatic alkyl) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphonates, thiols and lactones.
    According to a preferred embodiment, the stabilizing compound is a C3 to C6 alkene and comprising a single double bond.
    Preferably, the stabilizing compound is chosen from the group consisting of propene, butenes, pentenes and hexenes. Butenes and pentenes are preferred. Pentenes are even more particularly preferred.
    The C3 to C6 alkene stabilizing compounds may be straight or branched chain. They are preferably branched chain.
    Preferably, said stabilizing compounds have a boiling temperature less than or equal to 100 ° C, more preferably less than or equal to 75 ° C, and more particularly preferably less than or equal to 50 ° C.
    In the context of the invention, by "boiling temperature" means the boiling temperature at a pressure of 101.325 kPa, as determined according to standard NF EN 378-1 of April 2008.
    Preferably also, they have a solidification temperature less than or equal to 0 ° C, preferably less than or equal to -25 ° C, and more particularly preferably less than or equal to -50 ° C.
    The solidification temperature is determined according to Test No. 102: Melting point / melting range (OECD Guidelines for the Testing of Chemicals, Section 1, OECD Publishing, Paris, 1995, available at http://dx.doi.Org/10.1787/9789264069534-fr).
    Preferred stabilizing compounds of the invention are chosen from the following group:
    - goal-1-ene;
    - cis-but-2-ene;
    - trans-but-2-ene;
    - 2-methylprop-1-ene;
    - pent-1-ene;
    - cis-pent-2-ene;
    - trans-pent-2-ene;
    - 2-methylbut-1-ene;
    - 2-methylbut-2-ene; and
    - 3-methylbut-1-ene.
    Among the preferred compounds, mention may be made of 2-methyl-but-2-ene, of formula (CH3) 2C = CH-CH3 (boiling temperature of approximately 39 ° C); and 3-methyl-but-1-ene, of formula CH3-CH (CH3) -CH = CH2 (boiling temperature of approximately 25 ° C).
    Two or more of two of the above compounds can also be used in combination.
    The mass proportion of the stabilizing compound (s), as described above, in the refrigerant F can in particular be: from 0.01 to 0.05%; or from 0.05 to 0.1%; or from 0.1 to 0.2%, or from 0.2 to 0.3%; or from 0.3 to 0.4%; or from 0.4 to 0.5%; or from 0.5 to 0.6%; or from 0.6 to 0.7%; or from 0.7 to 0.8%; or from 0.8 to 0.9%; or from 0.9 to 1%; or from 1 to 1.2%; or from 1.2 to 1.5%, or from 1.5 to 2%; or from 2 to 3%; or from 3 to 4%; or from 4 to 5%, based on the total mass of the refrigerant F.
    According to a preferred embodiment, the refrigerant F consists of 1chloro-3,3,3-trifluoropropene (HCFO-1233zd) and at least one alkene stabilizing compound at C3 to C6 and comprising a single double bond, said compound stabilizer preferably being 2-methyl-but-2-ene.
    In refrigerant F, HCFO-1233zd can be in the form of HCFO1233zdE, or in the form of a mixture of HCFO-1233zdE and HCFO-1233zdZ.
    According to a preferred embodiment, the mass proportion of HCFO1233zdE, relative to the total of HCFO-1233zd, is greater than or equal to 90%, or to 91%, or to 92%, or to 93%, or to 94%, or 95%, or 96%, or 97%, or 98%, or 99%, or 99.1%, or 99.2%, or 99.3%, or 99, 4%, or 99.5%, or 99.6%, or 99.7%, or 99.8%, or 99.9%, or 99.91%, or 99.92 %, or 99.93%, or 99.94%, or 99.95%, or 99.96%, or 99.97%, or 99.98%, or 99.99% .
    The presence of stabilizing compound (s) in the refrigerant F makes it possible in particular to limit or prevent an increase in the proportion of HCFO1233zdZ in the composition over time and / or in the case of application of relatively high temperatures. .
    In the composition of the invention, the mass proportion of HCFO-1233zd can represent in particular from 1 to 5% of the composition; or from 5 to 10% of the composition; or from 10 to 15% of the composition; or from 15 to 20% of the composition; or from 20 to 25% of the composition; or from 25 to 30% of the composition; or from 30 to 35% of the composition; or from 35 to 40% of the composition; or from 40 to 45% of the composition; or from 45 to 50% of the composition; or from 50 to 55% of the composition; or from 55 to 60% of the composition; or from 60 to 65% of the composition; or from 65 to 70% of the composition; or from 70 to 75% of the composition; or from 75 to 80% of the composition; or from 80 to 85% of the composition; or from 85 to 90% of the composition; or from 90 to 95% of the composition; or from 95 to 99% of the composition; or from 99 to 99.5% of the composition; or from 99.5 to 99.9% of the composition; or more than 99.9% of the composition. The content of HCFO-1233zd can also vary in several of the above ranges: for example from 50 to 55% and from 55 to 60%, i.e. from 50 to 60%, etc.
    Preferably, the composition of the invention comprises more than 50% by weight of HCFO-1233zd, preferably from 50% to 99%.
    Lubricant
    According to the invention, the lubricant can comprise one or more polyol esters.
    According to one embodiment, the polyol esters are obtained by reaction of at least one polyol, with a carboxylic acid or with a mixture of carboxylic acids.
    In the context of the invention, and unless otherwise stated, the term "polyol" means a compound containing at least two hydroxyl groups (-OH).
    Polyol esters A)
    According to one embodiment, the polyol esters according to the invention correspond to the following formula (I):
    R 1 [OC (O) R 2 ] n (I) in which:
    R 1 is a linear or branched hydrocarbon radical, optionally substituted with at least one hydroxyl group and / or comprising at least one heteroatom chosen from the group consisting of -O-, -N-, and -S-;
    each R 2 is, independently of each other, chosen from the group consisting of:
    o i) H;
    o ii) an aliphatic hydrocarbon radical; o iii) a branched hydrocarbon radical;
    o iv) a mixture of a radical ii) and / or iii), with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms; and n is an integer of at least 2.
    In the context of the invention, the term “hydrocarbon radical” is understood to mean a radical composed of carbon and hydrogen atoms.
    According to one embodiment, the polyols have the following general formula (II):
    R 1 (OH) n (II) in which:
    R 1 is a linear or branched hydrocarbon radical, optionally substituted by at least one hydroxyl group, preferably by two hydroxyl groups, and / or comprising at least one heteroatom chosen from the group consisting of -O-, -N-, and -S-; and n is an integer of at least 2.
    Preferably, R 1 is a hydrocarbon radical, linear or branched, comprising from 4 to 40 carbon atoms, preferably from 4 to 20 carbon atoms.
    Preferably, R 1 is a linear or branched hydrocarbon radical comprising at least one oxygen atom.
    Preferably, R 1 is a branched hydrocarbon radical comprising from 4 to 10 carbon atoms, preferably 5 carbon atoms, substituted by two hydroxyl groups.
    According to a preferred embodiment, the polyols comprise from 2 to 10 hydroxyl groups, preferably from 2 to 6 hydroxyl groups.
    The polyols according to the invention may comprise one or more oxyalkylene groups, in this particular case it is polyether polyols.
    The polyols according to the invention can also comprise one or more nitrogen atoms. For example, the polyols can be alkanol amines containing from 3 to 6 OH groups. Preferably, the polyols are alkanol amines containing at least two OH groups, and preferably at least three.
    According to the present invention, the preferred polyols are chosen from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentyl glycol, 1,2-butanediol, 1,4-butanediol, 1,3-butanediol, pentaerythritol, dipentaerythritol, tripentaerythritol, triglycerol, trimethylolpropane, sorbitol, hexaglycerol, and mixtures thereof.
    According to the invention, the carboxylic acids can correspond to the following general formula (III):
    R 2 COOH (III) in which:
    R 2 is chosen from the group consisting of: ο i) H;
    o ii) an aliphatic hydrocarbon radical; o iii) a branched hydrocarbon radical;
    o iv) a mixture of a radical ii) and / or iii), with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms.
    Preferably, R 2 is an aliphatic hydrocarbon radical comprising from 1 to 10, preferably from 1 to 7 carbon atoms, and in particular from 1 to 6 carbon atoms.
    Preferably, R 2 is a branched hydrocarbon radical comprising from 4 to 20 carbon atoms, in particular from 5 to 14 carbon atoms, and preferably from 6 to 8 carbon atoms.
    According to a preferred embodiment, a branched hydrocarbon radical has the following formula (IV):
    -C (R 3 ) R 4 ) (R 5 ) (IV) in which R 3 , R 4 and R 5 are, independently of each other, an alkyl group, and at least one of the alkyl groups contains at least two atoms of carbon. Such branched alkyl groups, once linked to the carboxyl group, are known under the name "neo group", and the corresponding acid as "neo acid". Preferably, R 3 and R 4 are methyl groups and R 10 is an alkyl group comprising at least two carbon atoms.
    According to the invention, the radical R 2 may comprising one or more carboxy groups, or ester groups such as -COOR 6 , with R 6 representing an alkyl, hydroxyalkyl radical or a hydroxyalkyloxy alkyl group.
    Preferably, the acid R 2 COOH of formula (III) is a monocarboxylic acid.
    Examples of carboxylic acids in which the hydrocarbon radical is aliphatic are in particular: formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid and heptanoic acid .
    Examples of carboxylic acids in which the hydrocarbon radical is branched are in particular: 2-ethyl-n-butyric acid, 2-hexyldecanoic acid, isostearic acid, 2-methyl-hexanoic acid, 2-methylbutanoic acid, 3methylbutanoic acid, 3,5,5-trimethyl-hexanoic acid, 2-ethylhexanoic acid, neoheptanoic acid, and neodecanoic acid.
    The third type of carboxylic acids which can be used in the preparation of polyol esters of formula (I) are carboxylic acids comprising an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms. Mention may for example be made of: decanoic acid, dodecanoic acid, lauric acid, stearic acid, myristic acid, behenic acid, etc. Among the dicarboxylic acids, mention may be made of maleic acid , succinic acid, adipic acid, sebacic acid ...
    According to a preferred embodiment, the carboxylic acids used to prepare the polyol esters of formula (I) comprise a mixture of monocarboxylic and dicarboxylic acids, the proportion of monocarboxylic acids being in the majority. The presence of dicarboxylic acids results in particular in the formation of polyol esters of high viscosity.
    In particular, the reaction for forming the polyol esters of formula (I) by reaction between the carboxylic acid and the polyols is an acid-catalyzed reaction. These include a reversible reaction, which can be completed by the use of a large amount of acid or by removing the water formed during the reaction.
    The esterification reaction can be carried out in the presence of organic or inorganic acids, such as sulfuric acid, phosphoric acid, etc.
    Preferably, the reaction is carried out in the absence of a catalyst.
    The amount of carboxylic acid and polyol can vary in the mixture depending on the desired results. In the particular case where all the hydroxyl groups are esterified, a sufficient quantity of carboxylic acid must be added to react with all the hydroxyls.
    According to one embodiment, when using mixtures of carboxylic acids, these can react sequentially with the polyols.
    According to a preferred embodiment, when using a mixture of carboxylic acids, a polyol reacts first with a carboxylic acid, typically the highest molecular weight carboxylic acid, followed by the reaction with the acid. carboxylic having an aliphatic hydrocarbon chain.
    According to one embodiment, the esters can be formed by reaction between the carboxylic acids (or their anhydride derivatives or esters) with the polyols, in the presence of acids at high temperature, while removing the water formed during the reaction. . Typically, the reaction can be carried out at a temperature of from 75 to 200 ° C.
    According to another embodiment, the polyol esters formed may comprise hydroxyl groups which have not all reacted, in this case these are partially esterified polyol esters.
    According to a preferred embodiment, the polyol esters are obtained from pentaerythritol alcohol, and from a mixture of carboxylic acids: isononanoic acid, at least one acid having an aliphatic hydrocarbon radical comprising from 8 to 10 carbon atoms, and heptanoic acid. The preferred polyol esters are obtained from pentaerythritol, and from a mixture of 70% isononanoic acid, 15% of at least one carboxylic acid having an aliphatic hydrocarbon radical comprising from 8 to 10 carbon atoms, and 15% heptanoic acid. We can for example cite Solest 68 oil sold by CPI Engineering Services
    Inc.
    Polyol esters B)
    According to another embodiment, the polyol esters of the invention comprise at least one ester of one or more branched carboxylic acids comprising at most 8 carbon atoms. The ester is obtained in particular by reacting said branched carboxylic acid with one or more polyols.
    Preferably, the branched carboxylic acid comprises at least 5 carbon atoms. In particular, the branched carboxylic acid contains from 5 to 8 carbon atoms, and preferably it contains 5 carbon atoms.
    Preferably, the above-mentioned branched carboxylic acid does not contain 9 carbon atoms. In particular, said carboxylic acid is not 3,5,5-trimethylhexanoic acid.
    According to a preferred embodiment, the branched carboxylic acid is chosen from 2-methylbutanoic acid, 3-methylbutanoic acid, and their mixtures.
    According to a preferred embodiment, the polyol is chosen from the group consisting of neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and their mixtures.
    According to a preferred embodiment, the polyol esters are obtained from:
    i) a carboxylic acid chosen from 2-methylbutanoic acid, 3methylbutanoic acid, and mixtures thereof; and ii) a polyol selected from the group consisting of neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.
    Preferably, the polyol ester is that got at go of the acid methylbutanoic and pentaerythritol. Preferably, the polyol ester is thatmethylbutanoic acid and dipentaerythritol. got at go of the acid Preferably, the polyol ester is thatmethylbutanoic and pentaerythritol. got at go of the acid Preferably, the polyol ester is thatmethylbutanoic acid and dipentaerythritol. got at go of the acid
    Preferably, the polyol ester is that obtained from 2methylbutanoic acid and neopentyl glycol.
    Polyol esters C)
    According to another embodiment, the polyol esters according to the invention are poly (neopentylpolyol) esters obtained by:
    i) reaction of a neopentylpolyol having the following formula (V):
    HO-CH2-C-CH2-OR • H (V) in which:
    each R represents, independently of one another, CH3, C2H5 or CH2OH;
    p is an integer ranging from 1 to 4;
    with at least one monocarboxylic acid having 2 to 15 carbon atoms, and in the presence of an acid catalyst, the molar ratio between the carboxyl groups and the hydroxyl groups being less than 1: 1, to form a poly (neopentyl ) partially esterified polyol; and ii) reaction of the partially esterified poly (neopentyl) polyol composition obtained at the end of step i), with another carboxylic acid having from 2 to 15 carbon atoms, to form the final composition of esters) poly (neopentylpolyol).
    Preferably, reaction i) is carried out with a molar ratio ranging from 1: 4 to 1: 2. Preferably, the neopentylpolyol has the following formula (VI):
    ch 2 oh
    R— C — R
    CH 2 OH (VI) in which each R represents, independently of one another, CH3, C2H5 or
    CH2OH.
    Preferred neopentyl polyols are those chosen from pentaerythritol, dipentaerythritol, tri pentaerythritol, tetraerythritol, trimethylolpropane, trimethylolethane, and neopentyl glycol. In particular, neopentylpolyol is pentaerythritol.
    Preferably, a single neopentylpolyol is used to produce the POE-based lubricant. In some cases, two or more neopentylpolyols are used. This is especially the case when a commercial pentaerythritol product includes small amounts of dipentaerythritol, tripentaerythritol, and tetraerythritol.
    According to a preferred embodiment, the abovementioned monocarboxylic acid comprises from 5 to 11 carbon atoms, preferably from 6 to 10 carbon atoms.
    The monocarboxylic acids have in particular the following general formula (VII):
    R’C (O) OH (VII) in which R ’is a linear or branched C1-C12 alkyl radical, a C6-C12 aryl radical, a C6-C30 aralkyl radical. Preferably, R ’is a C4-C10, and preferably C5-C9, alkyl radical.
    In particular, the monocarboxylic acid is chosen from the group consisting of butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, n-octanoic acid, n acid -nonanoic, n-decanoic acid, 3-methylbutanoic acid, 2-methylbutanoic acid, 2,4dimethylpentanoic acid, 2-ethylhexanoic acid, 3.3 acid , 5 trimethylhexanoic acid, benzoic acid, and mixtures thereof.
    According to a preferred embodiment, the monocarboxylic acid is nheptanoic acid, or a mixture of n-heptanoic acid with another linear monocarboxylic acid, in particular n-octanoic acid and / or ndecanoic acid. Such a mixture of monocarboxylic acid can comprise between 15 and 100 mol% of heptanoic acid and between 85 and 0 mol% of other monocarboxylic acid (s). In particular, the mixture comprises between 75 and 100 mol% of heptanoic acid, and between 25 and 0 mol% of a mixture of octanoic acid and decanoic acid in a 3: 2 molar ratio.
    According to a preferred embodiment, the polyol esters comprise: i) from 45% to 55% by weight of a monopentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms;
    ii) less than 13% by weight of a dipentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms;
    iii) less than 10% by weight of a tripentaerythritol ester with at least one monocarboxylic acid having from 2 to 15 carbon atoms; and iv) at least 25% by weight of an ester of tetraerythritol and other pentaerythritol oligomers, with at least one monocarboxylic acid having 2 to 15 carbon atoms.
    Polyol esters D)
    According to another embodiment, the polyol esters according to the invention have the following formula (VIII):
    (VIII) in which:
    R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are, independently of each other, H or CH3; a, b, c, y, x and z, are, independently of each other, an integer; a + x, b + y, and c + z are, independently of each other, integers ranging from 1 to 20;
    R 13 , R 14 and R 15 are, independently of each other, chosen from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyle, arylcycloalkylalkyle, arylalkylcycloalkyle, cycloalkylalkylaryl and cycloalkylarylalkyle,
    R 13 , R 14 and R 15 , having from 1 to 17 carbon atoms, and which may be optionally substituted.
    According to a preferred embodiment, each of R 13 , R 14 and R 15 represents, independently of each other, a linear or branched alkyl group, an alkenyl group, a cycloalkyl group, said alkyl, alkenyl or cycloalkyl groups which may comprise at least at least one heteroatom chosen from N, O, Si, F or S. Preferably, each of R 13 , R 14 and R 15 has, independently of each other, from 3 to 8 carbon atoms, preferably from 5 to 7 carbon atoms.
    Preferably, a + x, b + y, and c + z are, independently of each other, integers ranging from 1 to 10, preferably from 2 to 8, and even more preferably from 2 to 4.
    Preferably, R 7 , R 8 , R 9 , R 10 , R 11 and R 12 represent H.
    The polyol esters of formula (VIII) above can typically be prepared as described in paragraphs [0027] to [0030] of international application WO2012 / 177742.
    In particular, the polyol esters of formula (VIII) are obtained by esterification of glycerol alkoxylates (as described in paragraph [0027] of WO2012 / 177742) with one or more monocarboxylic acids having from 2 to 18 carbon atoms.
    According to a preferred embodiment, the monocarboxylic acids have one of the following formulas:
    R 13 COOH
    R 14 COOH and
    R 15 COOH in which R 13 , R 14 and R 15 are as defined above. Derivatives of carboxylic acids can also be used, such as anhydrides, esters and acyl halides.
    The esterification can be carried out with one or more monocarboxylic acids. Preferred monocarboxylic acids are those chosen from the group consisting of acetic acid, propanoic acid, butyric acid, isobutanoic acid, pivalic acid, pentanoic acid, isopentanoic acid, acid hexanoic, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, palmitoleic acid, lemonellic acid, undecenoic acid, lauric acid, undecylenic acid, linolenic acid, arachidic acid, behenic acid, tetrahydrobenzoic acid, abietic acid, hydrogenated or not, 2-ethylhexanoic acid, furoic acid, benzoic acid, 4acetylbenzoic acid, pyruvic acid, 4-tert-butyl-benzoic acid, naphthenic acid, 2-methyl benzoic acid, salicylic acid, their isomers, their methyl esters, and mixtures thereof.
    Preferably, the esterification is carried out with one or more monocarboxylic acids chosen from the group consisting of pentanoic acid, 2methylbutanoic acid, n-hexanoic acid, n-heptanoic acid, 3,3,5-trimethylhexanoic , 2-ethylhexanoic acid, n-octanoic acid, nnonanoic acid and isononanoic acid.
    Preferably, the esterification is carried out with one or more monocarboxylic acids chosen from the group consisting of butyric acid, isobutyric acid, n-pentanoic acid, 2-methylbutanoic acid, 3methylbutanoic acid, l n-hexanoic greedy, n-heptanoic greedy, n-octanoic acid, 2-ethylhexanoic acid, 3,3,5-trimethylhexanoic acid, n-nonanoic acid, decanoic acid, undecanoic acid, undecelenic acid, lauric acid, stearic acid, isostearic acid, and mixtures thereof.
    According to another embodiment, the polyol esters according to the invention have the following formula (IX):
    .19 in which:
    each of R 17 and R 18 , is, independently of each other, H or CH3; each of m and n, is, independently of one another, an integer, with m + n, being an integer ranging from 1 to 10;
    R 16 and R 19 are, independently of one another, chosen from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyle, arylcycloalkylalkyle, arylalkylcycloalkyle, cycloalkylalkylaryl and cycloalkylarylalkyle,
    R 16 and R 19 , having from 1 to 17 carbon atoms, and which may be optionally substituted.
    According to a preferred embodiment, each of R 16 and R 19 represents, independently of one another, a linear or branched alkyl group, an alkenyl group, a cycloalkyl group, said alkyl, alkenyl or cycloalkyl groups which may comprise at least at least one heteroatom chosen from N, O, Si, F or S. Preferably, each of R 16 and R 19 has, independently of one another, from 3 to 8 carbon atoms, preferably from 5 to 7 carbon atoms.
    According to a preferred embodiment, each of R 17 and R 18 represents H, and / or m + n is an integer ranging from 2 to 8, from 4 to 10, from 2 to 5, or from 3 to 5. In particular , m + n is 2, 3 or 4.
    According to a preferred embodiment, the polyol esters of formula (IX) above are diesters of triethylene glycol, diesters of tetraethylene glycol, in particular with one or two monocarboxylic acids having from 4 to 9 carbon atoms.
    The polyol esters of formula (IX) above can be prepared by esterifications of an ethylene glycol, of a propylene glycol, or of an oligo- or polyalkylene glycol, (which can be an oligo- or polyethylene glycol, oligo- or polypropylene glycol, or an ethylene glycol-propylene glycol block copolymer), with one or two monocarboxylic acids having from 2 to 18 carbon atoms. The esterification can be carried out in an identical manner to the esterification reaction used to prepare the polyol esters of formula (VIII) above.
    In particular, monocarboxylic acids identical to those used to prepare the polyol esters of formula (VIII) above, can be used to form the polyol esters of formula (IX).
    According to one embodiment, the lubricant based on polyol esters according to the invention comprises from 20 to 80%, preferably from 30 to 70%, and preferably from 40 to 60% by weight of at least one ester of polyol of formula (VIII), and from 80 to 20%, preferably from 70 to 30%, and preferably from 60 to 40% by weight of at least one polyol ester of formula (IX).
    In general, certain alcohol functions may not be esterified during the esterification reaction, however their proportion remains low. Thus, the POEs can comprise between 0 and 5 mol% relative of CH2OH units with respect to the -CH 2 -OC (= O) - units.
    The preferred POE lubricants according to the invention are those having a viscosity of 1 to 1000 centiStokes (cSt) at 40 ° C, preferably from 10 to 200 cSt, even more preferably from 20 to 100 cSt, and advantageously from 30 to 80 cSt .
    The international classification of oils is given by standard ISO3448 (NF T60141) and according to which oils are designated by their class of average viscosity measured at a temperature of 40 ° C.
    Composition
    In the composition of the invention, the mass proportion of refrigerant F can represent in particular from 1 to 5% of the composition; or from 5 to 10% of the composition; or from 10 to 15% of the composition; or from 15 to 20% of the composition; or from 20 to 25% of the composition; or from 25 to 30% of the composition; or from 30 to 35% of the composition; or from 35 to 40% of the composition; or from 40 to 45% of the composition; or from 45 to 50% of the composition; or from 50 to 55% of the composition; or from 55 to 60% of the composition; or from 60 to 65% of the composition; or from 65 to 70% of the composition; or from 70 to 75% of the composition; or from 75 to 80% of the composition; or from 80 to 85% of the composition; or from 85 to 90% of the composition; or from 90 to 95% of the composition; or from 95 to 99% of the composition; or from 99 to 99.5% of the composition; or from 99.5 to 99.9% of the composition; or more than 99.9% of the composition. The content of refrigerant F can also vary in several of the above ranges: for example from 50 to 55%, and from 55 to 60%, that is to say from 50 to 60%, etc.
    According to a preferred embodiment, the composition of the invention comprises more than 50% by weight of refrigerant F, and in particular from 50% to 99% by weight, relative to the total weight of the composition.
    In the composition of the invention, the mass proportion of lubricant based on polyol esters (POE) can represent in particular from 1 to 5% of the composition; or from 5 to 10% of the composition; or from 10 to 15% of the composition; or from 15 to 20% of the composition; or from 20 to 25% of the composition; or from 25 to 30% of the composition; or from 30 to 35% of the composition; or from 35 to 40% of the composition; or from 40 to 45% of the composition; or from 45 to 50% of the composition; or from 50 to 55% of the composition; or from 55 to 60% of the composition; or from 60 to 65% of the composition;
    or from 65 to 70% of the composition; or from 70 to 75% of the composition; or from 75 to 80% of the composition; or from 80 to 85% of the composition; or from 85 to 90% of the composition; or from 90 to 95% of the composition; or from 95 to 99% of the composition; or from 99 to 99.5% of the composition; or from 99.5 to 99.9% of the composition; or more than 99.9% of the composition. The lubricant content can also vary in several of the above ranges: for example from 50 to 55%, and from 55 to 60%, ie from 50 to 60%, etc. For example, the content of lubricant represents between 10 and 50% by weight of the composition.
    According to one embodiment, the composition according to the invention comprises:
    - A refrigerant F comprising 1-chloro-3,3,3-trifluoropropene (HCFO1233zd), and optionally a C3 to C6 alkene stabilizing compound and comprising a single double bond as described above; and
    at least one lubricant based on polyol esters (POE), in particular chosen from the polyol esters A), B), C) or D) described above, in particular the polyol esters of formulas (I), (VIII) or (XI).
    According to a preferred embodiment, the composition comprises:
    - a refrigerant F comprising 1-chloro-3,3,3-trifluoropropene (HCFO1233zd), the mass proportion of HCFO-1233zdE, relative to the total of HCFO-1233zd, being in particular greater than or equal to 95%, or 99%, or 99.9%, and a stabilizing compound selected from 2-methyl-but-2-ene and 3-methyl-but-2ene; and
    - at least one lubricant based on polyol esters, in particular of formula (I).
    The composition according to the invention may comprise one or more additives (which are essentially not heat transfer compounds for the intended application).
    The additives can in particular be chosen from nanoparticles, stabilizers (different from the stabilizing compounds of the invention), surfactants, tracer agents, fluorescent agents, odorous agents and solubilizing agents.
    Preferably, the additives are not lubricants.
    According to one embodiment, the composition of the invention is a heat transfer composition.
    According to a preferred embodiment, the present invention relates to a heat transfer composition comprising:
    a refrigerant F comprising 1-chloro-3,3,3-trifluoropropene (HCFO1233zd), at least one lubricant based on polyol esters (POE); and at least one additive chosen from nanoparticles, stabilizers (different from the stabilizing compounds of the invention), surfactants, tracer agents, fluorescent agents, odorous agents and solubilizing agents.
    The stabilizer or stabilizers, when they are present, preferably represent at most 5% by mass in the heat transfer composition. Among the stabilizers, mention may in particular be made of nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-ter-butyl-4-methylphenol, epoxides (optionally fluorinated or perfluorinated or alkenyl or aromatic alkyl) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphonates, thiols and lactones.
    As nanoparticles, it is possible in particular to use carbon nanoparticles, metal oxides (copper, aluminum), T1O2, AI2O3, M0S2 ...
    As tracer agents (capable of being detected), mention may be made of hydrofluorocarbons, deuterated or not, deuterated hydrocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide and combinations thereof. The tracer is different from the heat transfer compound (s) making up the heat transfer fluid (refrigerant F).
    As solubilizers, mention may be made of hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1.1 , 1trifluoroalkanes. The solubilizer is different from the heat transfer compound (s) making up the heat transfer fluid (refrigerant F).
    Mention may be made, as fluorescent agents, of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanhtenes, fluoresceins and derivatives and combinations thereof.
    As odorants, mention may be made of alkylacrylates, allylacrylates, acrylic acids, acrylesters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulfides, allylisothiocyanates, alkanoic acids , amines, norbornenes, norbornene derivatives, cyclohexene, heterocyclic aromatics, ascaridole, o-methoxy (methyl) -phenol and combinations thereof.
    The composition according to the invention can also comprise at least one other heat transfer compound, in addition to HCFO-1233zd. Such another optional heat transfer compound may in particular be a hydrocarbon, ether, hydrofluoroether, hydrofluorocarbon, hydrochlorofluorocarbon, hydrofluoroolefin, hydrochloroolefin or hydrochlorofluoroolefin compound.
    By way of example, said other heat transfer compound can be chosen from 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mmz, E or Z isomer), 3.3 , 4,4,4pentafluorobut-1-ene (HFO-1345fz), 2,4,4,4-tetrafluorobut-1-ene (HFO-1354mfy), 1,1,1,3,3-pentafluoropropane (HFC -245fa), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), difluoromethane (HFC-32), 1,1,1 , 2tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1difluoroethane (HFC-152a), pentafluoroethane (HFC-125), 1,1,1,3 , 3pentafluorobutane (HFC-365mfc), methoxynonafluorobutane (HFE7100), butane (HC-600), 2-methylbutane (HC-601a), pentane (HC-601), ethyl ether, methyl acetate and combinations of these.
    By “heat transfer compound”, respectively “heat transfer fluid” or “refrigerant”, is meant a compound, respectively a fluid, capable of absorbing heat by evaporating at low temperature and low pressure and to reject heat by condensing at high temperature and high pressure, in a vapor compression circuit. Generally, a heat transfer fluid can comprise a single, two, three or more of three heat transfer compounds. In particular, the refrigerant F is a heat transfer fluid.
    By "heat transfer composition" is meant a composition comprising a heat transfer fluid and optionally one or more additives which are not heat transfer compounds for the intended application. In particular, the composition according to the invention is a heat transfer composition.
    Uses
    The present invention also relates to the use of the above composition, as a heat transfer composition, in a vapor compression circuit. The present invention relates to the use of the composition according to the invention, as a heat transfer composition in a vapor compression system, or in a heat engine.
    The present invention also relates to a heat transfer method based on the use of an installation comprising a vapor compression system which contains the composition of the invention as a heat transfer composition. The heat transfer process can be a process of heating or cooling a fluid or a body.
    According to one embodiment, the vapor compression system is;
    - an air conditioning system; or
    - a refrigeration system; or
    - a freezing system; or
    - a heat pump system.
    The composition of the invention can also be used in a process for the production of mechanical work or electricity, in particular in accordance with a Rankine cycle.
    The invention also relates to a heat transfer installation comprising a vapor compression circuit containing the above composition as a heat transfer composition.
    According to one embodiment, this installation is chosen from mobile or stationary refrigeration, heating (heat pump), air conditioning and freezing installations, and heat engines.
    It can notably be a heat pump installation, in which case the fluid or body that is heated (generally air and possibly one or more products, objects or organisms) is located in a room or a vehicle interior (for mobile installation). According to a preferred embodiment, it is an air conditioning installation, in which case the fluid or body which is cooled (generally air and possibly one or more products, objects or organisms) is located in a room or vehicle interior (for mobile installation). It can be a refrigeration installation or a freezing installation (or cryogenic installation), in which case the fluid or body that is cooled generally comprises air and one or more products, objects or organisms , located in a room or container.
    The invention also relates to a method of heating or cooling a fluid or a body by means of a vapor compression system containing a heat transfer composition, said method successively comprising the evaporation of the heat transfer composition, compression of the heat transfer composition, condensation of the heat transfer composition and expansion of the heat transfer composition, wherein the heat transfer composition is the composition described above above.
    The invention also relates to a method of producing electricity by means of a heat engine, said method successively comprising evaporating the heat transfer composition, the expansion of the heat transfer composition in a turbine allowing generating electricity, condensing the heat transfer composition and compressing the heat transfer composition, wherein the heat composition is the composition described above.
    The vapor compression circuit containing a heat transfer composition includes at least one evaporator, compressor, condenser and expander, as well as lines for transporting heat transfer fluid therebetween. The evaporator and the condenser include a heat exchanger allowing heat exchange between the heat transfer composition and another fluid or body.
    As a compressor, it is possible in particular to use a centrifugal compressor with one or more stages or a centrifugal mini-compressor. Rotary, piston or screw compressors can also be used. The compressor can be driven by an electric motor or by a gas turbine (for example powered by vehicle exhaust gases, for mobile applications) or by gear.
    A centrifugal compressor is characterized in that it uses rotary elements to radially accelerate the heat transfer composition; it typically comprises at least one rotor and one diffuser housed in an enclosure. The heat transfer composition is introduced into the center of the rotor and circulates towards the periphery of the rotor undergoing acceleration. Thus, on the one hand the static pressure increases in the rotor, and especially on the other hand at the level of the diffuser, the speed is converted into an increase in the static pressure. Each rotor / diffuser assembly constitutes a stage of the compressor. Centrifugal compressors can have from 1 to 12 stages, depending on the desired final pressure and the volume of fluid to be treated.
    The compression ratio is defined as the ratio of the absolute pressure of the heat transfer composition at the outlet to the absolute pressure of said composition at the inlet.
    The speed of rotation for large centrifugal compressors ranges from 3000 to 7000 rpm. Small centrifugal compressors (or mini centrifugal compressors) generally operate at a rotational speed ranging from 40,000 to 70,000 revolutions per minute and have a small rotor (generally less than 0.15 m).
    A multistage rotor can be used to improve compressor efficiency and limit energy costs (compared to a single stage rotor). For a two-stage system, the output of the first stage of the rotor feeds the inlet of the second rotor. The two rotors can be mounted on a single axis. Each stage can provide a fluid compression ratio of approximately 4 to 1, that is, the absolute outlet pressure can be approximately four times the absolute suction pressure. Examples of two-stage centrifugal compressors, in particular for automotive applications, are described in documents US 5,065,990 and US 5,363,674.
    The centrifugal compressor can be driven by an electric motor or by a gas turbine (for example powered by vehicle exhaust gases, for mobile applications) or by gear.
    The installation may include a coupling of the regulator with a turbine to generate electricity (Rankine cycle).
    The installation may also optionally include at least one heat transfer fluid circuit used to transmit heat (with or without change of state) between the circuit of the heat transfer composition and the fluid or body to be heated or cooled.
    The installation can also optionally include two (or more) vapor compression circuits, containing identical or distinct heat transfer compositions. For example, the vapor compression circuits can be coupled together.
    The vapor compression circuit operates according to a conventional vapor compression cycle. The cycle includes changing the state of the heat transfer composition from a liquid phase (or two-phase liquid / vapor) to a vapor phase at a relatively low pressure, then compressing the composition in the vapor phase to a relatively high pressure, the change of state (condensation) of the heat transfer composition from the vapor phase to the liquid phase at a relatively high pressure, and the reduction in pressure to restart the cycle.
    In the case of a cooling process, heat from the fluid or from the body which is cooled (directly or indirectly, via a heat transfer fluid) is absorbed by the heat transfer composition, upon evaporation of the latter, and at a relatively low temperature compared to the environment. The cooling methods include the methods of air conditioning (with mobile installations, for example in vehicles, or stationary), refrigeration and freezing or cryogenics.
    In the case of a heating process, heat is transferred (directly or indirectly, via a heat transfer fluid) from the heat transfer composition, during the condensation thereof, to the fluid or to the body that the it is heated to a relatively high temperature compared to the environment. The installation for carrying out the heat transfer is called in this case "heat pump".
    It is possible to use any type of heat exchanger for implementing the heat transfer compositions according to the invention, and in particular co-current heat exchangers or, preferably, counter heat exchangers. -current.
    However, according to a preferred embodiment, the invention provides that the cooling and heating methods, and the corresponding installations, include a counter-current heat exchanger, either in the condenser or in the evaporator. In fact, the heat transfer compositions according to the invention are particularly effective with counter-current heat exchangers. Preferably, both the evaporator and the condenser include a counter-current heat exchanger.
    According to the invention, by "counter-current heat exchanger" means a heat exchanger in which heat is exchanged between a first fluid and a second fluid, the first fluid at the inlet of the exchanger exchanging heat with the second fluid at the outlet of the exchanger, and the first fluid at the outlet of the exchanger exchanging heat with the second fluid at the inlet of the exchanger.
    For example, counter-current heat exchangers include devices in which the flow of the first fluid and the flow of the second fluid are in opposite directions, or almost opposite. Exchangers operating in cross-current mode with counter-current tendency are also included among the counter-current heat exchangers within the meaning of the present application.
    In "low temperature refrigeration" processes, the inlet temperature of the heat transfer composition to the evaporator is preferably
    -45 ° C to -15 ° C, in particular from -40 ° C to -20 ° C, more particularly preferably from -35 ° C to -25 ° C and for example around -30 ° C; and the temperature at the start of the condensation of the heat transfer composition in the condenser is preferably from 25 ° C to 80 ° C, in particular from 30 ° C to 60 ° C, more particularly from 35 ° C to 55 ° C and for example around 40 ° C.
    In "moderate temperature cooling" processes, the inlet temperature of the heat transfer composition to the evaporator is preferably from -20 ° C to 10 ° C, especially from -15 ° C to 5 ° C , more particularly preferably from -10 ° C to 0 ° C and for example around -5 ° C; and the temperature at the start of the condensation of the heat transfer composition in the condenser is preferably from 25 ° C to 80 ° C, in particular from 30 ° C to 60 ° C, more particularly from 35 ° C to 55 ° C and for example around 50 ° C. These methods can be refrigeration or air conditioning methods.
    In “moderate temperature heating” processes, the inlet temperature of the heat transfer composition to the evaporator is preferably from -20 ° C to 10 ° C, especially from -15 ° C to 5 ° C , more particularly preferably from -10 ° C to 0 ° C and for example around -5 ° C; and the temperature at the start of the condensation of the heat transfer composition in the condenser is preferably from 25 ° C to 80 ° C, in particular from 30 ° C to 60 ° C, more particularly from 35 ° C to 55 ° C and for example around 50 ° C.
    In "high temperature heating" processes, the inlet temperature of the heat transfer composition to the evaporator is preferably from -20 ° C to 90 ° C, in particular from 10 ° C to 90 ° C, more particularly preferably from 50 ° C to 90 ° C and for example about 80 ° C; and the temperature at the start of the condensation of the heat transfer composition in the condenser is preferably from 70 ° C to 160 ° C, in particular from 90 ° C to 150 ° C, more particularly from 110 ° C to 140 ° C and for example around 135 ° C.
    The compositions according to the invention are particularly advantageous in refrigerated transport.
    Any movement of perishable products under refrigerated space is considered to be refrigerated transport. Food or pharmaceutical products represent an important part of perishable products.
    Refrigerated transport can be carried out by truck, rail or boat, possibly using multi-platform containers which can be adapted as well on trucks, rails or boats.
    In refrigerated transport, the temperature of the refrigerated spaces is between -30 ° C and 16 ° C. The refrigerant charge in transport by truck, rail or multi-platform containers varies between 4 kg and 8 kg of refrigerant. Installations in boats can contain between 100 and 500kg.
    The most widely used refrigerant to date is R404A.
    The operating temperatures of the refrigeration systems depend on the refrigeration temperature requirements and the outdoor climatic conditions. The same refrigeration installation must be able to cover a wide range of temperatures between -30 ° C and 16 ° C and operate in both cold and hot climates.
    The most restrictive condition in evaporation temperature is -30 ° C.
    Preferably also, in the installation according to the invention, the temperature of the composition used as a heat transfer composition remains higher than the solidification temperature of the stabilizing compound as defined above, in order to avoid any deposition solid matter in the circuit.
    All of the embodiments described above can be combined with each other. Thus, each preferred compound of the composition can be combined with each preferred polyol ester (esters A, B, C or D), in the various proportions mentioned. The various preferred compositions can be used in the various applications described above.
    The following examples illustrate the invention without, however, limiting it.
    EXAMPLES
    The thermal stability tests were carried out according to standard ASHRAE 97-2007: “sealed glass tube method to test the Chemical stability of materials for use within refrigerant Systems”.
    The test conditions are as follows: mass of fluid (with stabilizer): 2 g mass of lubricant: 5 g dry air: 0.2 milli-moles temperature: 180 ° C. duration: 14 days commercial lubricants were tested:
    - PVE Bitzer 32 oil (Bitzer / ldemitsu);
    - Solest 68 oil (CPI Engineering services inc).
    The refrigerant F includes:
    - 0.5% by weight of 2-methyl-2-butene; and
    - 99.5% by weight of HCFO-1233zd.
    The lubricant was introduced into a 16 ml glass tube. The tube was then drawn under vacuum and the fluid F was added to it as well as the air. The tube was then welded to close it and placed in an oven at 180 ° C for 14 days.
    At the end of the test, the gas phase was recovered to be analyzed by gas chromatography: the main impurities were identified by GC / MS (gas chromatography coupled to mass spectrometry).
    Invention Comparative Oil Solest 68 PVE Bitzer 32 %molar HFO-1233zdE 98,691 92.623 88,194 90,070 HFO-1233zdZ 0.039 0.040 0.035 0.034 2-methyl-2-butene 0.838 0.860 0.924 0.944 Original impurities(in the fluidrefrigerant, beforemix with thelubricant) <0.1 <0.1 <0.1 <0.1 New impurities 0.387 0.420 10,748 8.87
    The CG analysis shows the formation of a very high percentage of new impurities (greater than 8 mol%) with PVE oil compared to a very low percentage with POE oil (less than 0.5 mol%).
    Thus, tests show that the HFO-1233zd / POE oil mixture is more thermally stable than the HFO-1233zd / PVE oil mixture.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. Composition comprising at least one lubricant based on polyol esters and a refrigerant F comprising 1-chloro-3,3,3-trifluoropropene.
    [2" id="c-fr-0002]
    2. Composition according to Claim 1, in which the refrigerant F comprises at least one stabilizing compound, preferably a C 3 to C 6 alkene and comprising a single double bond, in particular chosen from 2-methyl-but-2-ene and 3-methyl-but-1-ene.
    [3" id="c-fr-0003]
    3. Composition according to any one of claims 1 or 2, in which the 1-chloro-3,3,3-trifluoropropene is in trans form in a mass proportion greater than or equal to 90%, preferably greater than or equal to 95 %, preferably greater than or equal to 99%, ideally greater than or equal to 99.5%, or even greater than 99.9%.
    [4" id="c-fr-0004]
    4. Composition according to any one of claims 1 to 3, in which the polyol esters correspond to the following formula (I) below:
    R 1 [OC (O) R 2 ] n (I) in which:
    - R 1 is a linear or branched hydrocarbon radical, optionally substituted with at least one hydroxyl group and / or comprising at least one heteroatom chosen from the group consisting of -O-, -N-, and -S-;
    - each R 2 is, independently of each other, chosen from the group consisting of:
    o I) H;
    o ii) an aliphatic hydrocarbon radical; o iii) a branched hydrocarbon radical;
    o iv) a mixture of a radical ii) and / or iii), with an aliphatic hydrocarbon radical comprising from 8 to 14 carbon atoms; and
    - n is an integer of at least 2.
    [5" id="c-fr-0005]
    5. Composition according to any one of claims 1 to 3, in which the polyol esters are obtained from polyol chosen from the group consisting of neopentyl glycol, glycerol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol , and their mixtures.
    [6" id="c-fr-0006]
    6. Composition according to any one of claims 1 to 3 and 5, in which the polyol esters are obtained from at least one branched carboxylic acid comprising from 5 to 8 carbon atoms.
    [7" id="c-fr-0007]
    7. Composition according to any one of claims 1 to 3, in which the polyol esters are poly (neopentylpolyol) esters obtained by:
    i) reaction of a neopentylpolyol having the following formula (V):
    HO
    CH2-C-CH2-O (V) in which:
    o each R represents, independently of each other, CH3, C2H5 or CH2OH;
    where p is an integer ranging from 1 to 4;
    with at least one monocarboxylic acid having 2 to 15 carbon atoms, in the presence of an acid catalyst, the molar ratio between the carboxyl groups and the hydroxyl groups being less than 1: 1, to form a poly (neopentyl) composition partially esterified polyol; and ii) reaction of the partially esterified poly (neopentyl) polyol composition obtained at the end of step i), with another carboxylic acid having from 2 to 15 carbon atoms, to form the composition of poly esters (neopentylpolyol).
    [8" id="c-fr-0008]
    8. Composition according to any one of claims 1 to 3, in which the polyol esters have one of the following formulas (VIII) or (IX):
    (VIII) in which:
    R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are, independently of each other, H or CH3; a, b, c, y, x and z, are, independently of each other, an integer; a + x, b + y, and c + z are, independently of each other, integers ranging from 1 to 20;
    R 13 , R 14 and R 15 are, independently of each other, chosen from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls, arylcycloalkyls cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyle, arylcycloalkylalkyle, arylalkylcycloalkyle, cycloalkylalkylaryl and cycloalkylarylalkyle,
    R 13 , R 14 and R 15 , having from 1 to 17 carbon atoms, and which may be optionally substituted.
    or (IX) in which:
    each of R 17 and R 18 , is, independently of each other, H or CH3; each of m and n, is, independently of one another, an integer, with m + n, being an integer ranging from 1 to 10;
    R 13 * * 16 and R 19 are, independently of one another, chosen from the group consisting of aliphatic or branched alkyls, alkenyls, cycloalkyls, aryls, alkylaryls, arylalkyls, alkylcycloalkyls, cycloalkylalkyls , arylcycloalkyls of cycloalkylaryls, alkylcycloalkylaryles, alkylarylcycloalkyles, arylcycloalkylalkyles, arylalkylcycloalkyles, cycloalkylalkylaryl and cycloalkylarylalkyles,
    R 16 and R 19 , having from 1 to 17 carbon atoms, and which may be optionally substituted.
    [9" id="c-fr-0009]
    9. Composition according to any one of claims 1 to 8, in which the lubricant represents between 10 and 50% by weight of the composition.
    [10" id="c-fr-0010]
    10. Use of the composition according to any one of claim 1 to 9, as a heat transfer composition in a vapor compression system, or in a heat engine.
    [11" id="c-fr-0011]
    11. A heat transfer installation comprising a circuit containing a composition according to any one of claims 1 to 9, as a heat transfer composition.
    [12" id="c-fr-0012]
    12. Installation according to claim 11, chosen from mobile or stationary installations for heating by heat pump, air conditioning, refrigeration, freezing and heat engines.
    [13" id="c-fr-0013]
    13. A method of producing electricity by means of a heat engine, said method successively comprising the evaporation of the heat transfer composition, the expansion of the heat transfer composition in a turbine making it possible to generate electricity, condensing the heat transfer composition and compressing the heat transfer composition, wherein the heat transfer composition is a composition according to one of claims 1 to 9.
    [14" id="c-fr-0014]
    14. A method of heating or cooling a fluid or a body by means of a vapor compression system containing a heat transfer composition, said method comprising successively
    Evaporation of the heat transfer composition, compression of the heat transfer composition, condensation of the heat composition and expansion of the heat transfer composition, wherein the heat transfer composition is a composition according to one of claims 1 to 9.
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    同族专利:
    公开号 | 公开日
    US10669465B2|2020-06-02|
    CN109790445A|2019-05-21|
    EP3516007B1|2022-01-05|
    FR3056222B1|2020-01-10|
    JP2019535841A|2019-12-12|
    WO2018051036A1|2018-03-22|
    CA3036255A1|2018-03-22|
    US20190276721A1|2019-09-12|
    CN109790445B|2021-05-04|
    MX2019003081A|2019-08-05|
    DK3516007T3|2022-02-28|
    EP3516007A1|2019-07-31|
    JP6980771B2|2021-12-15|
    KR20190054116A|2019-05-21|
    引用文献:
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    法律状态:
    2017-08-10| PLFP| Fee payment|Year of fee payment: 2 |
    2018-03-23| PLSC| Publication of the preliminary search report|Effective date: 20180323 |
    2018-08-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-08-15| PLFP| Fee payment|Year of fee payment: 4 |
    2020-08-12| PLFP| Fee payment|Year of fee payment: 5 |
    2021-08-12| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1658751A|FR3056222B1|2016-09-19|2016-09-19|COMPOSITION BASED ON 1-CHLORO-3,3,3-TRIFLUOROPROPENE|
    FR1658751|2016-09-19|FR1658751A| FR3056222B1|2016-09-19|2016-09-19|COMPOSITION BASED ON 1-CHLORO-3,3,3-TRIFLUOROPROPENE|
    DK17780816.9T| DK3516007T3|2016-09-19|2017-09-15|COMPOSITION INCLUDING 1-CHLORO-3,3,3-TRIFLUOROPROPENE|
    KR1020197010640A| KR20190054116A|2016-09-19|2017-09-15|Composition comprising 1-chloro-3,3,3-trifluoropropene|
    PCT/FR2017/052473| WO2018051036A1|2016-09-19|2017-09-15|Composition comprising 1-chloro-3,3,3-trifluoropropene|
    EP17780816.9A| EP3516007B1|2016-09-19|2017-09-15|Composition comprising 1-chloro-3,3,3-trifluoropropene|
    CA3036255A| CA3036255A1|2016-09-19|2017-09-15|Composition comprising 1-chloro-3,3,3-trifluoropropene|
    CN201780057560.2A| CN109790445B|2016-09-19|2017-09-15|Compositions comprising 1-chloro-3, 3, 3-trifluoropropene|
    MX2019003081A| MX2019003081A|2016-09-19|2017-09-15|Composition comprising 1-chloro-3,3,3-trifluoropropene.|
    US16/333,003| US10669465B2|2016-09-19|2017-09-15|Composition comprising 1-chloro-3,3,3-trifluoropropene|
    JP2019515333A| JP6980771B2|2016-09-19|2017-09-15|Compositions based on 1-chloro-3,3,3-trifluoropropene|
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