WO2010098447A1 - Refrigerant composition containing hydrofluoropropane with low-global warming potential - Google Patents

Refrigerant composition containing hydrofluoropropane with low-global warming potential Download PDF

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Publication number
WO2010098447A1
WO2010098447A1 PCT/JP2010/053095 JP2010053095W WO2010098447A1 WO 2010098447 A1 WO2010098447 A1 WO 2010098447A1 JP 2010053095 W JP2010053095 W JP 2010053095W WO 2010098447 A1 WO2010098447 A1 WO 2010098447A1
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WIPO (PCT)
Prior art keywords
refrigerant composition
refrigerant
hydrofluoropropene
hfo
stabilizer
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PCT/JP2010/053095
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French (fr)
Japanese (ja)
Inventor
立美 土屋
俊 柴沼
康夫 山田
眸 有元
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ダイキン工業株式会社
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Priority to JP2011501670A priority Critical patent/JP5590023B2/en
Publication of WO2010098447A1 publication Critical patent/WO2010098447A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/102—Alcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/101—Containing Hydrofluorocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants

Definitions

  • the present invention relates to a stabilized refrigerant composition containing hydrofluoropropene such as 2,3,3,3-tetrafluoropropene having a low global warming potential.
  • chlorofluorofluorocarbon CFC
  • hydrochlorofluorocarbon HCFC
  • chlorofluorocarbons CFC
  • chlorofluorocarbons released into the atmosphere destroy the ozone layer and have a serious adverse effect on the earth's ecosystem including humans. Therefore, the use and production of Freon, which already has a high risk of ozone depletion, has been regulated by international agreements.
  • dichlorodifluoromethane (CFC-12) has been mainly used as a refrigerant for household refrigerators, car air conditioners, turbo chillers, container refrigeration equipment, etc., but it is a hydrofluorocarbon due to the aforementioned regulations.
  • 1,1,2-tetrafluoroethane (HFC-134a).
  • HFO-1225ye 1,2,3,3,3-pentafluoro-1-propene
  • HFO-1234yf 2,3,3,3 Hydrofluoropropenes
  • Patent Document 1 and the like report a stabilization technique.
  • Patent Document 1 describes that stabilizers such as phenolic compounds, thiophosphates, benzoquinones, and arylalkyl ethers are added to the fluoroolefin.
  • the present invention provides a refrigerant composition containing hydrofluoropropene having a low global warming potential (GWP), which can maintain a stable state for a long time even in the presence of air (oxygen).
  • GWP global warming potential
  • the present inventor has at least one stabilizer (antioxidant) selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohols. It has been found that a refrigerant composition containing an agent can maintain a stable state for a long time even in the presence of air (oxygen). Such a refrigerant composition can maintain stability over a long period of time even when air (oxygen) is mixed during refrigerant filling construction of a stationary air conditioner such as a home air conditioner.
  • the conventional mechanism for decomposing HFC refrigerants without unsaturated bonds is the reduction of halogen atoms, and the durability of the refrigerant is determined by tests taking into account decomposition acceleration factors such as temperature, metal (catalyst), moisture, and air. Evaluating stability.
  • a mixture of air and a metal catalyst (Fe, Cu, or Al) in refrigeration oil and refrigerant (HFO-1225ye) at 175 ° C. is 2 After heating for a week, the appearance of the mixture is evaluated. That is, the evaluation is performed by the same thermal stability acceleration test as that of the conventional (HFC refrigerant).
  • this method merely evaluates the appearance of the liquid phase of the mixture (coloring grade; Rating), and does not allow the acid in the system to corrode or reduce the refrigeration capacity when hydrofluoropropene is used as a refrigerant. Sufficient evaluation has not been made on the occurrence.
  • the decomposition mechanism of the refrigerant composition containing hydrofluoropropene is dominated by the oxidation reaction between the unsaturated bond and oxygen, and CF 3 COOH, HF, which is the main cause of the above problem due to the oxidation reaction. It has been clarified that acids such as these are formed, and the evaluation method has been established. Specifically, after treating a refrigerant composition containing hydrofluoropropene at a predetermined temperature for a predetermined time, and evaluating the acid content of the refrigerant composition after the treatment, the thermal stability of hydrofluoropropene more realistically Evaluation of sex became possible.
  • the present invention relates to a refrigerant composition containing the following hydrofluoropropene.
  • a refrigerant composition comprising hydrofluoropropene and a stabilizer, wherein the stabilizer is at least one selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohol valences.
  • the hydrofluoropropene is 2,3,3,3-tetrafluoropropene (HFO-1234yf), (Z or E-) 1,3,3,3-tetrafluoropropene (HFO-1234ze), (Z or E- ) 1,2,3,3,3-pentafluoropropene (HFO-1225ye), (Z or E-) 1,1,3,3,3-pentafluoropropene (HFO-1225zc), and (Z or E Item 2)
  • the refrigerant composition according to item 1 which is at least one selected from the group consisting of 3,3,3-trifluoropropene (HFO-1243zf).
  • the refrigerant composition according to Item 1 wherein the content of the stabilizer relative to 100 parts by weight of hydrofluoropropene is 0.1 to 5.0 parts by weight. 4).
  • Item 2. The refrigerant composition according to Item 1, further comprising refrigerating machine oil. 5).
  • the refrigerant composition is selected from the group consisting of a vapor compression heat pump such as a refrigerator, a refrigerator, a mobile air conditioner, a refrigerator (chiller), a container refrigeration apparatus, a home air conditioner, a commercial air conditioner, or a water heater.
  • a vapor compression heat pump such as a refrigerator, a refrigerator, a mobile air conditioner, a refrigerator (chiller), a container refrigeration apparatus, a home air conditioner, a commercial air conditioner, or a water heater.
  • Item 6 The refrigerant composition according to any one of Items 1 to 5, which is used in 7).
  • a method for stabilizing a refrigerant composition comprising hydrofluoropropene the method comprising stabilizing at least one selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohol valences
  • a stabilizing method comprising adding an agent. 8).
  • a method for evaluating the stability of a refrigerant composition containing hydrofluoropropene and a stabilizer wherein the refrigerant composition is heated in a sealed container in the presence and / or absence of oxygen, and then treated.
  • the evaluation method characterized by analyzing the acid content of a refrigerant composition after.
  • the refrigerant composition of the present invention does not contain chlorine and bromine, there is no danger of destroying the ozone layer even if released into the atmosphere.
  • the global warming potential is low, the stability in the presence of air (oxygen) is at the same level as that of existing HFC refrigerants, and it has sufficient durability even when used as a refrigerant composition for stationary refrigerators.
  • the refrigerant composition of the present invention contains hydrofluoropropene and a stabilizer, and the stabilizer is at least one selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohol valences. It is characterized by being.
  • refrigerant hydrofluoropropene examples include 2,3,3,3-tetrafluoropropene (HFO-1234yf) and (Z or E-) 1,3,3,3-tetrafluoropropene (HFO-1234ze). , (Z or E-) 1,2,3,3,3-pentafluoropropene (HFO-1225ye), (Z or E-) 1,1,3,3,3-pentafluoropropene (HFO-1225zc) (Z or E-) 3,3,3-trifluoropropene (HFO-1243zf) and the like. These hydrofluoropropenes can be used alone or in admixture of two or more.
  • the refrigerant composition of the present invention may be further mixed with an existing HFC refrigerant in addition to the hydrofluoropropene.
  • the content ratio of the HFC refrigerant is 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less based on the total weight of the refrigerant.
  • the refrigerant composition of the present invention may contain refrigerating machine oil in addition to hydrofluoropropene depending on applications.
  • refrigerating machine oil A well-known thing can be used as refrigerating machine oil.
  • at least one of poly (oxy) alkylene glycols, polyvinyl ethers, and polyol esters is particularly preferable.
  • the kinematic viscosity of the refrigerating machine oil at 40 ° C. is preferably 5 to 400 cSt, more preferably 30 to 400 cSt.
  • the kinematic viscosity in this specification is a value measured with a capillary viscometer among viscometers defined in JIS Z 8803 (liquid viscosity-measurement method).
  • the amount of refrigerant containing hydrofluoropropene is usually 16 to 50 parts by weight with respect to 10 parts by weight of refrigerating machine oil, but it varies depending on the specifications of the oil tank of the refrigerating machine. It is not particularly limited to this range.
  • the refrigerant composition of the present invention comprises an aliphatic alcohol having 1 to 4 carbon atoms and an alcohol number of 1 to 4 as a stabilizer (antioxidant) in order to impart stability to oxygen of a refrigerant containing hydrofluoropropene. Contained as.
  • examples of the monohydric alcohol include C 1 to C 4 linear and branched alcohols.
  • the alkyl group of the alcohol may contain an ether bond.
  • Specific examples include methanol, ethanol, (n-, iso-) propyl alcohol, (n-, sec-, tert-) butanol and the like, preferably methanol, isopropyl alcohol, sec-butanol and tert-butanol. is there.
  • polyhydric alcohol examples include C 2 -C 4 alcohols having 2 to 4 hydroxyl groups, and the hydrocarbon chain in the alcohol may contain an ether bond.
  • specific examples include ethylene glycol, propylene glycol, glycerol, erythritol and the like. Ethylene glycol is preferable.
  • the aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 carbon numbers, which are stabilizers, can be used alone or in admixture of two or more.
  • the blending amount of the stabilizer is usually 0.1 to 5.0 parts by weight, more preferably 0.3 to 3.0 parts by weight with respect to 100 parts by weight of hydrofluoropropene.
  • the content of the stabilizer relative to the hydrofluoropropene is too small, the effect cannot be obtained, and if it is too large, it is not preferable from the viewpoint of sludge generation and economy, so the above range is suitable.
  • a solvent may be optionally added within a range that does not adversely affect the stability of oxygen and hydrofluoropropene.
  • a solvent include glyme compounds, preferably diglyme.
  • the addition amount of the solvent is 30% by weight or less, preferably 15 to 25% by weight, more preferably 15 to 20% by weight, based on the total weight of the stabilizer.
  • the stabilizer used in the present invention has a very high stabilizing (acid value prevention) effect compared to that exemplified in Patent Document 1 (see Examples and Comparative Examples).
  • Patent Document 1 merely evaluates the appearance of the liquid phase of the mixture (coloring grade; Rating), and the corrosion in the system due to the oxidative decomposition of hydrofluoropropene and the reduction of the refrigerating capacity. This is because the generation of acid, which is the main cause of this, has not been evaluated.
  • the heat treatment of the refrigerant composition in a sealed container in the presence and / or absence of oxygen, the acid content of the refrigerant composition after the treatment is performed. It is characterized by analyzing.
  • a shield tube for example, a shielded Pyrex (registered trademark) glass tube or the like
  • the evaluation method of the present invention corresponds to a so-called acceleration test, for example, the heating temperature can be set in the range of 90 to 200 ° C.
  • the heat treatment time can be set in the range of 72 to 720 hours.
  • coolant composition after a process it can implement by the method as described in an Example.
  • the evaluation method of the present invention it is possible to appropriately evaluate the generation of acids such as CF 3 COOH and HF due to an oxidation reaction, which is the main cause of problems such as corrosion in the system and a decrease in refrigeration capacity. Therefore, if the evaluation method of the present invention is used, it becomes possible to screen for a more realistic stabilizer.
  • the refrigerant composition of the present invention is described in, for example, Japanese Patent Application Laid-Open No. 2000-178543, Japanese Patent Application Laid-Open No. 2008-308610, Japanese Patent No. 2863159 and the like when a high degree of thermal stability is required.
  • An HFC refrigerant used in a conventional HFC refrigerant system or a heat stabilizer for refrigeration oil can be used in combination.
  • heat stabilizer examples include (i) aliphatic nitro compounds such as nitromethane, nitroethane and nitropropane, aromatic nitro compounds such as nitrobenzene and nitrostyrene, and aromatics such as p-isopropenyltoluene and diisopropenylbenzene. (Ii) phenols such as 2,6-di-t-butyl-p-cresol, epoxies such as 1,2-butylene oxide, and amines such as phenyl- ⁇ -naphthylamine Can be mentioned.
  • aliphatic nitro compounds such as nitromethane, nitroethane and nitropropane
  • aromatic nitro compounds such as nitrobenzene and nitrostyrene
  • aromatics such as p-isopropenyltoluene and diisopropenylbenzene.
  • phenols such as 2,6-di-t-butyl-p-
  • one or more compounds selected from the above (i) and (ii) can be used, and in this case, two or more compounds from the above (i) or (ii) are used. May be.
  • the amount of heat stabilizer used varies depending on the type of the stabilizer, but should be such that it does not interfere with the properties of the refrigerant performance.
  • the amount of heat stabilizer used is usually preferably about 0.1 to 5% by weight, more preferably about 0.3 to 3% by weight in the refrigerant composition.
  • the refrigerant composition of the present invention can be used for various applications such as a refrigerant, a heat transfer medium, a working fluid, and a foaming agent in the same manner as conventional chlorofluorocarbon.
  • refrigerant compositions for refrigerators, refrigerators, mobile air conditioners, refrigerators (chillers), container refrigeration equipment, household air conditioners, commercial air conditioners, steam compression heat pumps for water heaters, and other various low-temperature equipment Useful as.
  • it is useful as a refrigerant composition for use in stationary air conditioners and the like that require on-site refrigerant filling and have a high possibility of oxygen contamination.
  • Examples 1 to 10 and Comparative Examples 1 to 10 (Preparation of refrigerant composition) The following were prepared as refrigerants.
  • X: HFO-1234yf (CF 3 CF CH 2 manufactured by Daikin Industries)
  • Y comparative product
  • HFC-32 manufactured by CF 2 H 2 Daikin Industries
  • Z HFO-1225ye (CF 3 CH ⁇ CF 2 manufactured by Daikin Industries)
  • Each refrigerant composition was prepared so as to have the composition shown in Table 1 below.
  • Test example 1 Pyrex (registered trademark) glass tubes (ID8mm ⁇ ⁇ OD12mm ⁇ ⁇ L300mm) are filled with a total of 20 types of refrigerant compositions (Examples 1-10, Comparative Examples 1-10) shown in Table 1 (refrigerant + stabilizer). Further, an air test was carried out so that the oxygen concentration shown in Table 1 was adjusted, and after enclosing, an accelerated test was performed in which heating was performed at a temperature of 150 ° C. for one week (168 hours).
  • Total acid value analysis of refrigerating machine oil The total acid value of the refrigerating machine oil after gas recovery was measured by a method based on the total acid value analysis method of JIS K-2211 (refrigerating machine oil). Refrigeration machine oil after acceleration test is weighed, dissolved in toluene / isopropanol / water mixed solvent, neutralized with 1 / 100N KOH / ethanol solution using ⁇ -naphtholbenzein as indicator, and frozen from titration. The machine oil total acid value (mg ⁇ KOH / g) was measured.
  • Comparative Examples 1 to 3 each consisted of HFO-1234yf, HFC-32, and HFO-1225ye, all of which were evaluated for stability under anoxic conditions, and no signs of decomposition (acid generation) were observed. .
  • Comparative Examples 4 to 6 are obtained by coexisting oxygen with Comparative Examples 1 to 3, respectively.
  • the production of acid content is greatly increased in HFO-1234yf and HFO-1225ye, which are hydrofluoropropenes. This indicates that the stability of hydrofluoropropene in the presence of oxygen is extremely low compared to that of the conventional HFC refrigerant (HFC-32).
  • Comparative Example 7 a mixture of HFO-1234yf and HFC-32 and oxygen coexist, but the amount of acid content generated is approximately 80% of HFO-1234yf (Comparative Example 4) and is proportional to the composition ratio.
  • the acid content in Examples 1 to 9 is lower than that in Comparative Examples 4 to 9, indicating that the oxidation of hydrofluoropropene by oxygen is suppressed.
  • Example 2 HFO-1225ye is used as the refrigerant, but the effect of the stabilizer (B: methanol) can be confirmed in the same manner as HFO-1234yf alone (Example 1). Hydrofluoropropenes other than HFO-1234yf The inhibitory effect was recognized.
  • Example 8 a mixture of HFO-1234yf and HFC-32 was used as the refrigerant, but as with HFO-1234yf alone (Example 1), its inhibitory effect was also observed as a mixture with HFC-32.
  • Example 10 and Comparative Example 10 are refrigerant compositions containing refrigerating machine oil, and their performance is compared with and without a stabilizer.
  • Example 10 both the acid content in the gas and the total acid value of the refrigerating machine oil are reduced as compared with Comparative Example 10. This is presumably because the inhibitory effect of the stabilizer suppresses the oxidation of ether oil by oxygen as well as the suppression of acid generation by the reaction of HFO-1234yf and oxygen.
  • hydrofluoropropene such as 2,3,3,3-tetrafluoropropene and its composition are stabilized by a stabilizer so that they are equally stable to oxygen even in the presence of air (oxygen). I confirmed what I showed. Therefore, by adding the stabilizer of the present invention to hydrofluoropropene having an unsaturated bond, the stability in the presence of oxygen could be improved to the same level as that of the HFC refrigerant (HFC-32). Therefore, it has been found that the refrigerant composition of the present invention is useful as a refrigerant composition for stationary air conditioners that does not affect the global environment as much as possible and exhibits the same stability as conventional HFC refrigerants.

Abstract

Disclosed is a stabilized refrigerant composition that contains a hydrofluoropropane with low-global warming potential (GWP), whereby the refrigerant composition is able to maintain a stable state for a long period of time even in the presence of air (oxygen). Specifically disclosed is a refrigerant composition that contains a hydrofluoropropane and a stabilizer, and the stabilizer is at least one type selected from the group consisting of aliphatic alcohols with 1‑4 carbons and with an alcohol valence of 1‑4.

Description

温暖化係数の低いハイドロフルオロプロペンを含む冷媒組成物Refrigerant composition containing hydrofluoropropene with low global warming potential
　本発明は、温暖化係数の低い2,3,3,3－テトラフルオロプロペン等のハイドロフルオロプロペンを含む安定化された冷媒組成物に関する。 The present invention relates to a stabilized refrigerant composition containing hydrofluoropropene such as 2,3,3,3-tetrafluoropropene having a low global warming potential.
　従来、冷凍機における冷媒、ヒートポンプにおける熱媒体等として、クロロフルオロフルオロカーボン（CFC）、ハイドロクロロフルオロカーボン（HCFC）が使用されている。これらの単体、共沸組成物、混合物等はフロン又はフロン類と称されている。近年、大気中に放出されたフロン類がオゾン層を破壊し、人類を含む地球上の生態系に重大な悪影響を及ぼすことが指摘されている。そのため、既にオゾン層破壊の危険性が高いフロンについては国際的な取り決めにより、使用及び生産が規制されるに至っている。 Conventionally, chlorofluorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) have been used as refrigerants in refrigerators, heat media in heat pumps, and the like. These simple substances, azeotropic compositions, mixtures and the like are referred to as chlorofluorocarbons or chlorofluorocarbons. In recent years, it has been pointed out that chlorofluorocarbons released into the atmosphere destroy the ozone layer and have a serious adverse effect on the earth's ecosystem including humans. Therefore, the use and production of Freon, which already has a high risk of ozone depletion, has been regulated by international agreements.
　具体的には、ジクロロジフルオロメタン（CFC-12）は主に家庭用冷蔵庫、カーエアコン、ターボ冷凍機、コンテナ用冷凍装置等の冷媒として使用されてきたが、前述の規制によりハイドロフルオロカーボンである1,1,1,2－テトラフルオロエタン（HFC-134a）に代替されている。 Specifically, dichlorodifluoromethane (CFC-12) has been mainly used as a refrigerant for household refrigerators, car air conditioners, turbo chillers, container refrigeration equipment, etc., but it is a hydrofluorocarbon due to the aforementioned regulations. 1,1,2-tetrafluoroethane (HFC-134a).
　しかしながら、規制はより厳格化されてきている。例えば、ＥＵでは、Regulation on certain fluorinated greenhouse gases 及びDirective relating to emissions of f-gas form air conditioning systems fitted to carsの２つの法規制（Ｆガス規制）が２００６年６月に公布された。これによれば、２０１１年から新たに出荷される新型車及び２０１７年からは全ての車両に搭載されるモバイル型空調機器（カーエアコン）について、地球温暖化係数（ＧＷＰ）１５０以下の冷媒の使用が義務付けられた。そのため、現在搭載されているHFC-134aについても、ＧＷＰ１３００であることから代替候補としてＣＯ２等が提案されているものの、機器の改良の点、ＣＯ２が臨界流体であるため高温時の冷凍能力が不十分である点等、様々な問題を抱えている。また、一部の電気冷蔵庫の冷媒として、イソブタン（i-C4H10）等が用いられているが、非常に大きい燃焼力をもつため全ての分野で代替はされていない。 However, regulations are becoming stricter. For example, in the EU, two laws and regulations (F gas regulation) were promulgated in June 2006: Regulation on certain fluorinated greenhouse gases and Directive relating to emissions of f-gas form air conditioning systems fitted to cars. According to this, the use of refrigerants with a global warming potential (GWP) of 150 or less for new models shipped from 2011 and mobile type air conditioners (car air conditioners) installed in all vehicles from 2017 Was required. Therefore, although H2C-134a that is currently installed is GWP1300, CO 2 etc. have been proposed as an alternative candidate. However, since the CO 2 is a critical fluid, the refrigeration capacity at high temperature is improved. There are various problems such as insufficient points. In addition, isobutane (iC 4 H 10 ) or the like is used as a refrigerant in some electric refrigerators, but it has not been replaced in all fields because of its very large combustion power.
　上記を踏まえ、低ＧＷＰで、且つエネルギー効率、冷媒特性（冷凍能力、沸点、圧力等）を含むＬＣＣＰ（Life Cycle Climate Performance；製品寿命気候負荷）評価でHFC-134aとほぼ同等以上であり、機器の改良の必要性がないか又は軽微である、冷媒の開発が望まれている。 Based on the above, low GWP, energy efficiency, refrigerant characteristics (refrigeration capacity, boiling point, pressure, etc.), LCCP (Life Cycle Climate Performance) evaluation is almost equal to or higher than HFC-134a. There is a need to develop refrigerants that do not require or are minimally improved.
　この点、温暖化係数が低く分子内に不飽和結合を有する化合物として、例えば、1,2,3,3,3－ペンタフルオロ－１－プロペン（HFO-1225ye）、2,3,3,3－テトラフルオロ－１－プロペン（HFO-1234yf）等のハイドロフルオロプロペンが知られている。これらの化合物は地球温暖化係数が飽和ＨＦＣ化合物と比較すると低いため、それゆえ大気圏中の安定性が飽和ＨＦＣ化合物よりも劣る事が予想された。 In this respect, as a compound having a low warming potential and an unsaturated bond in the molecule, for example, 1,2,3,3,3-pentafluoro-1-propene (HFO-1225ye), 2,3,3,3 Hydrofluoropropenes such as tetrafluoro-1-propene (HFO-1234yf) are known. Since these compounds have a lower global warming potential than saturated HFC compounds, it was therefore expected that their stability in the atmosphere would be inferior to saturated HFC compounds.
　そこで本発明者は、ハイドロフルオロプロペンについての安定性を評価したところ、空気（酸素）共存下での安定性に問題が認められた。具体的には、冷媒組成物の実際の使用で到達すると考えられる温度域でも酸化分解が進行し、ＣＦ３ＣＯＯＨ、ＨＦなどの酸の生成が確認された。そのため、システム内の腐食や冷凍能力の低下、キャピラリーの閉塞等の問題が予想された。 Then, when this inventor evaluated the stability about hydrofluoro propene, the problem was recognized by stability in air (oxygen) coexistence. Specifically, oxidative decomposition proceeded even in a temperature range that would be reached by actual use of the refrigerant composition, and generation of acids such as CF 3 COOH and HF was confirmed. For this reason, problems such as corrosion in the system, a decrease in refrigeration capacity, and capillary blockage were expected.
　一般に、モバイルエアコンのように工場で冷媒が充填される装置であれば、施工管理がなされているため空気（酸素）の混入の可能性はほとんどない。しかしながら、定置式空調機等の装置の場合は、現場での冷媒充填施工が必要である。該冷媒充填施工は、施工業者の管理能力に委ねられており、これまでも冷凍能力低下等の不具合やトラブルの主原因として、空気（酸素）の混入が考えられた。 Generally, if a device such as a mobile air conditioner is filled with refrigerant in a factory, the construction management is performed, so there is almost no possibility of air (oxygen) mixing. However, in the case of a device such as a stationary air conditioner, on-site refrigerant filling construction is required. The refrigerant filling construction is left to the management ability of the contractor, and air (oxygen) has been considered as the main cause of troubles and troubles such as a decrease in the freezing capacity.
　従来のＨＦＣ冷媒では、このような不具合が発生した場合に冷媒の入れ替えのみで対応可能であったが、ハイドロフルオロプロペンを含む冷媒の場合には冷媒の酸化分解により大量の酸を生成するため、システムの金属腐食等が生じるおそれがあり、それに伴い機器の交換の必要も考えられる。このように、ハイドロフルオロプロペンを含む冷媒を用いる場合には、据え付け作業及びメンテナンス等の問題が発生する可能性がある。そのため、ハイドロフルオロプロペンを冷媒組成物の成分として用いる場合には、該冷媒組成物について空気（酸素）共存下における安定性を高める技術が必要である。 In the conventional HFC refrigerant, when such a problem occurred, it was possible to cope with only replacement of the refrigerant, but in the case of a refrigerant containing hydrofluoropropene, a large amount of acid is generated by oxidative decomposition of the refrigerant. There is a risk of metal corrosion of the system, etc., and it may be necessary to replace the equipment. Thus, when a refrigerant containing hydrofluoropropene is used, problems such as installation work and maintenance may occur. Therefore, when hydrofluoropropene is used as a component of the refrigerant composition, a technique for improving the stability of the refrigerant composition in the presence of air (oxygen) is necessary.
　例えば、特許文献１等には、安定化技術が報告されている。特許文献１には、フルオロオレフィン対して、フェノール系化合物、チオフォスフェート類、ベンゾキノン類、アリールアルキルエーテル等の安定化剤を添加することが記載されている。 For example, Patent Document 1 and the like report a stabilization technique. Patent Document 1 describes that stabilizers such as phenolic compounds, thiophosphates, benzoquinones, and arylalkyl ethers are added to the fluoroolefin.
国際公開第２００８／０２７５１１号パンフレットInternational Publication No. 2008/027511 Pamphlet
　本発明は、地球温暖化係数（ＧＷＰ）が低いハイドロフルオロプロペンを含む冷媒組成物であって、空気（酸素）共存下においても安定な状態を長期間維持できる安定化された冷媒組成物を提供することを目的とする。 The present invention provides a refrigerant composition containing hydrofluoropropene having a low global warming potential (GWP), which can maintain a stable state for a long time even in the presence of air (oxygen). The purpose is to do.
　本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、炭素数１～４でアルコール価数１～４の脂肪族アルコールからなる群より選ばれる少なくとも１種の安定化剤（酸化防止剤）を含む冷媒組成物が、空気（酸素）共存下においても安定な状態を長期間維持できることを見出した。かかる冷媒組成物は、家庭用エアコン等の定置型空調機の冷媒充填施工時に空気（酸素）が混入しても、長期にわたって安定性が保持できる。 As a result of intensive studies to achieve the above object, the present inventor has at least one stabilizer (antioxidant) selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohols. It has been found that a refrigerant composition containing an agent can maintain a stable state for a long time even in the presence of air (oxygen). Such a refrigerant composition can maintain stability over a long period of time even when air (oxygen) is mixed during refrigerant filling construction of a stationary air conditioner such as a home air conditioner.
　また、従来の不飽和結合を持たないＨＦＣ冷媒の分解機構はハロゲン原子の還元が主であり、温度、金属（触媒）、水分、空気等の分解加速要因を考慮した試験などによりその冷媒の耐久安定性を評価している。一方、ハイドロフルオロプロペンの安定性評価については、例えば、特許文献１では、冷凍機油及び冷媒（HFO-1225ye）に空気及び金属触媒（Ｆｅ，Ｃｕ又はＡｌ）を共存させた混合物を１７５℃で２週間加熱した後、該混合物の外観を評価している。即ち、従来（ＨＦＣ冷媒）と同じ熱安定性加速試験で評価を行っている。 In addition, the conventional mechanism for decomposing HFC refrigerants without unsaturated bonds is the reduction of halogen atoms, and the durability of the refrigerant is determined by tests taking into account decomposition acceleration factors such as temperature, metal (catalyst), moisture, and air. Evaluating stability. On the other hand, regarding the stability evaluation of hydrofluoropropene, for example, in Patent Document 1, a mixture of air and a metal catalyst (Fe, Cu, or Al) in refrigeration oil and refrigerant (HFO-1225ye) at 175 ° C. is 2 After heating for a week, the appearance of the mixture is evaluated. That is, the evaluation is performed by the same thermal stability acceleration test as that of the conventional (HFC refrigerant).
　しかし、この方法では単に混合物の液相の外観（着色の等級；Rating）を評価するのみであり、ハイドロフルオロプロペンを冷媒として用いる際のシステム内の腐食や冷凍能力の低下の原因となる酸の発生について充分な評価がなされていない。 However, this method merely evaluates the appearance of the liquid phase of the mixture (coloring grade; Rating), and does not allow the acid in the system to corrode or reduce the refrigeration capacity when hydrofluoropropene is used as a refrigerant. Sufficient evaluation has not been made on the occurrence.
　本発明では、ハイドロフルオロプロペンを含む冷媒組成物の分解機構が、その不飽和結合と酸素との酸化反応が支配的であること、該酸化反応により上記問題の主原因であるＣＦ３ＣＯＯＨ、ＨＦなどの酸が生成することを明らかにし、その評価方法を確立するに至った。具体的には、ハイドロフルオロプロペンを含む冷媒組成物を所定温度で所定時間処理した後、その処理後の冷媒組成物の酸分を評価することにより、より現実に則したハイドロフルオロプロペンの熱安定性の評価が可能となった。 In the present invention, the decomposition mechanism of the refrigerant composition containing hydrofluoropropene is dominated by the oxidation reaction between the unsaturated bond and oxygen, and CF 3 COOH, HF, which is the main cause of the above problem due to the oxidation reaction. It has been clarified that acids such as these are formed, and the evaluation method has been established. Specifically, after treating a refrigerant composition containing hydrofluoropropene at a predetermined temperature for a predetermined time, and evaluating the acid content of the refrigerant composition after the treatment, the thermal stability of hydrofluoropropene more realistically Evaluation of sex became possible.
　かかる知見に基づき、更に検討を加えた結果、本発明を完成するに至った。 As a result of further studies based on such knowledge, the present invention has been completed.
　即ち、本発明は以下のハイドロフルオロプロペンを含む冷媒組成物に関する。
１．　ハイドロフルオロプロペン及び安定化剤を含む冷媒組成物であって、該安定化剤が、炭素数１～４でアルコール価数１～４の脂肪族アルコールからなる群より選ばれる少なくとも１種であることを特徴とする冷媒組成物。
２．　ハイドロフルオロプロペンが、2,3,3,3－テトラフルオロプロペン（HFO-1234yf）、（Z又はE-）1,3,3,3－テトラフルオロプロペン（HFO-1234ze）、(Z又はE-)1,2,3,3,3－ペンタフルオロプロペン（HFO-1225ye）、（Z又はE-）1,1,3,3,3－ペンタフルオロプロペン（HFO-1225zc）、及び(Z又はE-)3,3,3－トリフルオロプロペン（HFO-1243zf）からなる群より選ばれる少なくとも１種である、項１に記載の冷媒組成物。
３．　ハイドロフルオロプロペン１００重量部に対する安定化剤の含有量が０．１～５．０重量部である、項１に記載の冷媒組成物。
４．　更に冷凍機油を含有する、項１に記載の冷媒組成物。
５．　冷凍機油が、ポリアルキレングリコール、ポリオールエステル及びポリビニルエーテルからなる群より選ばれる少なくとも１種を含み、４０℃における動粘度が５～４００ｃＳｔである、項４に記載の冷媒組成物。
６．　冷媒組成物が、冷凍機、冷蔵庫、モバイルエアコン、冷却機（チラー）、コンテナ用冷凍装置、家庭用エアコン、業務用エアコン、給湯器等の蒸気圧縮式ヒートポンプからなる群より選ばれる１種の用途に用いられる、項１～５のいずれかに記載の冷媒組成物。
７．　ハイドロフルオロプロペンを含む冷媒組成物の安定化方法であって、該冷媒組成物に、炭素数１～４でアルコール価数１～４の脂肪族アルコールからなる群より選ばれる少なくとも１種の安定化剤を添加することを特徴とする安定化方法。
８．　ハイドロフルオロプロペン及び安定化剤を含む冷媒組成物の安定性の評価方法であって、密閉容器中で、酸素の存在下及び／又は不存在下に、該冷媒組成物を加熱処理した後、処理後の冷媒組成物の酸分を分析することを特徴とする評価方法。 That is, the present invention relates to a refrigerant composition containing the following hydrofluoropropene.
1. A refrigerant composition comprising hydrofluoropropene and a stabilizer, wherein the stabilizer is at least one selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohol valences. A refrigerant composition characterized by the above.
2. The hydrofluoropropene is 2,3,3,3-tetrafluoropropene (HFO-1234yf), (Z or E-) 1,3,3,3-tetrafluoropropene (HFO-1234ze), (Z or E- ) 1,2,3,3,3-pentafluoropropene (HFO-1225ye), (Z or E-) 1,1,3,3,3-pentafluoropropene (HFO-1225zc), and (Z or E Item 2) The refrigerant composition according to item 1, which is at least one selected from the group consisting of 3,3,3-trifluoropropene (HFO-1243zf).
3. Item 2. The refrigerant composition according to Item 1, wherein the content of the stabilizer relative to 100 parts by weight of hydrofluoropropene is 0.1 to 5.0 parts by weight.
4). Item 2. The refrigerant composition according to Item 1, further comprising refrigerating machine oil.
5). Item 5. The refrigerant composition according to Item 4, wherein the refrigerating machine oil contains at least one selected from the group consisting of polyalkylene glycol, polyol ester, and polyvinyl ether, and has a kinematic viscosity at 40 ° C of 5 to 400 cSt.
6). One type of use in which the refrigerant composition is selected from the group consisting of a vapor compression heat pump such as a refrigerator, a refrigerator, a mobile air conditioner, a refrigerator (chiller), a container refrigeration apparatus, a home air conditioner, a commercial air conditioner, or a water heater. Item 6. The refrigerant composition according to any one of Items 1 to 5, which is used in
7). A method for stabilizing a refrigerant composition comprising hydrofluoropropene, the method comprising stabilizing at least one selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohol valences A stabilizing method comprising adding an agent.
8). A method for evaluating the stability of a refrigerant composition containing hydrofluoropropene and a stabilizer, wherein the refrigerant composition is heated in a sealed container in the presence and / or absence of oxygen, and then treated. The evaluation method characterized by analyzing the acid content of a refrigerant composition after.
　本発明の冷媒組成物は、塩素及び臭素を含まないために、大気中に放出されてもオゾン層を破壊する危険性がない。また、地球温暖化係数も低く且つ空気（酸素）共存下における安定性が既存のＨＦＣ冷媒と同等レベルであり、定置式冷凍機用の冷媒組成物として使用しても充分な耐久性を有する。 Since the refrigerant composition of the present invention does not contain chlorine and bromine, there is no danger of destroying the ozone layer even if released into the atmosphere. In addition, the global warming potential is low, the stability in the presence of air (oxygen) is at the same level as that of existing HFC refrigerants, and it has sufficient durability even when used as a refrigerant composition for stationary refrigerators.
　本発明の冷媒組成物は、ハイドロフルオロプロペン及び安定化剤を含み、該安定化剤が、炭素数１～４でアルコール価数１～４の脂肪族アルコールからなる群より選ばれる少なくとも１種であることを特徴とする。 The refrigerant composition of the present invention contains hydrofluoropropene and a stabilizer, and the stabilizer is at least one selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohol valences. It is characterized by being.
　冷媒であるハイドロフルオロプロペンとしては、例えば、2,3,3,3－テトラフルオロプロペン（HFO-1234yf）、（Z又はE-）1,3,3,3－テトラフルオロプロペン（HFO-1234ze）、(Z又はE-)1,2,3,3,3－ペンタフルオロプロペン（HFO-1225ye）、（Z又はE-）1,1,3,3,3－ペンタフルオロプロペン（HFO-1225zc）、(Z又はE-)3,3,3－トリフルオロプロペン（HFO-1243zf）等が挙げられる。これらのハイドロフルオロプロペンは単独又は２種以上を混合して使用できる。 Examples of the refrigerant hydrofluoropropene include 2,3,3,3-tetrafluoropropene (HFO-1234yf) and (Z or E-) 1,3,3,3-tetrafluoropropene (HFO-1234ze). , (Z or E-) 1,2,3,3,3-pentafluoropropene (HFO-1225ye), (Z or E-) 1,1,3,3,3-pentafluoropropene (HFO-1225zc) (Z or E-) 3,3,3-trifluoropropene (HFO-1243zf) and the like. These hydrofluoropropenes can be used alone or in admixture of two or more.
　本発明の冷媒組成物は、上記ハイドロフルオロプロペンに加えて、更に既存のＨＦＣ冷媒を混合しても良い。 The refrigerant composition of the present invention may be further mixed with an existing HFC refrigerant in addition to the hydrofluoropropene.
　上記ＨＦＣ冷媒の含有割合は、冷媒の全重量に対し５０重量％以下、好ましくは３０重量％以下、より好ましくは２０重量％以下である。 The content ratio of the HFC refrigerant is 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less based on the total weight of the refrigerant.
　本発明の冷媒組成物は、用途によってハイドロフルオロプロペンに加えて冷凍機油を含んでいてもよい。冷凍機油としては、公知のものを用いることができる。例えば、ポリ（オキシ）アルキレングリコール類、ポリビニルエーテル類、ポリフェニルエーテル類、ポリ（オキシ）アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体、ポリオールエステル類、ポリカーボネート類、シリコーン、ポリシロキサン、パーフルオロエーテル類、鉱油、オレフィン重合体、アルキルジフェニルアルカン類、アルキルナフタレン類、アルキルベンゼン類等が挙げられる。これらの冷凍機油の中でも、特にポリ（オキシ）アルキレングリコール類、ポリビニルエーテル類、ポリオールエステル類の少なくとも１種が好ましい。 The refrigerant composition of the present invention may contain refrigerating machine oil in addition to hydrofluoropropene depending on applications. A well-known thing can be used as refrigerating machine oil. For example, poly (oxy) alkylene glycols, polyvinyl ethers, polyphenyl ethers, poly (oxy) alkylene glycols or their monoether and polyvinyl ether copolymers, polyol esters, polycarbonates, silicones, polysiloxanes, Examples include perfluoroethers, mineral oil, olefin polymers, alkyldiphenylalkanes, alkylnaphthalenes, alkylbenzenes, and the like. Among these refrigerating machine oils, at least one of poly (oxy) alkylene glycols, polyvinyl ethers, and polyol esters is particularly preferable.
　これらの冷凍機油は単独又は混合して用いることができる。冷凍機油の４０℃における動粘度は、好ましくは５～４００ｃＳｔであり、より好ましくは３０～４００ｃＳｔである。なお、本明細書における動粘度は、JIS Z 8803（液体の粘度－測定方法）に規定されている粘度計のうち毛細管粘度計により測定した値である。 These refrigerating machine oils can be used alone or in combination. The kinematic viscosity of the refrigerating machine oil at 40 ° C. is preferably 5 to 400 cSt, more preferably 30 to 400 cSt. The kinematic viscosity in this specification is a value measured with a capillary viscometer among viscometers defined in JIS Z 8803 (liquid viscosity-measurement method).
　冷凍機油を用いる場合には、ハイドロフルオロプロペンを含む冷媒の使用量は、冷凍機油１０重量部に対して、通常１６～５０重量部であるが、冷凍機のオイルタンクの仕様により異なるもので、特にこの範囲に限定されるものではない。 When using refrigerating machine oil, the amount of refrigerant containing hydrofluoropropene is usually 16 to 50 parts by weight with respect to 10 parts by weight of refrigerating machine oil, but it varies depending on the specifications of the oil tank of the refrigerating machine. It is not particularly limited to this range.
　本発明の冷媒組成物は、ハイドロフルオロプロペンを含む冷媒の酸素に対する安定性を付与するために、炭素数１～４、アルコール価数１～４の脂肪族アルコールを安定化剤（酸化防止剤）として含有する。 The refrigerant composition of the present invention comprises an aliphatic alcohol having 1 to 4 carbon atoms and an alcohol number of 1 to 4 as a stabilizer (antioxidant) in order to impart stability to oxygen of a refrigerant containing hydrofluoropropene. Contained as.
　上記の安定化剤のうち、１価のアルコールとしては、Ｃ１～Ｃ４の直鎖状、分岐状のアルコールが挙げられる。該アルコールのアルキル基にはエーテル結合を含んでいても良い。具体的には、メタノール、エタノール、(n-,iso-)プロピルアルコール、(n-,sec-,tert-)ブタノール等が例示され、好ましくはメタノール、イソプロピルアルコール、sec-ブタノール、tert-ブタノールである。 Among the above-mentioned stabilizers, examples of the monohydric alcohol include C 1 to C 4 linear and branched alcohols. The alkyl group of the alcohol may contain an ether bond. Specific examples include methanol, ethanol, (n-, iso-) propyl alcohol, (n-, sec-, tert-) butanol and the like, preferably methanol, isopropyl alcohol, sec-butanol and tert-butanol. is there.
　また、多価アルコールとしては、水酸基を２～４個保有するＣ２～Ｃ４のアルコールが挙げられ、該アルコール中の炭化水素鎖にはエーテル結合を含んでいても良い。具体的にはエチレングリコール、プロピレングリコール、グリセロール、エリスリトール等が挙げられる。好ましくは、エチレングリコールである。 Examples of the polyhydric alcohol include C 2 -C 4 alcohols having 2 to 4 hydroxyl groups, and the hydrocarbon chain in the alcohol may contain an ether bond. Specific examples include ethylene glycol, propylene glycol, glycerol, erythritol and the like. Ethylene glycol is preferable.
　安定化剤である炭素数１～４でアルコール価数１～４の脂肪族アルコールは、それぞれ単独で又は２種以上を混合して用いることができる。 The aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 carbon numbers, which are stabilizers, can be used alone or in admixture of two or more.
　安定化剤の配合量は、ハイドロフルオロプロペン１００重量部に対して、通常０．１～５．０重量部、より好ましくは０．３～３．０重量部である。 The blending amount of the stabilizer is usually 0.1 to 5.0 parts by weight, more preferably 0.3 to 3.0 parts by weight with respect to 100 parts by weight of hydrofluoropropene.
　ハイドロフルオロプロペンに対する安定化剤の含有量は少な過ぎてもその効果が得られず、多すぎてもスラッジ発生の原因や経済性の観点から好ましくないため、上記範囲であれば好適である。 If the content of the stabilizer relative to the hydrofluoropropene is too small, the effect cannot be obtained, and if it is too large, it is not preferable from the viewpoint of sludge generation and economy, so the above range is suitable.
　なお、安定化剤が冷凍機油に対して難溶性の場合には、酸素とハイドロフルオロプロペンとの安定性に悪影響を及ばさない範囲で任意に溶媒を添加してもよい。かかる溶媒としては、グライム化合物が挙げられ、好ましくはジグライムである。溶媒の添加量は、安定化剤の全重量の３０重量％以下、好ましくは１５～２５重量％、より好ましくは１５～２０重量％である。 In addition, when the stabilizer is hardly soluble in the refrigerating machine oil, a solvent may be optionally added within a range that does not adversely affect the stability of oxygen and hydrofluoropropene. Examples of such a solvent include glyme compounds, preferably diglyme. The addition amount of the solvent is 30% by weight or less, preferably 15 to 25% by weight, more preferably 15 to 20% by weight, based on the total weight of the stabilizer.
　本発明で用いる安定化剤は、特許文献１で例示されるものに比べて、安定化（酸価防止）効果が極めて高い（実施例及び比較例を参照）。 The stabilizer used in the present invention has a very high stabilizing (acid value prevention) effect compared to that exemplified in Patent Document 1 (see Examples and Comparative Examples).
　これは、特許文献１の安定性評価方法では、単に混合物の液相の外観（着色の等級；Rating）を評価するのみであり、ハイドロフルオロプロペンの酸化分解によるシステム内の腐食や冷凍能力の低下の主原因である酸の発生の評価ができていないからである。 This is because the stability evaluation method of Patent Document 1 merely evaluates the appearance of the liquid phase of the mixture (coloring grade; Rating), and the corrosion in the system due to the oxidative decomposition of hydrofluoropropene and the reduction of the refrigerating capacity. This is because the generation of acid, which is the main cause of this, has not been evaluated.
　これに対して、本発明の安定性評価方法は、密閉容器中で、酸素の存在下及び／又は不存在下に、冷媒組成物を加熱処理した後、処理後の冷媒組成物の酸分を分析することを特徴とする。 On the other hand, in the stability evaluation method of the present invention, the heat treatment of the refrigerant composition in a sealed container in the presence and / or absence of oxygen, the acid content of the refrigerant composition after the treatment is performed. It is characterized by analyzing.
　酸素不存在下の分析結果（酸素不存在下で酸が発生しないことの確認）と酸素存在下での分析結果との差を比較することにより、安定化剤の効果及びその程度を確実に評価することができる。 By comparing the difference between the analysis results in the absence of oxygen (confirmation that no acid is generated in the absence of oxygen) and the analysis results in the presence of oxygen, the effect and extent of the stabilizer can be reliably evaluated. can do.
　密閉容器としては、シールドチューブ（例えば、シールドされたパイレックス（登録商標）ガラス製チューブ等）が用いられる。本発明の評価方法は、いわゆる加速試験に相当するため、例えば加熱温度は９０～２００℃の範囲から設定できる。また、加熱処理時間は７２～７２０時間の範囲から設定できる。処理後の冷媒組成物の酸分の分析方法については、実施例に記載の方法により実施することができる。 As the sealed container, a shield tube (for example, a shielded Pyrex (registered trademark) glass tube or the like) is used. Since the evaluation method of the present invention corresponds to a so-called acceleration test, for example, the heating temperature can be set in the range of 90 to 200 ° C. The heat treatment time can be set in the range of 72 to 720 hours. About the analysis method of the acid content of the refrigerant | coolant composition after a process, it can implement by the method as described in an Example.
　本発明の評価方法によれば、システム内の腐食や冷凍能力の低下という問題の主原因である、酸化反応によるＣＦ３ＣＯＯＨ、ＨＦなどの酸の発生を適切に評価できる。そのため、本発明の評価方法を用いれば、より現実に即した安定化剤のスクリーニングが可能となる。 According to the evaluation method of the present invention, it is possible to appropriately evaluate the generation of acids such as CF 3 COOH and HF due to an oxidation reaction, which is the main cause of problems such as corrosion in the system and a decrease in refrigeration capacity. Therefore, if the evaluation method of the present invention is used, it becomes possible to screen for a more realistic stabilizer.
　本発明の冷媒組成物は、高度の熱安定性を要求される場合には、例えば、特開２０００－１７８５４３号公報、特開２００８－３０８６１０号公報、特許第２８６３１５９号公報等に記載されている従来のＨＦＣ冷媒システムで用いられるＨＦＣ冷媒又は冷凍機油の熱安定化剤を併用することもできる。 The refrigerant composition of the present invention is described in, for example, Japanese Patent Application Laid-Open No. 2000-178543, Japanese Patent Application Laid-Open No. 2008-308610, Japanese Patent No. 2863159 and the like when a high degree of thermal stability is required. An HFC refrigerant used in a conventional HFC refrigerant system or a heat stabilizer for refrigeration oil can be used in combination.
　上記熱安定化剤としては、（i）ニトロメタン、ニトロエタン、ニトロプロパン等の脂肪族ニトロ化合物類、ニトロベンゼン、ニトロスチレン等の芳香族ニトロ化合物類、p-イソプロペニルトルエン、ジイソプロペニルベンゼン等の芳香族不飽和脂肪化合物類、（ii）2,6-ジ-ｔ-ブチル-ｐ-クレゾール等のフェノール類、1,2-ブチレンオキサイド等のエポキシ類等、フェニル-α-ナフチルアミン等のアミン類が挙げられる。 Examples of the heat stabilizer include (i) aliphatic nitro compounds such as nitromethane, nitroethane and nitropropane, aromatic nitro compounds such as nitrobenzene and nitrostyrene, and aromatics such as p-isopropenyltoluene and diisopropenylbenzene. (Ii) phenols such as 2,6-di-t-butyl-p-cresol, epoxies such as 1,2-butylene oxide, and amines such as phenyl-α-naphthylamine Can be mentioned.
　熱安定化剤は上記（i）及び（ii）より選択された化合物の１類又は２種以上を用いることができ、この場合上記の（i）又は（ii）から２種以上の化合物を用いてもよい。 As the heat stabilizer, one or more compounds selected from the above (i) and (ii) can be used, and in this case, two or more compounds from the above (i) or (ii) are used. May be.
　熱安定化剤の使用量は、その種類により異なるが、冷媒性能の性質に支障のない程度とする。熱安定化剤の使用量は、通常、冷媒組成物中に０．１～５重量％程度とすることが好ましく、０．３～３重量％程度とすることがより好ましい。 使用 The amount of heat stabilizer used varies depending on the type of the stabilizer, but should be such that it does not interfere with the properties of the refrigerant performance. The amount of heat stabilizer used is usually preferably about 0.1 to 5% by weight, more preferably about 0.3 to 3% by weight in the refrigerant composition.
　本発明の冷媒組成物は、従来のフロンと同様に冷媒、熱移動媒体、動作流体、発泡剤などの各種の用途に用いることができる。例えば、冷凍機、冷蔵庫、モバイルエアコン、冷却機（チラー）、コンテナ用冷凍装置、家庭用エアコン、業務用エアコン、給湯器等の蒸気圧縮式ヒートポンプなどをはじめ、その他各種低温機器用の冷媒組成物として有用である。特に、現場での冷媒充填施工が必要で、酸素混入の可能性の高い定置式空調機等に用いる冷媒組成物として有用である。 The refrigerant composition of the present invention can be used for various applications such as a refrigerant, a heat transfer medium, a working fluid, and a foaming agent in the same manner as conventional chlorofluorocarbon. For example, refrigerant compositions for refrigerators, refrigerators, mobile air conditioners, refrigerators (chillers), container refrigeration equipment, household air conditioners, commercial air conditioners, steam compression heat pumps for water heaters, and other various low-temperature equipment Useful as. In particular, it is useful as a refrigerant composition for use in stationary air conditioners and the like that require on-site refrigerant filling and have a high possibility of oxygen contamination.
　以下、実施例及び比較例を示して本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.
　実施例１～１０及び比較例１～１０
（冷媒組成物の調製）
　冷媒として次のものを用意した。
Ｘ：ＨＦＯ－１２３４ｙｆ（ＣＦ３ＣＦ＝ＣＨ２ダイキン工業製）
Ｙ（比較品）：ＨＦＣ－３２（ＣＦ２Ｈ２ダイキン工業製）
Ｚ：ＨＦＯ－１２２５ｙｅ（ＣＦ３ＣＨ＝ＣＦ２ダイキン工業製）
　安定化剤として次のものを用意した。
Ａ（比較品）：エチルメルカプタン
Ｂ：メタノール
Ｃ：エタノール
Ｄ：イソプロパノール
Ｅ：２－ブタノール
Ｆ：ｔｅｒｔ－ブタノール
Ｇ：エチレングリコール
　冷凍機油として、下記一般式（ｉ）で表される構成単位を有するポリビニルエーテル系化合物を主成分とする４０℃における動粘度が７０ｍｍ２／ｓ程度である冷凍機油を用意した。 Examples 1 to 10 and Comparative Examples 1 to 10
(Preparation of refrigerant composition)
The following were prepared as refrigerants.
X: HFO-1234yf (CF 3 CF = CH 2 manufactured by Daikin Industries)
Y (comparative product): HFC-32 (manufactured by CF 2 H 2 Daikin Industries)
Z: HFO-1225ye (CF 3 CH═CF 2 manufactured by Daikin Industries)
The following were prepared as stabilizers.
A (comparative product): ethyl mercaptan B: methanol C: ethanol D: isopropanol E: 2-butanol F: tert-butanol G: ethylene glycol Polyvinyl having a structural unit represented by the following general formula (i) as a refrigerating machine oil A refrigerating machine oil having a kinematic viscosity at 40 ° C. of about 70 mm 2 / s containing an ether compound as a main component was prepared.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　下記表１に示す組成となるように各冷媒組成物を調製した。 Each refrigerant composition was prepared so as to have the composition shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　試験例１
　パイレックス（登録商標）ガラス製チューブ（ID8mmΦ×OD12mmΦ×L300mm）に表１に示される計２０種類（実施例１～１０、比較例１～１０）の冷媒組成物（冷媒＋安定化剤）を入れ、更に表１に示される酸素濃度になるよう空気を入れて調整し封入後、温度１５０℃で１週間（１６８時間）加熱する加速試験を行った。 Test example 1
Pyrex (registered trademark) glass tubes (ID8mmΦ × OD12mmΦ × L300mm) are filled with a total of 20 types of refrigerant compositions (Examples 1-10, Comparative Examples 1-10) shown in Table 1 (refrigerant + stabilizer). Further, an air test was carried out so that the oxygen concentration shown in Table 1 was adjusted, and after enclosing, an accelerated test was performed in which heating was performed at a temperature of 150 ° C. for one week (168 hours).
（酸分の分析方法）
　加速試験後のシールドチューブを液体窒素にてガスを完全に凝固させた。その後開封し、徐々に解凍し気化したガスをテドラーバッグに回収した。テドラーバッグに純水５ｇを注入し回収ガスとよく接触させ酸分を抽出し、抽出液をイオンクロマトグラフィーにてフッ化物イオン（Ｆ－）及びトリフルオロ酢酸イオン（ＣＦ３ＣＯＯ－）の含有量（重量ｐｐｍ）を測定した。 (Analytical analysis method)
The shield tube after the acceleration test was completely solidified with liquid nitrogen. Thereafter, it was opened, and the gas that was gradually thawed and vaporized was collected in a Tedlar bag. 5 g of pure water was injected into the Tedlar bag, and the acid content was extracted by making good contact with the recovered gas. The extract was subjected to ion chromatography to contain fluoride ions (F − ) and trifluoroacetate ions (CF 3 COO − ) ( Weight ppm) was measured.
（冷凍機油の全酸価分析）
　ＪＩＳ Ｋ－２２１１（冷凍機油）の全酸価分析方法に準拠した方法で、ガス回収後の冷凍機油全酸価値の測定を行った。加速試験後の冷凍機油を秤量し、トルエン／イソプロパノール／水混合溶媒に溶解させ、指示薬としてα－ナフトールベンゼインを用いて1/100N－ＫＯＨ・エタノール溶液にて中和滴定し、滴定量から冷凍機油全酸価（mg・KOH／g）を測定した。 (Total acid value analysis of refrigerating machine oil)
The total acid value of the refrigerating machine oil after gas recovery was measured by a method based on the total acid value analysis method of JIS K-2211 (refrigerating machine oil). Refrigeration machine oil after acceleration test is weighed, dissolved in toluene / isopropanol / water mixed solvent, neutralized with 1 / 100N KOH / ethanol solution using α-naphtholbenzein as indicator, and frozen from titration. The machine oil total acid value (mg · KOH / g) was measured.
　比較例の結果を下記表２に示し、実施例の結果を下記表３に示す。 The results of the comparative examples are shown in Table 2 below, and the results of the examples are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
（結　果）
　比較例１～７は、いずれも安定化剤を用いていない。 (Result)
In Comparative Examples 1 to 7, none of the stabilizers is used.
　比較例１～３はそれぞれHFO-1234yf、HFC-32、HFO-1225yeからなり、いずれも無酸素状態での安定性を評価しており、特に分解の兆候（酸の発生）は認められていない。 Comparative Examples 1 to 3 each consisted of HFO-1234yf, HFC-32, and HFO-1225ye, all of which were evaluated for stability under anoxic conditions, and no signs of decomposition (acid generation) were observed. .
　比較例４～６は、それぞれ比較例１～３に酸素を共存させたものである。比較例４及び６ではハイドロフルオロプロペンであるHFO-1234yf、HFO-1225yeにおいて酸分の生成が大幅に増加している。これは、ハイドロフルオロプロペンの酸素共存下における安定性が、従来ＨＦＣ冷媒（HFC-32）のそれと比較して極めて低いことを示している。 Comparative Examples 4 to 6 are obtained by coexisting oxygen with Comparative Examples 1 to 3, respectively. In Comparative Examples 4 and 6, the production of acid content is greatly increased in HFO-1234yf and HFO-1225ye, which are hydrofluoropropenes. This indicates that the stability of hydrofluoropropene in the presence of oxygen is extremely low compared to that of the conventional HFC refrigerant (HFC-32).
　比較例７ではHFO-1234yfとHFC-32の混合物と酸素を共存させているが、酸分生成量はHFO-1234yf（比較例４）に対しほぼ８０％と組成比に比例している。 In Comparative Example 7, a mixture of HFO-1234yf and HFC-32 and oxygen coexist, but the amount of acid content generated is approximately 80% of HFO-1234yf (Comparative Example 4) and is proportional to the composition ratio.
　比較例８及び９では　特許文献１（ＷＯ２００８／０２７５１１号）に記載のエチルメルカプタンを安定化剤Ａとして添加しているが、安定化剤を添加していない比較例４、６と酸分の生成量はほぼ同等であり安定化効果が認められないことが分かる。 In Comparative Examples 8 and 9, ethyl mercaptan described in Patent Document 1 (WO2008 / 027511) is added as a stabilizer A, but Comparative Examples 4 and 6 without addition of a stabilizer and generation of acid content It can be seen that the amounts are almost equal and no stabilizing effect is observed.
　実施例１～９における酸分は、比較例４～９と比べると低い値を示しており、ハイドロフルオロプロペンの酸素による酸化が抑制されていることが分かる。 The acid content in Examples 1 to 9 is lower than that in Comparative Examples 4 to 9, indicating that the oxidation of hydrofluoropropene by oxygen is suppressed.
　実施例２では、HFO-1225yeを冷媒としているが、HFO-1234yf単独（実施例１）と同様に安定化剤（Ｂ：メタノール）による効果が確認できており、HFO-1234yf以外のハイドロフルオロプロペンに対してもその抑制効果が認められた。 In Example 2, HFO-1225ye is used as the refrigerant, but the effect of the stabilizer (B: methanol) can be confirmed in the same manner as HFO-1234yf alone (Example 1). Hydrofluoropropenes other than HFO-1234yf The inhibitory effect was recognized.
　実施例８では、HFO-1234yfとHFC-32の混合物を冷媒としているが、HFO-1234yf単独（実施例１）と同様に、HFC-32との混合物としてもその抑制効果が認められた。 In Example 8, a mixture of HFO-1234yf and HFC-32 was used as the refrigerant, but as with HFO-1234yf alone (Example 1), its inhibitory effect was also observed as a mixture with HFC-32.
　実施例１０と比較例１０は冷凍機油を含む冷媒組成物であり、安定化剤の有無で性能を比較している。実施例１０では、ガス中の酸分及び冷凍機油全酸価のいずれも比較例１０より低減されている。これは安定化剤による抑制効果がHFO-1234yfと酸素との反応による酸生成の抑制と共に酸素によるエーテル油の酸化も抑制しているためと考えられる。 Example 10 and Comparative Example 10 are refrigerant compositions containing refrigerating machine oil, and their performance is compared with and without a stabilizer. In Example 10, both the acid content in the gas and the total acid value of the refrigerating machine oil are reduced as compared with Comparative Example 10. This is presumably because the inhibitory effect of the stabilizer suppresses the oxidation of ether oil by oxygen as well as the suppression of acid generation by the reaction of HFO-1234yf and oxygen.
　以上の結果から、2,3,3,3－テトラフルオロプロペン等のハイドロフルオロプロペン及びその組成物が安定化剤により、空気（酸素）共存下においてもＨＦＣ冷媒と等しく酸素に対して安定性を示す事を確認した。よって、不飽和結合を有するハイドロフルオロプロペンに本発明の安定化剤を添加することにより、酸素共存下における安定性をＨＦＣ冷媒（HFC-32）と同等レベルに改善することができた。そのため、本発明の冷媒組成物は、地球環境に極力影響を及ぼさず従来ＨＦＣ冷媒と同等の安定性を示す定置式空調機用の冷媒組成物として有用であることを見出した。 From the above results, hydrofluoropropene such as 2,3,3,3-tetrafluoropropene and its composition are stabilized by a stabilizer so that they are equally stable to oxygen even in the presence of air (oxygen). I confirmed what I showed. Therefore, by adding the stabilizer of the present invention to hydrofluoropropene having an unsaturated bond, the stability in the presence of oxygen could be improved to the same level as that of the HFC refrigerant (HFC-32). Therefore, it has been found that the refrigerant composition of the present invention is useful as a refrigerant composition for stationary air conditioners that does not affect the global environment as much as possible and exhibits the same stability as conventional HFC refrigerants.

Claims (8)

  1. ハイドロフルオロプロペン及び安定化剤を含む冷媒組成物であって、該安定化剤が、炭素数１～４でアルコール価数１～４の脂肪族アルコールからなる群より選ばれる少なくとも１種であることを特徴とする冷媒組成物。 A refrigerant composition comprising hydrofluoropropene and a stabilizer, wherein the stabilizer is at least one selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohol valences. A refrigerant composition characterized by the above.
  2. ハイドロフルオロプロペンが、2,3,3,3－テトラフルオロプロペン（HFO-1234yf）、（Z又はE-）1,3,3,3－テトラフルオロプロペン（HFO-1234ze）、(Z又はE-)1,2,3,3,3－ペンタフルオロプロペン（HFO-1225ye）、（Z又はE-）1,1,3,3,3－ペンタフルオロプロペン（HFO-1225zc）、及び(Z又はE-)3,3,3－トリフルオロプロペン（HFO-1243zf）からなる群より選ばれる少なくとも１種である、請求項１に記載の冷媒組成物。 The hydrofluoropropene is 2,3,3,3-tetrafluoropropene (HFO-1234yf), (Z or E-) 1,3,3,3-tetrafluoropropene (HFO-1234ze), (Z or E- ) 1,2,3,3,3-pentafluoropropene (HFO-1225ye), (Z or E-) 1,1,3,3,3-pentafluoropropene (HFO-1225zc), and (Z or E The refrigerant composition according to claim 1, which is at least one selected from the group consisting of-) 3,3,3-trifluoropropene (HFO-1243zf).
  3. ハイドロフルオロプロペン１００重量部に対する安定化剤の含有量が０．１～５．０重量部である、請求項１に記載の冷媒組成物。 The refrigerant composition according to claim 1, wherein the content of the stabilizer with respect to 100 parts by weight of hydrofluoropropene is 0.1 to 5.0 parts by weight.
  4. 更に冷凍機油を含有する、請求項１に記載の冷媒組成物。 Furthermore, the refrigerant | coolant composition of Claim 1 containing refrigeration oil.
  5. 冷凍機油が、ポリアルキレングリコール、ポリオールエステル及びポリビニルエーテルからなる群より選ばれる少なくとも１種を含み、４０℃における動粘度が５～４００ｃＳｔである、請求項４に記載の冷媒組成物。 The refrigerant composition according to claim 4, wherein the refrigerating machine oil contains at least one selected from the group consisting of polyalkylene glycol, polyol ester and polyvinyl ether, and has a kinematic viscosity at 40 ° C of 5 to 400 cSt.
  6. 冷媒組成物が、冷凍機、冷蔵庫、モバイルエアコン、冷却機（チラー）、コンテナ用冷凍装置、家庭用エアコン、業務用エアコン、給湯器等の蒸気圧縮式ヒートポンプからなる群より選ばれる１種の用途に用いられる、請求項１～５のいずれかに記載の冷媒組成物。 One type of use in which the refrigerant composition is selected from the group consisting of a vapor compression heat pump such as a refrigerator, a refrigerator, a mobile air conditioner, a refrigerator (chiller), a container refrigeration apparatus, a home air conditioner, a commercial air conditioner, or a water heater. The refrigerant composition according to any one of claims 1 to 5, which is used in the above.
  7. ハイドロフルオロプロペンを含む冷媒組成物の安定化方法であって、該冷媒組成物に、炭素数１～４でアルコール価数１～４の脂肪族アルコールからなる群より選ばれる少なくとも１種の安定化剤を添加することを特徴とする安定化方法。 A method for stabilizing a refrigerant composition comprising hydrofluoropropene, wherein the refrigerant composition comprises at least one stabilization selected from the group consisting of aliphatic alcohols having 1 to 4 carbon atoms and 1 to 4 alcohol valences. A stabilizing method comprising adding an agent.
  8. ハイドロフルオロプロペン及び安定化剤を含む冷媒組成物の安定性の評価方法であって、密閉容器中で、酸素の存在下及び／又は不存在下に、該冷媒組成物を加熱処理した後、処理後の冷媒組成物の酸分を分析することを特徴とする評価方法。 A method for evaluating the stability of a refrigerant composition containing hydrofluoropropene and a stabilizer, wherein the refrigerant composition is heated in a sealed container in the presence and / or absence of oxygen, and then treated. The evaluation method characterized by analyzing the acid content of a refrigerant composition after.
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