WO2014065250A1 - ビスペンタエリスリトールモノホルマールのヘキサエステル - Google Patents
ビスペンタエリスリトールモノホルマールのヘキサエステル Download PDFInfo
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- WO2014065250A1 WO2014065250A1 PCT/JP2013/078513 JP2013078513W WO2014065250A1 WO 2014065250 A1 WO2014065250 A1 WO 2014065250A1 JP 2013078513 W JP2013078513 W JP 2013078513W WO 2014065250 A1 WO2014065250 A1 WO 2014065250A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/305—Saturated compounds containing more than one carboxyl group containing ether groups, groups, groups, or groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/33—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with hydroxy compounds having more than three hydroxy groups
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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
- C09K5/042—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 compounds containing carbon and hydrogen only
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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
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- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
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- 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
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
-
- 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
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- 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
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
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- 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
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- 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
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
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- 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
- C10N2030/02—Pour-point; Viscosity index
-
- 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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- 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
- C10N2030/08—Resistance to extreme temperature
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- 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
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- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- the present invention relates to a hexaester of bispentaerythritol monoformal excellent in oxidation stability and the like, and a refrigeration having excellent performance such as oxidation stability, lubricity and low temperature characteristics containing the hexaester of bispentaerythritol monoformal It relates to a machine oil composition.
- HFCs hydrofluorocarbons
- GWP global warming potential
- HFC is a stable refrigerant compared to chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC), and has little influence on lubricating oil, organic materials, and metals.
- CFC chlorofluorocarbon
- HCFC hydrochlorofluorocarbon
- lubricity of the refrigerant itself cannot be expected, refrigerating machine oil with high lubricity is required for the refrigerating machine oil for HFC.
- a refrigerating machine oil having high thermal and chemical stability is required (Non-Patent Document 1).
- the refrigeration oil in the refrigeration cycle, is partially circulated in the cycle together with the refrigerant, so that it is exposed to a high temperature region and a low temperature region. Particularly in the low temperature range, a part of the refrigerating machine oil discharged from the compressor may stay. If the refrigerating machine oil remains in the low temperature region for a long time, it may crystallize, resulting in a problem that the circulation amount of the refrigerant decreases in the refrigeration cycle, resulting in poor cooling. Therefore, development of highly stable refrigerating machine oil that does not precipitate for a long time even in a low temperature region is extremely important from the viewpoint of the reliability of the refrigeration apparatus (Patent Document 1).
- Patent Document 2 discloses an additive polyol ester oil for refrigerating machine oil
- Patent Document 3 discloses dipentaerythritol, 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid as a lubricating oil for a compression refrigerating machine. Hexaesters are described. However, the oxidation stability of the hexaester is not satisfactory.
- An object of the present invention is to provide excellent performance such as bispentaerythritol monoformal hexaester having excellent oxidation stability, and oxidation stability, lubricity, low temperature characteristics and the like containing the bispentaerythritol monoformal hexaester. It is providing the refrigerator oil composition which has.
- the present invention provides the following [1] to [4].
- [1] Formula (I) A mixed ester of bispentaerythritol monoformal and carboxylic acid represented by the formula: wherein the carboxylic acid is selected from among branched aliphatic monocarboxylic acids having 9 carbon atoms and aliphatic monocarboxylic acids having 4 to 8 carbon atoms. Hexaester of bispentaerythritol monoformal comprising one kind of carboxylic acid selected.
- [2] The hexaester of bispentaerythritol monoformal according to [1], wherein the branched aliphatic monocarboxylic acid having 9 carbon atoms is 3,5,5-trimethylhexanoic acid.
- [3] A refrigerating machine oil composition containing the hexaester of bispentaerythritol monoformal according to [1] or [2].
- [4] A working fluid composition for a refrigerator, comprising the refrigerator oil composition according to [3] and a refrigerant.
- a hexaester of bispentaerythritol monoformal excellent in oxidation stability and the like, and a refrigeration having excellent performance such as oxidation stability, lubricity, and low temperature characteristics containing the hexaester of bispentaerythritol monoformal A machine oil composition can be provided.
- FIG. 2 is a chart showing a nuclear magnetic resonance spectrum of a hexaester of bispentaerythritol monoformal obtained in Example 1.
- FIG. 4 is a chart showing a nuclear magnetic resonance spectrum of a hexaester of bispentaerythritol monoformal obtained in Example 3.
- FIG. 4 is a chart showing a nuclear magnetic resonance spectrum of a hexaester of bispentaerythritol monoformal obtained in Example 3.
- Example 6 is a chart showing a nuclear magnetic resonance spectrum of a hexaester of bispentaerythritol monoformal obtained in Example 4.
- Example 6 is a chart showing a nuclear magnetic resonance spectrum of a hexaester of bispentaerythritol monoformal obtained in Example 5.
- the hexaester of bispentaerythritol monoformal of the present invention has the formula (I) A mixed ester of bispentaerythritol monoformal and carboxylic acid represented by the formula: wherein the carboxylic acid is selected from among branched aliphatic monocarboxylic acids having 9 carbon atoms and aliphatic monocarboxylic acids having 4 to 8 carbon atoms. It is a hexaester of bispentaerythritol monoformal consisting of one kind of carboxylic acid selected.
- carboxylic acid constituting the hexaester of the bispentaerythritol monoformal of the present invention is referred to as a constituent carboxylic acid.
- the hexaesters of the present invention include the following (i) to (iii): (I) Bispentaene in which the constituent carboxylic acids in the same molecule are both a branched aliphatic monocarboxylic acid having 9 carbon atoms and a kind of carboxylic acid selected from aliphatic monocarboxylic acids having 4 to 8 carbon atoms.
- Hexaester of erythritol monoformal (ii) hexaester of bispentaerythritol monoformal and branched aliphatic monocarboxylic acid having 9 carbon atoms, and bispentaerythritol monoformal and aliphatic monocarboxylic acid having 4 to 8 carbon atoms
- Mixtures of hexaesters with one kind of carboxylic acid selected from (iii) Each embodiment of the mixture of (i) and (ii) above is contained.
- the hexaester of bispentaerythritol monoformal of the present invention contains, as impurities, a partial ester of bispentaerythritol monoformal, in which part of the hydroxyl group of bispentaerythritol monoformal is not esterified and remains as a hydroxyl group. May be.
- Examples of the branched aliphatic monocarboxylic acid having 9 carbon atoms constituting the hexaester of bispentaerythritol monoformal of the present invention include, for example, 2-methyloctanoic acid, 2,2-dimethylheptanoic acid, 2-propyl-4- Examples thereof include branched aliphatic monocarboxylic acids having 9 carbon atoms selected from methylpentanoic acid, 3,5,5-trimethylhexanoic acid, and the like. Among these, 3,5,5-trimethylhexanoic acid is preferable.
- Examples of the carboxylic acid selected from aliphatic monocarboxylic acids having 4 to 8 carbon atoms that constitute the hexaester of bispentaerythritol monoformal of the present invention include, for example, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid , Octanoic acid, isobutyric acid, 2-methylbutyric acid, 3-methylbutyric acid, 2,2-dimethylpropanoic acid, 2-ethylbutyric acid, 2-methylpentanoic acid, 4-methylpentanoic acid, 2-methylhexanoic acid, 2- Ethylpentanoic acid, 2-ethyl-2-methylbutyric acid, 2,2-dimethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 2-ethyl-2-methylpentanoic acid, 2 -Ethy
- the carboxylic acid selected from among aliphatic monocarboxylic acids of several 4 to 8 is preferably in the range of 90:10 to 10:90. A range of 80:20 to 30:70 is more preferable.
- the bispentaerythritol monoformal constituting the hexaester of the bispentaerythritol monoformal of the present invention can be obtained by a known method, for example, a non-patent document (“South African Journal of Chemistry”, 1991, vol. 4, No. 122, p.122). According to the method described in), pentaerythritol is triacetylated with acetic anhydride, the resulting pentaerythritol triacetate is condensed with dimethoxymethane in the presence of an acid catalyst, and the acetyl group of the resulting condensate is hydrolyzed. Can be obtained. Further, for example, in accordance with the method described in US Pat.
- the hexaester of bispentaerythritol monoformal of the present invention is selected from, for example, bispentaerythritol monoformal, branched aliphatic monocarboxylic acid having 9 carbon atoms, and aliphatic monocarboxylic acid having 4 to 8 carbon atoms. It can be produced by reacting with a kind of carboxylic acid at 120 to 300 ° C. for 5 to 60 hours (hereinafter, this method is referred to as Production Method 1). At this time, each carboxylic acid may be added to the reaction system all at once, or may be added sequentially.
- a catalyst may be used, and examples of the catalyst include mineral acids, organic acids, Lewis acids, organic metals, solid acids and the like.
- the mineral acid include hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid and the like.
- the organic acid include p-toluenesulfonic acid, benzenesulfonic acid, butanesulfonic acid, propanesulfonic acid, ethanesulfonic acid, methanesulfonic acid and the like.
- Specific examples of the Lewis acid include boron trifluoride, aluminum chloride, tin tetrachloride, titanium tetrachloride and the like.
- Specific examples of the organic metal include tetrapropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, and the like.
- Specific examples of the solid acid include a cation exchange resin.
- the total amount of branched aliphatic monocarboxylic acid having 9 carbon atoms and one kind of carboxylic acid selected from aliphatic monocarboxylic acids having 4 to 8 carbon atoms is less than the hydroxyl group of bispentaerythritol monoformal. Thus, it is preferably 1.1 to 1.4 times mol.
- the hexaester of bispentaerythritol monoformal of the present invention includes, for example, bispentaerythritol monoformal, an anhydride of a branched aliphatic monocarboxylic acid having 9 carbon atoms, and an aliphatic monocarboxylic acid having 4 to 8 carbon atoms. It is also possible to produce a carboxylic acid anhydride selected from among them by reacting at 50 to 100 ° C. for 1 to 10 hours (this method is hereinafter referred to as Production Method 2). At this time, the anhydrides of the respective carboxylic acids may be added to the reaction system all at once or sequentially, for example.
- a catalyst may be used, and examples of the catalyst include organic bases, organic salts, solid acids, and the like.
- the organic base include pyridine and N, N-dimethyl-4-aminopyridine.
- the organic salt include sodium acetate, scandium (III) trifluoromethanesulfonate imide, trimethylsilyl trifluoromethanesulfonate, and the like.
- Specific examples of the solid acid include a cation exchange resin.
- the total amount of anhydrides of branched aliphatic monocarboxylic acid having 9 carbon atoms and one kind of carboxylic acid anhydride selected from aliphatic monocarboxylic acids having 4 to 8 carbon atoms is The molar amount is preferably 0.5 to 1.4 times the hydroxyl group of bispentaerythritol monoformal.
- the molar ratio may differ from the molar ratio at the time of charging.
- a solvent may be used, and examples of the solvent include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, isohexane, isooctane, isononane, decane, and the like.
- a method in which the hexaester of the bispentaerythritol monoformal of the present invention is usually used in organic synthetic chemistry (washing with water and / or aqueous alkali solution, activated carbon , Treatment with an adsorbent, etc., various chromatography, distillation, etc.).
- the hexaester of bispentaerythritol monoformal of the present invention is one kind selected from bispentaerythritol monoformal, a branched aliphatic monocarboxylic acid having 9 carbon atoms, and an aliphatic monocarboxylic acid having 4 to 8 carbon atoms. Since it is composed of carboxylic acid, it has excellent performance such as oxidation stability.
- the hexaester of bispentaerythritol monoformal of the present invention has sufficient low temperature characteristics, sufficient low temperature fluidity, and sufficient lubricity in addition to excellent oxidation stability.
- the refrigerating machine oil composition of the present invention refers to one containing the hexaester of the bispentaerythritol monoformal of the present invention.
- the refrigerating machine oil composition which consists only of this hexaester may be sufficient, and the refrigerating machine oil composition which consists of this hexaester and the base oil for refrigerating machine oil may be sufficient.
- the acid value of the hexaester is preferably 0.5 mgKOH / g or less, and more preferably 0.1 mgKOH / g or less.
- the hydroxyl value of the hexaester is 20 mgKOH / g Or less, more preferably 10 mgKOH / g or less.
- the refrigerating machine oil composition can be provided with excellent performance such as oxidation stability, lubricity and low temperature characteristics. .
- the hexaester of the bispentaerythritol monoformal of the present invention includes nuclear magnetic resonance spectroscopy (hereinafter referred to as NMR), gas chromatography (hereinafter referred to as GC), gas chromatography mass spectrometry (hereinafter referred to as GC-MS), etc. Identified by analytical method. Further, in the refrigerating machine oil composition of the present invention, the hexaester of the bispentaerythritol monoformal of the present invention contained in the refrigerating machine oil composition is identified by the same analysis method. Identification is facilitated by previously separating the hexaester of bispentaerythritol monoformal from the refrigerating machine oil composition by a method such as distillation, solvent extraction, or crystallization.
- NMR nuclear magnetic resonance spectroscopy
- GC gas chromatography
- GC-MS gas chromatography mass spectrometry
- the hexaester content of the bispentaerythritol monoformal of the present invention is not particularly limited as long as various performances such as lubricity, low temperature characteristics and oxidation stability are not impaired.
- the hexaester content in the refrigerating machine oil composition is preferably 0.1 to 50% by weight, and 1 to 30% by weight. More preferably, it is 1 to 10% by weight.
- examples of the refrigerating machine base oil include mineral oil and synthetic base oil.
- mineral oil examples include paraffin-based crude oil, intermediate-based crude oil, and naphthenic-based crude oil. Further, refined oils obtained by purifying these by distillation or the like can also be used.
- Synthetic base oils include, for example, poly- ⁇ -olefins (polybutene, polypropylene, ⁇ -olefin oligomers having 8 to 14 carbon atoms, etc.), aliphatic esters (fatty acid monoesters) other than the hexaester of bispentaerythritol monoformal of the present invention. Ester, fatty acid ester of polyhydric alcohol, aliphatic polybasic acid ester, etc.), aromatic ester (aromatic monoester, aromatic ester of polyhydric alcohol, aromatic polybasic acid ester, etc.), polyalkylene glycol, polyvinyl ether , Polycarbonate, alkylbenzene and the like.
- examples of the polyhydric alcohol include pentaerythritol, polypentaerythritol (condensates of pentaerythritol such as dipentaerythritol, tripentaerythritol, and tetrapentaerythritol), neopentyl glycol, trimethylolpropane, and the like.
- examples of the fatty acid include linear or branched aliphatic monocarboxylic acids having 4 to 18 carbon atoms.
- fatty acid ester of the polyhydric alcohol examples include an ester of pentaerythritol, isobutyric acid and 2-ethylhexanoic acid, an ester of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid, pentaerythritol, Esters of pentanoic acid and 3,5,5-trimethylhexanoic acid, pentaerythritol, pentanoic acid, heptanoic acid and 3,5,5-trimethylhexanoic acid, pentaerythritol, 2-methylbutyric acid and 2-ethylhexane Esters of acids, esters of pentaerythritol, 3-methylbutyric acid and 3,5,5-trimethylhexanoic acid, esters of pentaerythritol, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, est
- the refrigerating machine oil composition of the present invention may contain an additive for lubricating oil as necessary.
- lubricant additives include metal deactivators, antioxidants, wear reducers (antiwear agents, anti-seizure agents, extreme pressure agents, etc.), friction modifiers, acid scavengers, rust inhibitors. And antifoaming agents.
- the content of these additives is preferably 0.001 to 5% by weight in the refrigerating machine oil composition, respectively.
- the metal deactivator examples include benzotriazole (hereinafter referred to as BZT), N, N′-disalicylidene-1,2-diaminopropane, and the like, and equipment using a refrigerator oil composition or a refrigerator oil composition In order to prolong the service life, etc., it is dissolved in a refrigerator oil composition and used.
- BZT has a low solubility in mineral oil and / or synthetic oil (Japanese Patent Application Laid-Open No. 59-189195), so its use amount may be limited.
- the solubility of BZT in the refrigerating machine oil composition is improved and the amount of use is increased. be able to.
- the refrigerating machine oil composition of the present invention contains a hexaester of bispentaerythritol monoformal, it has excellent performance such as oxidation stability, lubricity and low temperature characteristics.
- Refrigerator oil compositions are used in refrigerators such as household room air conditioners, but when the refrigerator is installed, air may enter the refrigeration cycle and the refrigerator oil composition may be affected by oxygen. Therefore, the refrigerator oil composition needs high oxidation stability.
- the oxidation stability of the bispentaerythritol monoformal hexaester of the present invention and the refrigerating machine oil composition can be evaluated by measuring the RBOT life and the like by an oxidation stability test.
- the RBOT life is measured by the method described in the test examples described later.
- HFC refrigerant has a problem in lubricity because it does not contain chlorine in its molecular structure. Therefore, the refrigerating machine oil composition used for the HFC refrigerant is required to have better lubricity.
- the lubricity include friction reduction, wear reduction (wear resistance), extreme pressure, and the like.
- the refrigerating machine oil composition is preferably a refrigerating machine oil composition that does not have volatility in the high temperature range and does not solidify or precipitate in the low temperature range when stored or used for a long time in a place where the temperature change is large.
- the temperature range is not particularly limited, but a refrigerating machine oil composition that can be stably used at about 150 ° C. in a high temperature range and about ⁇ 20 ° C. in a low temperature range is preferable.
- a property that does not cause solidification or precipitation in a low temperature region is defined as a low temperature property.
- the refrigerating machine oil composition of the present invention has sufficient thermal stability and sufficient oxidation / hydrolysis stability in addition to excellent oxidation stability, lubricity and low temperature characteristics.
- the working fluid composition for a refrigerator of the present invention refers to one containing the refrigerator oil composition of the present invention and a refrigerant.
- the mixing ratio of the refrigerating machine oil composition of the present invention and the refrigerant is not particularly limited, but is preferably 1 to 1000 parts by weight of the refrigerating machine oil composition of the present invention with respect to 100 parts by weight of the refrigerant. More preferably, it is part.
- examples of the refrigerant of the working fluid composition for a refrigerator include a fluorine-containing refrigerant and a natural refrigerant.
- fluorine-containing refrigerant examples include difluoromethane (HFC32), trifluoromethane (HFC23), pentafluoroethane (HFC125), 1,1,2,2-tetrafluoroethane (HFC134), 1,1,1,2- Hydrofluorocarbons such as tetrafluoroethane (HFC134a) and 1,1,1-trifluoroethane (HFC143a), 2,3,3,3-tetrafluoropropene (HFO1234yf), 1,3,3,3-tetrafluoropropene (HFO1234ze), 1,2,3,3-tetrafluoropropene (HFO1234ye), 1,2,3,3,3-pentafluoropropene (HFO1225ye) and the like, and mixtures thereof It is done.
- HFC32 difluoromethane
- HFC23 trifluoromethane
- HFC125 1,1,2,2-tetrafluoroethane
- natural refrigerants include hydrocarbons such as propane, butane, and isobutane, carbon dioxide, and ammonia.
- the hexaester of bispentaerythritol monoformal according to the present invention is used in refrigeration oil compositions and working fluid compositions for refrigeration machines, as well as motor oils and greases used in engine oils, gear oils, hybrid cars and electric cars. It can also be used for additives for lubricating oils, detergents for metal parts, plasticizers, cosmetics and the like.
- the refrigerator oil composition and the working fluid composition for a refrigerator of the present invention are used for refrigeration of room air conditioners, packaged air conditioners, car air conditioners, dehumidifiers, refrigerators, freezers, refrigerators, vending machines, showcases, chemical plants, etc. It is preferably used for a machine.
- test solution 1) Preparation of bispentaerythritol monoformal test solution 10 mg of bispentaerythritol monoformal obtained in Production Example 1 below and 1 mL of a trimethylsilylating agent (product name: TMS-HT, manufactured by Tokyo Chemical Industry Co., Ltd.) And the mixture was stirred at 80 ° C. for 10 minutes. After the reaction, the reaction solution was filtered through a membrane filter (PTFE, 0.5 ⁇ m), and the filtrate was used as a test solution.
- a trimethylsilylating agent product name: TMS-HT, manufactured by Tokyo Chemical Industry Co., Ltd.
- ⁇ GC-MS> The esters obtained in Examples 1, 3 and 4 below were measured by GC-MS.
- the measurement by GC-MS was performed with the following measuring equipment and measurement conditions.
- LC high performance liquid chromatography
- test solution 2.5 mg of bispentaerythritol monoformal obtained in the following Production Example 1 and 497.5 mg of 0.1 wt% phosphoric acid aqueous solution were mixed to prepare a test solution.
- Measuring instrument Agilent 1200 Series (manufactured by Agilent Technologies) Measurement condition; Column: YMC-Pack ODS-AM (spherical, particle diameter 5 ⁇ m, pore diameter 12 nm, length 300 mm ⁇ inner diameter 4.6 mm) (manufactured by YMC) ⁇
- Developing solution 0.1 wt% phosphoric acid aqueous solution, flow rate 0.7 mL / min
- Sample injection volume 5 ⁇ L ⁇ Detector: RI
- the concentrated solution was washed once with 20 mL of an aqueous alkaline solution containing sodium hydroxide twice as much as the acid value of the concentrated solution and three times with 20 mL of water, and bubbled with nitrogen at 100 ° C. for 1 hour under a reduced pressure of 1.3 kPa. Dehydrated while performing. Next, 0.2 g of an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd., product name: KYOWARD 500) and 0.3 g of activated carbon (manufactured by Nippon Enviro Chemicals Co., Ltd., product name: Shirasagi P) are added, and the pressure is reduced to 110 kPa under a reduced pressure of 1.3 kPa.
- an adsorbent manufactured by Kyowa Chemical Industry Co., Ltd., product name: KYOWARD 500
- activated carbon manufactured by Nippon Enviro Chemicals Co., Ltd., product name: Shirasagi P
- hexaester 1 was obtained by filtering with a membrane filter (PTFE, 0.2 micrometer).
- the nuclear magnetic resonance spectrum of hexaester 1 was measured, and the molar ratio of 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid constituting hexaester 1 was calculated.
- a chart of the obtained nuclear magnetic resonance spectrum is shown in FIG.
- hexaester 1 was measured by GC and GC-MS. From GC, main peak retention times (66.3 minutes, 73.1 minutes, 80.7 minutes, 88.7 minutes, 96.6 minutes, 105.5 minutes, 115.5 minutes) were confirmed. GC-MS confirmed the retention time of the main peak and its fragment. The results of GC-MS are shown in Table 1.
- Peak 1-1 is a hexaester “molecular weight” where the molecular number of the carboxylic acid [3,5,5-trimethylhexanoic acid / 2-ethylhexanoic acid] bound to one molecule of bispentaerythritol monoformal is [0/6].
- Peak 1-2 is a peak of the hexaester “molecular weight 1056 g / mol” in which the number of molecules of the carboxylic acid is [1/5].
- Peak 1-3 is a peak of hexaester “molecular weight 1070 g / mol” in which the number of molecules of the carboxylic acid is [2/4].
- Peak 1-4 is a peak of the hexaester “molecular weight 1084 g / mol” in which the number of molecules of the carboxylic acid is [3/3].
- Peak 1-5 is a peak of the hexaester “molecular weight 1098 g / mol” in which the number of molecules of the carboxylic acid is [4/2].
- Peak 1-6 is a hexaester “molecular weight 1112 g / mol” peak in which the number of molecules of the carboxylic acid is [5/1].
- Peak 1-7 is a hexaester having a molecular weight of [6/0] and a molecular weight of 1126 g / mol.
- Example 2 [Hexane of bispentaerythritol monoformal having a molar ratio of 3,5,5-trimethylhexanoic acid to 2-ethylhexanoic acid (ratio of 3,5,5-trimethylhexanoic acid / 2-ethylhexanoic acid) of 74/26 Production of ester (hexaester 2)]
- the molar ratio of bispentaerythritol monoformal, 3,5,5-trimethylhexanoic anhydride and 2-ethylhexanoic anhydride used bispentaerythritol monoformal / 3,5,5-trimethylhexanoic acid
- the hexaester 2 was obtained in the same manner as in Example 1 except that the anhydride / 2-ethylhexanoic acid anhydride ratio was changed to 1.00 / 5.04 / 1.80.
- the nuclear magnetic resonance spectrum of hexaester 2 was measured, and the molar ratio of 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid constituting hexaester 2 was calculated. Further, when the hexaester 2 was measured by GC, a peak was detected at the same retention time as the hexaester 1 of Example 1.
- the hexaester 3 was obtained in the same manner as in Example 1.
- the nuclear magnetic resonance spectrum of hexaester 3 was measured, and the molar ratio of 3,5,5-trimethylhexanoic acid and isobutyric acid constituting hexaester 3 was calculated.
- a chart of the obtained nuclear magnetic resonance spectrum is shown in FIG.
- Hexaester 3 was measured by GC and GC-MS. From GC, main peak retention times (24.6 minutes, 27.9 minutes, 33.2 minutes, 41.9 minutes, 56.2 minutes, 79.5 minutes, 115.7 minutes) were confirmed. GC-MS confirmed the retention time of the main peak and its fragment. The results of GC-MS are shown in Table 2.
- Peak 3-1 is a hexaester “molecular weight 705 g / mol of carboxylic acid [3,5,5-trimethylhexanoic acid / isobutyric acid] bound to one molecule of bispentaerythritol monoformal [0/6].
- Peak 3-2 is a peak of the hexaester “molecular weight 775 g / mol” in which the number of molecules of the carboxylic acid is [1/5].
- Peak 3-3 is a hexaester “molecular weight of 845 g / mol” with the carboxylic acid molecular number [2/4].
- the peak 3-4 is a hexaester “molecular weight 915 g / mol” peak in which the number of molecules of the carboxylic acid is [3/3].
- Peak 3-5 is a peak of the hexaester “molecular weight 985 g / mol” in which the number of molecules of the carboxylic acid is [4/2].
- Peak 3-6 is a peak of the hexaester “molecular weight 1056 g / mol” in which the number of molecules of the carboxylic acid is [5/1].
- Peak 3-7 is a hexaester “molecular weight 1126 g / mol” peak where the number of molecules of the carboxylic acid is [6/0].
- Bispentaerythritol monoformal, 3,5,5-trimethylhexanoic acid anhydride and pentanoic acid anhydride Except that the molar ratio (bispentaerythritol monoformal / an anhydride of 3,5,5-trimethylhexanoic acid / anhydride ratio of pentanoic acid) is 1.00 / 5.76 / 1.20.
- the hexaester 4 was obtained in the same manner as in Example 1.
- the nuclear magnetic resonance spectrum of hexaester 4 was measured, and the molar ratio of 3,5,5-trimethylhexanoic acid and pentanoic acid constituting hexaester 4 was calculated.
- a chart of the obtained nuclear magnetic resonance spectrum is shown in FIG.
- hexaester 4 was measured by GC and GC-MS.
- GC confirmed the retention time of the main peak (34.0 minutes, 39.4 minutes, 46.8 minutes, 57.0 minutes, 70.6 minutes, 88.6 minutes, 111.4 minutes).
- GC-MS confirmed the retention time of the main peak and its fragment. The results of GC-MS are shown in Table 3.
- Peak 4-1 is a hexaester “molecular weight 789 g / mol of carboxylic acid [3,5,5-trimethylhexanoic acid / pentanoic acid] bound to one molecule of bispentaerythritol monoformal [0/6].
- Peak 4-2 is a peak of the hexaester “molecular weight 845 g / mol” where the number of molecules of the carboxylic acid is [1/5].
- Peak 4-3 is a hexaester “molecular weight 901 g / mol” peak in which the number of molecules of the carboxylic acid is [2/4].
- Peak 4-4 is a peak of the hexaester “molecular weight 957 g / mol” in which the number of molecules of the carboxylic acid is [3/3].
- Peak 4-5 is a peak of the hexaester “molecular weight 1013 g / mol” in which the number of molecules of the carboxylic acid is [4/2].
- Peak 4-6 is a hexaester “molecular weight 1070 g / mol” peak in which the number of molecules of the carboxylic acid is [5/1].
- Peak 4-7 is a peak of the hexaester “molecular weight 1126 g / mol” in which the number of molecules of the carboxylic acid is [6/0].
- Bispentaerythritol monoformal, 3,5,5-trimethylhexanoic acid anhydride and 3-methyl The molar ratio of butyric anhydride used (bispentaerythritol monoformal / 3,5,5-trimethylhexanoic anhydride / 3-methylbutyric anhydride) was 1.00 / 3.60 / 3.
- the hexaester 5 was obtained in the same manner as in Example 1 except that it was changed to 00.
- the nuclear magnetic resonance spectrum of hexaester 5 was measured, and the molar ratio of 3,5,5-trimethylhexanoic acid and 3-methylbutyric acid constituting hexaester 5 was calculated.
- FIG. 4 shows a chart of the obtained nuclear magnetic resonance spectrum. Moreover, when hexaester 5 was measured by GC, each peak (retention time: 28.8 minutes, 33.0 minutes, 39.4 minutes, 48.9 minutes, 62.8 minutes, 82.6 minutes, 110. 2 minutes
- the degassed mixture was stirred at 190-240 ° C. for 18 hours with nitrogen bubbling.
- the reaction solution was concentrated at 210 ° C. under reduced pressure of 1.3 kPa for 1 hour.
- the concentrate was washed once with 100 mL of an aqueous alkaline solution containing sodium hydroxide twice as much as the acid value of the concentrate and three times with 100 mL of water.
- the organic layer was dehydrated while bubbling nitrogen under reduced pressure of 1.3 kPa at 100 ° C. for 1 hour.
- Test Example 1 Measurement of kinematic viscosity of hexaester Using a Canon-Fenske viscometer, the kinematic viscosities of hexaesters 1 to 5 and hexaester A at 40 ° C. and 100 ° C. were measured according to the method of JIS K2283: 2000. . The results are shown in Table 4.
- Test Example 2 Evaluation of oxidation stability of hexaester (measurement of RBOT life) An oxidation stability test was performed using a rotary cylinder type oxidation stability tester RBOT-02 (manufactured by Koiso Co., Ltd.). 10 g of each of hexaesters 1 to 5 and hexaester A and electrolytic copper wire (diameter 1.6 mm, length 3 m) polished with sandpaper # 400 are placed in a pressure vessel, and then oxygen is injected into the pressure vessel up to 620 kPa. did. The pressure vessel was placed in a constant temperature bath at 150 ° C. and rotated at 100 revolutions per minute to start the test, and this time was recorded as the start of the test.
- the RBOT life of hexaester 1 is 100 minutes
- the RBOT life of hexaester 2 is 144 minutes
- the RBOT life of hexaester 3 is 142 minutes
- the RBOT life of hexaester 4 is 251 minutes.
- the RBOT life of hexaester 5 was 312 minutes, and hexaesters 1 to 5 showed excellent oxidation stability.
- the RBOT life of hexaester A is 58 minutes, and hexaester A is not sufficiently oxidatively stable.
- hexaesters 1 to 5 were not solidified, and no precipitate was observed. It can be seen that hexaesters 1 to 5 are excellent in balance between oxidation stability and low temperature characteristics.
- Example 6 [Preparation of Refrigerator Oil Composition 1] Refrigerating machine base oil A produced in Production Example 4 and hexaester 1 produced in Example 1 were mixed at a weight ratio of 70:30 (Base Oil A for Refrigerating Machine: Hexaester 1) to produce a refrigerating machine oil composition. Product 1 was prepared.
- Example 7 [Preparation of Refrigerator Oil Composition 2] Refrigerating machine base oil A produced in Production Example 4 and hexaester 1 produced in Example 1 were mixed at a weight ratio of 92: 8 (Refrigerating machine base oil A: Hexaester 1) to produce a refrigerating machine oil composition. Product 2 was prepared.
- Example 8 [Preparation of Refrigerator Oil Composition 3] Refrigerating machine base oil A produced in Production Example 4 and hexaester 1 produced in Example 1 were mixed at a weight ratio of 96: 4 (Refrigerating machine base oil A: Hexaester 1) to produce a refrigerating machine oil composition. Product 3 was prepared.
- Refrigerating machine base oil A produced in Production Example 4 and hexaester 1 produced in Example 1 were mixed at a weight ratio of 98: 2 (Refrigerating machine base oil A: Hexaester 1) to produce a refrigerating machine oil composition.
- Product 4 was prepared.
- Refrigerating machine base oil A produced in Production Example 4 and hexaester A produced in Comparative Example 1 were mixed at a weight ratio of 70:30 (Base Oil A for Refrigerating Machine: Hexaester A) to produce a refrigerating machine oil composition.
- Product 6 was prepared.
- Example 10 [Production of Refrigerator Oil Composition 7] Instead of dipentaerythritol, a mixture of pentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd., product name; pentalit-S) and bispentaerythritol monoformal produced in Production Example 1 was used.
- the molar ratio of the amounts of 5,5-trimethylhexanoic acid and 2-ethylhexanoic acid used is 1.00.
- a refrigerating machine oil composition 7 was obtained in the same manner as in Comparative Example 1 except that it was changed to /0.03/2.12/2.68.
- the refrigerator oil composition 7 was measured by NMR and GC, and it was confirmed that a hexaester composed of bispentaerythritol monoformal, 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid was contained. From GC, the area ratio of the peak of the hexaester was 1.89 area%. When the area% value was converted to weight% using the calibration curve method, the weight% value corresponded to a value about 1.3 to 2.0 times the area%.
- Example 11 [Production of Refrigerator Oil Composition 8] Instead of dipentaerythritol, a mixture of pentaerythritol (manufactured by Guangei Chemical Industry Co., Ltd., product name; pentalit-S) and bispentaerythritol monoformal prepared in Production Example 1 was used, and pentanoic acid ( (Made by Tokyo Chemical Industry Co., Ltd.), molar ratio of pentaerythritol, bispentaerythritol monoformal, 3,5,5-trimethylhexanoic acid and pentanoic acid used (pentaerythritol / bispentaerythritol monoformal / 3,5,5) Refrigerating machine oil composition 8 was obtained in the same manner as in Comparative Example 1 except that the ratio of 5-trimethylhexanoic acid / pentanoic acid was changed to 1.00 / 0.03 / 3.68 / 1.12.
- the refrigerator oil composition 8 was measured by NMR and GC, and it was confirmed that a hexaester composed of bispentaerythritol monoformal, 3,5,5-trimethylhexanoic acid and pentanoic acid was contained. Moreover, from GC, the area ratio of the peak of the hexaester was 2.35 area%. When the area% value was converted to weight% using the calibration curve method, the weight% value corresponded to a value about 1.3 to 2.0 times the area%.
- Test Example 4 Measurement of Kinematic Viscosity of Refrigerating Machine Oil Composition According to the method of Test Example 1, the kinematic viscosities of the refrigerating machine oil compositions 1 to 8 at 40 ° C. and 100 ° C. were measured. The results are shown in Tables 5 and 6.
- Test Example 5 Evaluation of oxidation stability of refrigerating machine oil composition (measurement of RBOT life) According to the method of Test Example 2, the oxidative stability tests of the refrigerator oil compositions 1 to 8 were performed. The results are shown in Tables 5 and 6. The longer the RBOT life, the better the oxidation stability of the refrigerating machine oil composition.
- the RBOT life of the refrigerator oil composition 1 is 109 minutes
- the RBOT life of the refrigerator oil composition 2 is 116 minutes
- the RBOT life of the refrigerator oil composition 3 is 106 minutes.
- the RBOT life of the machine oil composition 4 is 121 minutes
- the RBOT life of the refrigerator oil composition 7 is 116 minutes
- the RBOT life of the refrigerator oil composition 8 is 563 minutes
- the refrigerator oil composition 5 and the refrigerator oil composition Compared to product 6, the oxidation stability was excellent.
- the wear scar diameter of the refrigerator oil composition 1 is 0.22 mm
- the wear scar diameter of the refrigerator oil composition 2 is 0.21 mm
- the wear scar diameter of the refrigerator oil composition 3 is 0.22 mm
- the wear scar diameter of composition 4 is 0.21 mm
- the wear scar diameter of refrigerator oil composition 7 is 0.21 mm
- the wear scar diameter of refrigerator oil composition 8 is 0.20 mm
- the refrigerating machine oil compositions 1 to 4, 7 and 8 did not solidify or precipitate at ⁇ 20 ° C. even when containing 1.5% by weight of BZT, and compared with the refrigerating machine oil composition 5, BZT. It was shown that it was excellent in low-temperature characteristics when containing. Refrigerating machine oil compositions 1-4, 7 and 8 containing the hexaester of bispentaerythritol monoformal according to the present invention are excellent in balance in oxidation stability, lubricity, low temperature characteristics when containing BZT, and the like. Recognize.
- a hexaester of bispentaerythritol monoformal excellent in oxidation stability and the like, and a refrigeration having excellent performance such as oxidation stability, lubricity, and low temperature characteristics containing the hexaester of bispentaerythritol monoformal A machine oil composition can be provided.
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Abstract
Description
[1]式(I)
[2]前記炭素数9の分岐脂肪族モノカルボン酸が、3,5,5-トリメチルヘキサン酸である[1]に記載のビスペンタエリスリトールモノホルマールのヘキサエステル。
[3][1]または[2]に記載のビスペンタエリスリトールモノホルマールのヘキサエステルを含有する冷凍機油組成物。
[4][3]に記載の冷凍機油組成物と冷媒とを含有する冷凍機用作動流体組成物。
(i)同一分子内における構成カルボン酸が、炭素数9の分岐脂肪族モノカルボン酸と、炭素数4~8の脂肪族モノカルボン酸の中から選ばれる一種のカルボン酸の双方からなるビスペンタエリスリトールモノホルマールのヘキサエステル
(ii)ビスペンタエリスリトールモノホルマールと炭素数9の分岐脂肪族モノカルボン酸とのヘキサエステル、およびビスペンタエリスリトールモノホルマールと炭素数4~8の脂肪族モノカルボン酸の中から選ばれる一種のカルボン酸とのヘキサエステルの混合物
(iii)上記(i)および(ii)の混合物
の各態様が含有される。
以下の製造例1で得られたビスペンタエリスリトールモノホルマール、ならびに、製造例4、実施例1~5、10、11、および比較例1で得られたエステルおよび冷凍機油組成物を、NMRで測定した。NMRでの測定は、以下の測定機器、測定手法により行った。
測定機器;GSX-400(400MHz)(日本電子社製)
測定条件;
・核種;1H
・標準物;テトラメチルシラン
・溶媒;CDCl3またはd6-DMSO
以下の製造例1で得られたビスペンタエリスリトールモノホルマールの純度、ならびに、実施例1~5、10、および11で得られたエステルおよび冷凍機油組成物の主要ピークの保持時間をGCで測定した。GCでの測定は、以下の方法で検液を調製後、以下の測定機器、測定条件により行った。
1)ビスペンタエリスリトールモノホルマールの検液の調製
反応器に以下の製造例1で得られたビスペンタエリスリトールモノホルマール10mgとトリメチルシリル化剤(東京化成工業社製、製品名:TMS-HT)1mLとを仕込み、混合液を80℃で10分間攪拌した。反応後、反応液をメンブレンフィルター(PTFE、0.5μm)で濾過し、濾液を検液とした。
2)エステルおよび冷凍機油組成物の検液の調製
以下の実施例1~11、比較例2および比較例3で得られたエステルおよび冷凍機油組成物の各0.1gと、アセトン0.5gとを混合し、検液とした。
測定機器;Agilent7890A(アジレント・テクノロジー社製)
測定条件;
・カラム;HP-5(長さ30m×内径0.320mm×膜厚0.25μm)(アジレント・テクノロジー社製)
・キャリアガス;窒素、流量1.0mL/分
・INJ/DET温度;330℃/350℃
・注入法;スプリット法(1μL注入、比1/50)
・検出器;FID
・測定プログラム;100℃から10℃/分の速度で昇温し、325℃に達してからその温度で97.5分間保持
以下の実施例1、3および4で得られたエステルを、GC-MSで測定した。GC-MSでの測定は、以下の測定機器、測定条件により行った。
測定機器;Agilent7890A(アジレント・テクノロジー社製)
日本電子JMS-T100GCv質量分析計(日本電子社製)
測定条件;
・カラム; DB-5(長さ30m×内径0.25mm×膜厚0.25μm)(アジレント・テクノロジー社製)
・キャリアガス;ヘリウム、流量1.0mL/分
・注入温度;300℃
・注入法;スプリット法(比1/50)
・イオン化法;CI(反応ガス;アンモニア)、EI
・測定プログラム;100℃から10℃/分の速度で昇温し、325℃に達してからその温度で97.5分間保持
以下の製造例1で得られたビスペンタエリスリトールモノホルマールの純度を高速液体クロマトグラフィー(以下、LCという)で測定した。LCでの測定は、以下の方法で検液を調製後、以下の測定機器、測定条件により行った。
測定機器;Agilent1200Series(アジレント・テクノロジー社製)
測定条件;
・カラム;YMC-Pack ODS-AM(球状、粒子径5μm、細孔径12nm、長さ300mm×内径4.6mm)(ワイエムシィ社製)
・展開液;0.1重量%リン酸水溶液、流速0.7mL/分
・カラム温度;40℃
・サンプル注入量;5μL
・検出器;RI
[ビスペンタエリスリトールモノホルマールの製造]
(1)化合物(i)の製造
1H-NMR(CDCl3、δppm);1.46(s、3H)、3.47(s、2H)、4.02(s、6H)
1H-NMR(CDCl3、δppm);1.46(s、6H)、3.24(s、4H)、3.98(s、12H)、4.53(s、2H)
反応器に化合物(ii)78.3gと水320gとを仕込み、混合液を100℃で2時間撹拌した。次いで、強塩基性陰イオン交換樹脂1905.0g(三菱化学社製、製品名;ダイヤイオンSA11A)を加え、室温で1時間攪拌した。反応液を濾過した後、濾液を濃縮した。濃縮物をエタノール1.7Lで晶析して、ビスペンタエリスリトールモノホルマールを53.6g得た。
1H-NMR(d6-DMSO、δppm);3.32-3.40(m、16H)、4.25(t、6H)、4.54(s、2H)
GCで測定した純度:95面積%以上
LCで測定した純度:95面積%以上
[3,5,5-トリメチルヘキサン酸の無水物の製造]
反応器に3,5,5-トリメチルヘキサン酸633.0g(4.00モル、KHネオケム社製)と無水酢酸817.5g(8.00モル、和光純薬工業社製)とを仕込み、混合液を120℃で1時間撹拌した。反応後、反応液を0.4kPaの減圧下、157~162℃で蒸留して、3,5,5-トリメチルヘキサン酸の無水物を496.4g得た。
[2-エチルヘキサン酸の無水物の製造]
反応器に2-エチルヘキサン酸721.1g(5.00モル、KHネオケム社製)と無水酢酸919.7g(9.00モル、和光純薬工業社製)とを仕込み、混合液を120℃で1時間撹拌した。反応後、反応液を0.1kPaの減圧下、126~133℃で蒸留して、2-エチルヘキサン酸の無水物を509.8g得た。
[3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸のモル比(3,5,5-トリメチルヘキサン酸/2-エチルヘキサン酸比)が50/50であるビスペンタエリスリトールモノホルマールのヘキサエステル(ヘキサエステル1)の製造]
反応器に製造例1で製造したビスペンタエリスリトールモノホルマール8.5g(0.03モル)、製造例2で製造した3,5,5-トリメチルヘキサン酸の無水物32.2g(0.11モル) 、製造例3で製造した2-エチルヘキサン酸の無水物24.3g(0.09モル)およびピリジン42.7g(0.54モル、和光純薬工業社製)を仕込み、混合液を20kPaの減圧下、室温で15分間窒素バブリングを行うことで脱気した。次いで、脱気後の混合液を90℃で6時間、窒素バブリングを行いながら撹拌した。反応後、反応液を1.3kPaの減圧下、150~220℃で2時間濃縮した。濃縮液を濃縮液の酸価に対して2倍モルの水酸化ナトリウムを含むアルカリ水溶液20mLで1回、水20mLで3回洗浄し、1.3kPaの減圧下、100℃で1時間、窒素バブリングを行いながら脱水した。次いで、吸着剤0.2g(協和化学工業社製、製品名;キョーワード500)と活性炭0.3g(日本エンバイロケミカルズ社製、製品名;白鷺P)を加え、1.3kPaの減圧下、110℃で1時間、窒素バブリングを行いながら撹拌した。次いで、メンブレンフィルター(PTFE、0.2μm)で濾過することにより、ヘキサエステル1を24.7g得た。ヘキサエステル1の核磁気共鳴スペクトルを測定し、ヘキサエステル1を構成する3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸のモル比を算出した。得られた核磁気共鳴スペクトルのチャートを図1に示す。また、ヘキサエステル1をGCおよびGC-MSで測定した。GCより、主要なピークの保持時間(66.3分、73.1分、80.7分、88.7分、96.6分、105.5分、115.5分)を確認した。GC-MSより、主要なピークの保持時間とそのフラグメントを確認した。GC-MSの結果を表1に示す。
[3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸のモル比(3,5,5-トリメチルヘキサン酸/2-エチルヘキサン酸比)が74/26であるビスペンタエリスリトールモノホルマールのヘキサエステル(ヘキサエステル2)の製造]
ビスペンタエリスリトールモノホルマール、3,5,5-トリメチルヘキサン酸の無水物および2-エチルヘキサン酸の無水物の使用量のモル比(ビスペンタエリスリトールモノホルマール/3,5,5-トリメチルヘキサン酸の無水物/2-エチルヘキサン酸の無水物比)を1.00/5.04/1.80にする以外は、実施例1と同様に操作して、ヘキサエステル2を得た。ヘキサエステル2の核磁気共鳴スペクトルを測定し、ヘキサエステル2を構成する3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸のモル比を算出した。また、ヘキサエステル2をGCで測定したところ、実施例1のヘキサエステル1と同じ保持時間にピークが検出された。
[3,5,5-トリメチルヘキサン酸とイソ酪酸のモル比(3,5,5-トリメチルヘキサン酸/イソ酪酸比)が70/30であるビスペンタエリスリトールモノホルマールのヘキサエステル(ヘキサエステル3)の製造]
2-エチルヘキサン酸の無水物の代わりにイソ酪酸の無水物(和光純薬社製)を用い、ビスペンタエリスリトールモノホルマール、3,5,5-トリメチルヘキサン酸の無水物およびイソ酪酸の無水物の使用量のモル比(ビスペンタエリスリトールモノホルマール/3,5,5-トリメチルヘキサン酸の無水物/イソ酪酸の無水物比)を1.00/3.75/2.70にする以外は、実施例1と同様に操作して、ヘキサエステル3を得た。ヘキサエステル3の核磁気共鳴スペクトルを測定し、ヘキサエステル3を構成する3,5,5-トリメチルヘキサン酸とイソ酪酸のモル比を算出した。得られた核磁気共鳴スペクトルのチャートを図2に示す。また、ヘキサエステル3をGCおよびGC-MSで測定した。GCより、主要なピークの保持時間(24.6分、27.9分、33.2分、41.9分、56.2分、79.5分、115.7分)を確認した。GC-MSより、主要なピークの保持時間とそのフラグメントを確認した。GC-MSの結果を表2に示す。
[3,5,5-トリメチルヘキサン酸とペンタン酸のモル比(3,5,5-トリメチルヘキサン酸/ペンタン酸比)が71/29であるビスペンタエリスリトールモノホルマールのヘキサエステル(ヘキサエステル4)の製造]
2-エチルヘキサン酸の無水物の代わりにペンタン酸の無水物(東京化成工業社製)を用い、ビスペンタエリスリトールモノホルマール、3,5,5-トリメチルヘキサン酸の無水物およびペンタン酸の無水物の使用量のモル比(ビスペンタエリスリトールモノホルマール/3,5,5-トリメチルヘキサン酸の無水物/ペンタン酸の無水物比)を1.00/5.76/1.20にする以外は、実施例1と同様に操作して、ヘキサエステル4を得た。ヘキサエステル4の核磁気共鳴スペクトルを測定し、ヘキサエステル4を構成する3,5,5-トリメチルヘキサン酸とペンタン酸のモル比を算出した。得られた核磁気共鳴スペクトルのチャートを図3に示す。また、ヘキサエステル4をGCおよびGC-MSで測定した。GCより、主要なピークの保持時間(34.0分、39.4分、46.8分、57.0分、70.6分、88.6分、111.4分)を確認した。GC-MSより、主要なピークの保持時間とそのフラグメントを確認した。GC-MSの結果を表3に示す。
[3,5,5-トリメチルヘキサン酸と3-メチル酪酸のモル比(3,5,5-トリメチルヘキサン酸/3-メチル酪酸比)が66/34であるビスペンタエリスリトールモノホルマールのヘキサエステル(ヘキサエステル5)の製造]
2-エチルヘキサン酸の無水物の代わりに3-メチル酪酸の無水物(東京化成工業社製)を用い、ビスペンタエリスリトールモノホルマール、3,5,5-トリメチルヘキサン酸の無水物および3-メチル酪酸の無水物の使用量のモル比(ビスペンタエリスリトールモノホルマール/3,5,5-トリメチルヘキサン酸の無水物/3-メチル酪酸の無水物比)を1.00/3.60/3.00にする以外は、実施例1と同様に操作して、ヘキサエステル5を得た。ヘキサエステル5の核磁気共鳴スペクトルを測定し、ヘキサエステル5を構成する3,5,5-トリメチルヘキサン酸と3-メチル酪酸のモル比を算出した。得られた核磁気共鳴スペクトルのチャートを図4に示す。また、ヘキサエステル5をGCで測定したところ、各ピーク(保持時間:28.8分、33.0分、39.4分、48.9分、62.8分、82.6分、110.2分)が検出された。
[3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸のモル比(3,5,5-トリメチルヘキサン酸/2-エチルヘキサン酸比)が47/53であるジペンタエリスリトールのヘキサエステル(ヘキサエステルA)の製造]
ディーンスタークトラップを取り付けた反応器にジペンタエリスリトール63.6g(0.25モル、広栄化学工業社製、製品名;ジペンタリット)、3,5,5,-トリメチルヘキサン酸122.5g(0.77モル、KHネオケム社製)および2-エチルヘキサン酸148.0g(1.03モル、KHネオケム社製)を仕込み、混合液を20kPaの減圧下、室温で30分間窒素バブリングを行うことで脱気した。次いで、脱気後の混合液を190~240℃で18時間窒素バブリングを行いながら撹拌した。反応後、反応液を1.3kPaの減圧下、210℃で1時間濃縮した。濃縮液を、濃縮液の酸価に対して2倍モルの水酸化ナトリウムを含むアルカリ水溶液100mLで1回、水100mLで3回洗浄した。有機層を1.3kPaの減圧下、100℃で1時間、窒素バブリングを行いながら脱水した。次いで、吸着剤0.3g(協和化学工業社製、製品名;キョーワード500)と活性炭2.6g(日本エンバイロケミカルズ社製、製品名;白鷺P)を加え、1.3kPaの減圧下、100℃で1時間撹拌した。次いで、濾過助剤(昭和化学工業社製、製品名;ラヂオライト#500)を用いて濾過することにより、ヘキサエステルAを210.7g得た。ヘキサエステルAの核磁気共鳴スペクトルを測定し、ヘキサエステルAを構成する3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸のモル比を算出した。
キャノン-フェンスケ粘度計を用い、JIS K2283:2000の方法に準じてヘキサエステル1~5およびヘキサエステルAの40℃および100℃における動粘度を測定した。結果を表4に示す。
回転ボンベ式酸化安定度試験器RBOT-02(離合社製)を用い、酸化安定度試験を行った。ヘキサエステル1~5およびヘキサエステルAのそれぞれ10gと、紙やすり#400で磨いた電解銅線(直径1.6mm、長さ3m)を耐圧容器に入れ、次いで該耐圧容器に酸素を620kPaまで圧入した。該耐圧容器を150℃の恒温槽に入れ、毎分100回転で回転させて試験を開始し、この時を試験開始時として記録した。該耐圧容器の圧力が最高になったときから35kPaの圧力降下をしている点を終点とし、試験開始時から終点までの時間(RBOT寿命)を求めた。結果を表4に示す。RBOT寿命が長いほど、ヘキサエステルの酸化安定性が優れていることを表す。また、RBOT寿命が長いヘキサエステルほど、冷凍機油組成物の一成分として使用する場合に、その冷凍機油組成物の酸化安定性を長期間にわたり維持させることができる。
ヘキサエステル1~5のそれぞれ1gをガラス容器に入れ、-20℃に設定した恒温器中で24時間静置した。24時間静置後の固化、析出物の有無を目視にて確認した。結果を以下に示す。
試験例3において、ヘキサエステル1~5は固化せず、また析出物も確認されなかった。ヘキサエステル1~5は酸化安定性および低温特性がバランスよく優れていることがわかる。
[ペンタエリスリトールと、3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸のモル比(3,5,5-トリメチルヘキサン酸/2-エチルヘキサン酸比)が57/43であるテトラエステル(冷凍機用基油A)の製造]
ジペンタエリスリトールの代わりにペンタエリスリトール(広栄化学工業社製、製品名;ペンタリット-S)を用い、ペンタエリスリトール、3,5,5-トリメチルヘキサン酸および2-エチルヘキサン酸の使用量のモル比(ペンタエリスリトール/3,5,5-トリメチルヘキサン酸/2-エチルヘキサン酸比)を1.00/2.40/2.40にする以外は、比較例1と同様に操作して、冷凍機用基油Aを得た。冷凍機用基油Aの核磁気共鳴スペクトルを測定し、冷凍機用基油Aを構成する3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸のモル比を算出した。
[冷凍機油組成物1の調製]
製造例4で製造した冷凍機用基油Aと実施例1で製造したヘキサエステル1とを、70:30(冷凍機用基油A:ヘキサエステル1)の重量比率で混合し、冷凍機油組成物1を調製した。
[冷凍機油組成物2の調製]
製造例4で製造した冷凍機用基油Aと実施例1で製造したヘキサエステル1とを、92:8(冷凍機用基油A:ヘキサエステル1)の重量比率で混合し、冷凍機油組成物2を調製した。
[冷凍機油組成物3の調製]
製造例4で製造した冷凍機用基油Aと実施例1で製造したヘキサエステル1とを、96:4(冷凍機用基油A:ヘキサエステル1)の重量比率で混合し、冷凍機油組成物3を調製した。
[冷凍機油組成物4の調製]
製造例4で製造した冷凍機用基油Aと実施例1で製造したヘキサエステル1とを、98:2(冷凍機用基油A:ヘキサエステル1)の重量比率で混合し、冷凍機油組成物4を調製した。
[冷凍機油組成物5の調製]
製造例4で製造した冷凍機用基油Aを、冷凍機油組成物5とした。
[冷凍機油組成物6の調製]
製造例4で製造した冷凍機用基油Aと比較例1で製造したヘキサエステルAとを、70:30(冷凍機用基油A:ヘキサエステルA)の重量比率で混合し、冷凍機油組成物6を調製した。
[冷凍機油組成物7の製造]
ジペンタエリスリトールの代わりにペンタエリスリトール(広栄化学工業社製、製品名;ペンタリット-S)と製造例1で製造したビスペンタエリスリトールモノホルマールの混合物を用い、ペンタエリスリトール、ビスペンタエリスリトールモノホルマール、3,5,5-トリメチルヘキサン酸および2-エチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ビスペンタエリスリトールモノホルマール/3,5,5-トリメチルヘキサン酸/2-エチルヘキサン酸比)を1.00/0.03/2.12/2.68にする以外は、比較例1と同様に操作して、冷凍機油組成物7を得た。冷凍機油組成物7をNMRおよびGCで測定し、ビスペンタエリスリトールモノホルマールと3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸とからなるヘキサエステルが含まれていることを確認した。また、GCより、該ヘキサエステルのピークの面積比率は1.89面積%であった。検量線法を用いて、該面積%の値を重量%に換算した場合、該重量%の値は該面積%の1.3~2.0倍程度の値に相当した。
[冷凍機油組成物8の製造]
ジペンタエリスリトールの代わりにペンタエリスリトール(広栄化学工業社製、製品名;ペンタリット-S)と製造例1で製造したビスペンタエリスリトールモノホルマールの混合物を用い、2-エチルヘキサン酸の代わりにペンタン酸(東京化成工業社製)を用い、ペンタエリスリトール、ビスペンタエリスリトールモノホルマール、3,5,5-トリメチルヘキサン酸およびペンタン酸の使用量のモル比(ペンタエリスリトール/ビスペンタエリスリトールモノホルマール/3,5,5-トリメチルヘキサン酸/ペンタン酸比)を1.00/0.03/3.68/1.12にする以外は、比較例1と同様に操作して、冷凍機油組成物8を得た。冷凍機油組成物8をNMRおよびGCで測定し、ビスペンタエリスリトールモノホルマールと3,5,5-トリメチルヘキサン酸とペンタン酸とからなるヘキサエステルが含まれていることを確認した。また、GCより、該ヘキサエステルのピークの面積比率は2.35面積%であった。検量線法を用いて、該面積%の値を重量%に換算した場合、該重量%の値は該面積%の1.3~2.0倍程度の値に相当した。
試験例1の方法に準じて、冷凍機油組成物1~8の40℃および100℃における動粘度を測定した。結果を表5および表6に示す。
試験例2の方法に準じて、冷凍機油組成物1~8の酸化安定度試験を行った。結果を表5および表6に示す。RBOT寿命が長いほど冷凍機油組成物の酸化安定性が優れていることを表す。
シェル式四球摩擦試験機(神鋼造機社製)を用い、冷凍機油組成物1~8の摩耗痕径の測定を行った。荷重100N、回転数600rpm、時間10分間、温度40℃(試験球;SUJ-2)の条件で試験を行い、試験後の摩耗痕径を測定した。摩耗痕径は3つの固定球の垂直方向、水平方向全ての平均値とした。結果を表5および表6に示す。
(1)BZTを含有する冷凍機油組成物(BZTの含有量1.5重量%)の調製
冷凍機油組成物1の2.955gと、BZTの0.045gとを混合し、60℃で加熱して、冷凍機油組成物1とBZTとの冷凍機油組成物を調製した。同様の方法で、冷凍機油組成物2~8とBZTとの冷凍機油組成物を調製した。
(2)低温特性の評価
冷凍機油組成物1~8とBZTとの冷凍機油組成物のそれぞれ1gをガラス容器に入れ、-20℃に設定した恒温器中で24時間静置した。固化または析出物が認められなかったものを○、認められたものを×とした。結果を表5および表6に示す。
Claims (4)
- 前記炭素数9の分岐脂肪族モノカルボン酸が、3,5,5-トリメチルヘキサン酸である請求項1に記載のビスペンタエリスリトールモノホルマールのヘキサエステル。
- 請求項1または2に記載のビスペンタエリスリトールモノホルマールのヘキサエステルを含有する冷凍機油組成物。
- 請求項3に記載の冷凍機油組成物と冷媒とを含有する冷凍機用作動流体組成物。
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JP (1) | JP5572273B1 (ja) |
KR (1) | KR101535778B1 (ja) |
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WO2016052338A1 (ja) * | 2014-10-03 | 2016-04-07 | Jx日鉱日石エネルギー株式会社 | 潤滑油基油及び冷凍機油 |
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US10604720B2 (en) * | 2015-07-07 | 2020-03-31 | Exxonmobil Research And Engineering Company | Method and composition for preventing or reducing engine knock and pre-ignition in high compression spark ignition engines |
EP3555243A1 (en) * | 2016-12-19 | 2019-10-23 | ExxonMobil Research and Engineering Company | Composition and method for preventing or reducing engine knock and pre-ignition in high compression spark ignition engines |
CN115109630B (zh) * | 2021-11-30 | 2023-01-17 | 北京福润联石化科技开发有限公司 | 配合二氟甲烷制冷剂使用的冷冻机油组合物及其应用 |
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- 2013-10-22 JP JP2014501332A patent/JP5572273B1/ja active Active
- 2013-10-22 KR KR1020157013269A patent/KR101535778B1/ko active IP Right Grant
- 2013-10-22 WO PCT/JP2013/078513 patent/WO2014065250A1/ja active Application Filing
- 2013-10-24 TW TW102138542A patent/TWI492931B/zh active
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JPS5388825A (en) * | 1977-01-18 | 1978-08-04 | Mitsubishi Gas Chemical Co | Method of delaying hydrative reaction of quick lime |
JP2009079141A (ja) * | 2007-09-26 | 2009-04-16 | Nippon Oil Corp | 二酸化炭素冷媒用冷凍機油用基油及び二酸化炭素冷媒用冷凍機油 |
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WO2016052338A1 (ja) * | 2014-10-03 | 2016-04-07 | Jx日鉱日石エネルギー株式会社 | 潤滑油基油及び冷凍機油 |
JPWO2016052338A1 (ja) * | 2014-10-03 | 2017-07-13 | Jxtgエネルギー株式会社 | 潤滑油基油及び冷凍機油 |
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Also Published As
Publication number | Publication date |
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JP5572273B1 (ja) | 2014-08-13 |
CN104768915A (zh) | 2015-07-08 |
US9567284B2 (en) | 2017-02-14 |
US20160311751A1 (en) | 2016-10-27 |
TWI492931B (zh) | 2015-07-21 |
KR101535778B1 (ko) | 2015-07-09 |
KR20150061038A (ko) | 2015-06-03 |
JPWO2014065250A1 (ja) | 2016-09-08 |
TW201431838A (zh) | 2014-08-16 |
CN104768915B (zh) | 2016-05-04 |
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