WO2013014959A1 - Tétraester de pentaérythritol - Google Patents

Tétraester de pentaérythritol Download PDF

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Publication number
WO2013014959A1
WO2013014959A1 PCT/JP2012/054188 JP2012054188W WO2013014959A1 WO 2013014959 A1 WO2013014959 A1 WO 2013014959A1 JP 2012054188 W JP2012054188 W JP 2012054188W WO 2013014959 A1 WO2013014959 A1 WO 2013014959A1
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WIPO (PCT)
Prior art keywords
acid
tetraester
pentaerythritol
trimethylhexanoic
butyric
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PCT/JP2012/054188
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English (en)
Japanese (ja)
Inventor
聡 日吉
西村　拓也
稲山　俊宏
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KH Neochem Co Ltd
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KH Neochem Co Ltd
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Priority to CN201280037423.XA priority Critical patent/CN103732572B/zh
Priority to JP2013525595A priority patent/JP6035240B2/ja
Publication of WO2013014959A1 publication Critical patent/WO2013014959A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10N2030/02—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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • 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
    • C10N2040/25—Internal-combustion engines
    • 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
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • the present invention relates to a tetraester of pentaerythritol used for industrial lubricating oil such as refrigerator oil.
  • HFCs hydrofluorocarbons
  • GWP global warming potential
  • Difluoromethane refrigerant (HFC-32) is a refrigerant currently used by GWP [R-410A (mixture of difluoromethane and pentafluoroethane), R-407C (difluoromethane and pentafluoroethane and 1,1,1 , 2-tetrafluoroethane, etc.), etc.]
  • COP coefficient of performance
  • Patent Document 1 discloses an ester of pentaerythritol and a fatty acid used in a refrigerating machine oil for a difluoromethane refrigerant, but the compatibility of the ester with the difluoromethane refrigerant is not sufficient.
  • An object of the present invention is to provide a pentaerythritol tetraester used for refrigerating machine oil or the like having excellent compatibility with a difluoromethane refrigerant.
  • the present invention provides the following [1] to [9].
  • [1] A mixed ester of pentaerythritol and a carboxylic acid, wherein the carboxylic acid contains butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms. ester.
  • [2] The tetraester of pentaerythritol according to [1], wherein the carboxylic acid comprises butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms.
  • [3] The tetraester of pentaerythritol according to [1] or [2], wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is a branched aliphatic carboxylic acid having 5 or 6 carbon atoms.
  • [4] The tetraester of pentaerythritol according to any one of [1] to [3], wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is 2-methylbutyric acid.
  • [5] The tetraester of pentaerythritol according to any one of [1] to [3], wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is 3-methylbutyric acid.
  • [6] The tetraester of pentaerythritol according to any one of [1] to [3], wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is 2-methylpentanoic acid.
  • [7] The tetraester of pentaerythritol according to [1] or [2], wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is a linear aliphatic carboxylic acid having 5 to 7 carbon atoms.
  • [8] The tetraester of pentaerythritol according to any one of [1], [2], and [7], wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is pentanoic acid.
  • the tetraester of pentaerythritol of the present invention is a mixed ester of pentaerythritol and a carboxylic acid containing butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms.
  • the tetraester of pentaerythritol means a compound obtained by esterification using a plurality of carboxylic acids that form an ester with respect to pentaerythritol.
  • the “mixed ester” in the present invention includes the following (i) to (vi): (I) Tetraester of pentaerythritol in which the constituent carboxylic acid in the same molecule includes butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms (ii) The constituent carboxylic acid in the same molecule A tetraester of pentaerythritol containing two selected from the group of butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms; (iii) a carboxylic acid containing pentaerythritol and butyric acid; Tetraester of (iv) Tetraester of pentaerythritol and carboxylic acid containing 3,5,5-trimethylhexanoic acid (v) of pentaerythritol and carboxylic
  • the use of butyric acid, 3,5,5-trimethylhexanoic acid and an aliphatic carboxylic acid having 5 to 7 carbon atoms as the carboxylic acid improves compatibility with the difluoromethane refrigerant, and a wide range of temperatures. The viscosity change in the range can be reduced.
  • the carboxylic acid constituting the mixed ester may contain other carboxylic acids other than butyric acid, 3,5,5-trimethylhexanoic acid, and aliphatic carboxylic acids having 5 to 7 carbon atoms.
  • Other carboxylic acids include, for example, linear aliphatic carboxylic acids such as acetic acid, propionic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, 2-methylheptanoic acid, Branched fats such as 2-ethylhexanoic acid, 3-ethylhexanoic acid, 2-ethyl-2-methylpentanoic acid, 2-methyloctanoic acid, 2,2-dimethylheptanoic acid, isodecanoic acid, isotridecanoic acid and isostearic acid Group carboxylic acid and the
  • the content of other carboxylic acids in the carboxylic acid containing butyric acid, 3,5,5-trimethylhexanoic acid, and aliphatic carboxylic acid having 5 to 7 carbon atoms is such that the tetraester of pentaerythritol of the present invention has a low temperature. It may be in a range that does not impair excellent characteristics such as fluidity and compatibility with a difluoromethane refrigerant.
  • the carboxylic acid constituting the mixed ester is more preferably composed of butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms.
  • Examples of the aliphatic carboxylic acid having 5 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention include a linear aliphatic carboxylic acid having 5 to 7 carbon atoms or a branched aliphatic carboxylic acid having 5 to 7 carbon atoms. It is done.
  • Specific examples of the linear aliphatic carboxylic acid having 5 to 7 carbon atoms include pentanoic acid, hexanoic acid and heptanoic acid. Among them, pentanoic acid or hexanoic acid is preferable, and pentanoic acid is more preferable.
  • Examples of the branched aliphatic carboxylic acid having 5 to 7 carbon atoms include 2-methylbutyric acid, 3-methylbutyric acid, a mixture of 2-methylbutyric acid and 3-methylbutyric acid, 2,2-dimethylpropionic acid, 2-methylpentanoic acid, Examples include 2-ethylbutyric acid, 2-methylhexanoic acid, 3-methylhexanoic acid, and neoheptanoic acid. Among them, 2-methylbutyric acid, 3-methylbutyric acid, a mixture of 2-methylbutyric acid and 3-methylbutyric acid, or 2-methyl Pentanoic acid is preferred, and 2-methylbutyric acid or 3-methylbutyric acid is more preferred.
  • the aliphatic carboxylic acid having 5 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention is one aliphatic carboxylic acid selected from aliphatic carboxylic acids having 5 to 7 carbon atoms, or 5 to 7 carbon atoms. It is a mixture of two or more carboxylic acids selected from 7 aliphatic carboxylic acids, and among them, one aliphatic carboxylic acid selected from aliphatic carboxylic acids having 5 to 7 carbon atoms is preferable.
  • the aliphatic carboxylic acid having 5 to 7 carbon atoms may be a branched aliphatic carboxylic acid having 5 or 6 carbon atoms.
  • Examples of the branched aliphatic carboxylic acid having 5 or 6 carbon atoms include the branched aliphatic carboxylic acids having 5 or 6 carbon atoms among the branched aliphatic carboxylic acids having 5 to 7 carbon atoms.
  • the pentaerythritol of the present invention Tetraesters have a good balance of compatibility with difluoromethane refrigerant in a wide range of concentrations, excellent properties such as viscosity-temperature characteristics, low-temperature fluidity, low-temperature characteristics, and sufficient stability.
  • the aliphatic carboxylic acid having 5 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention is pentanoic acid, 2-methylbutyric acid, 3-methylbutyric acid or 2-methylpentanoic acid, butyric acid and 3,5,5 Molar ratio of pentanoic acid, 2-methylbutyric acid, 3-methylbutyric acid or 2-methylpentanoic acid to the sum of 5-trimethylhexanoic acid [(pentanoic acid, 2-methylbutyric acid, 3-methylbutyric acid or 2-methylpentanoic acid ) / (Butyric acid and 3,5,5-trimethylhexanoic acid) ratio] is preferably in the range of 5/100 to 250/100.
  • the tetraester of the present invention When the tetraester of the present invention is used as a lubricating oil, if the viscosity of the tetraester is too low, wear tends to increase and the life of equipment using the lubricating oil tends to be shortened, while the viscosity of the tetraester is high. If it is too high, the coefficient of friction tends to increase and the energy efficiency tends to decrease, so that the tetraester is required to have an appropriate viscosity range.
  • the tetraester of the present invention has 3,5,5-trimethylhexanoic acid with respect to the sum of butyric acid, 3,5,5-trimethylhexanoic acid and aliphatic carboxylic acid having 5 to 7 carbon atoms from the viewpoint of an appropriate viscosity range.
  • the molar ratio [3,5,5-trimethylhexanoic acid / (butyric acid, 3,5,5-trimethylhexanoic acid and aliphatic carboxylic acid having 5 to 7 carbon atoms)] of 15/100 to 65/100 A range is preferred.
  • the tetraester of pentaerythritol of the present invention includes, for example, pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid, an aliphatic carboxylic acid having 5 to 7 carbon atoms, and optionally other carboxylic acid. It can be produced by reacting at 120 to 250 ° C. for 5 to 60 hours.
  • 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 sum of the amount of butyric acid used, the amount of 3,5,5-trimethylhexanoic acid, the amount of aliphatic carboxylic acid having 5 to 7 carbon atoms and the amount of other carboxylic acid used is the hydroxyl group of pentaerythritol used.
  • the amount is preferably 1.1 to 1.4 times mol.
  • a solvent may be used.
  • the solvent include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, isohexane, isooctane, isononane, decane, and the like.
  • butyric acid 3,5,5-trimethylhexanoic acid and aliphatic carboxylic acid having 5 to 7 carbon atoms with respect to pentaerythritol, butyric acid constituting the obtained tetraester and 3,5,5
  • the molar ratio of 5-trimethylhexanoic acid to an aliphatic carboxylic acid having 5 to 7 carbon atoms may differ from that in the amount used to produce the tetraester.
  • the pentaerythritol tetraester of the present invention is a method usually used in organic synthetic chemistry (washing with water and / or alkaline aqueous solution, treatment with activated carbon, adsorbent, etc., various chromatographic methods, if necessary) It may be purified by a distillation method or the like.
  • the tetraester of pentaerythritol of the present invention is excellent in compatibility with not only a conventional difluoromethane mixed solvent (R-410A, R-407C) but also a difluoromethane refrigerant alone. In addition, it has excellent low temperature fluidity, excellent low temperature characteristics, sufficient viscosity-temperature characteristics, excellent lubricity, sufficient stability, and the like.
  • the compatibility with difluoromethane refrigerant is generally expressed using the two-layer separation temperature. It can be said that the lower the two-layer separation temperature, the better the compatibility on the low temperature side.
  • the two-layer separation temperature is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 20 ° C. or lower. preferable.
  • the compatibility of the ester with the refrigerant has a correlation with the property of the ester.
  • the viscosity-temperature characteristic is a change in kinematic viscosity with respect to a temperature change of an oil such as a lubricating oil.
  • Good viscosity-temperature characteristics means that the change in viscosity with respect to temperature changes is small, while poor ones mean that the viscosity increases rapidly in the low temperature range and the kinematic viscosity becomes lower than expected in the high temperature range. It is a thing.
  • this characteristic is expressed as a viscosity index, and it can be said that the higher the value, the better the viscosity-temperature characteristic.
  • the viscosity index is preferably 80 or more, and more preferably 90 or more.
  • the viscosity characteristic in a low temperature region is also called low temperature fluidity, and is expressed by a pour point, a freezing point, a channel point, and the like.
  • the pour point refers to the lowest temperature at which the oil agent flows when the oil agent such as lubricating oil is cooled according to the method of Japanese Industrial Standard (JIS) K2269.
  • JIS Japanese Industrial Standard
  • An oil agent with a low pour point does not deteriorate its fluidity even in low temperature environments such as in winter or in cold regions, or when operating as an evaporator in a refrigerator at low temperatures when used as refrigeration oil. It is preferable in that it does not cause malfunction of the equipment using the device.
  • an oil that is not volatile in a high temperature range and does not solidify or precipitate in a low temperature range is preferable.
  • the temperature range is not particularly limited, but an oil that can be stably used at about 150 ° C. on the high temperature side and about ⁇ 20 ° C. on the low temperature side is preferable.
  • the characteristic that solidification and precipitation do not occur in the low temperature range is defined as the low temperature characteristic.
  • Stability includes, for example, thermal stability, oxidation stability, oxidation / hydrolysis stability, shear stability, and the like in lubricating oil applications.
  • Lubricity includes friction reduction, wear reduction, extreme pressure and the like.
  • the kinematic viscosity at 100 ° C. of the tetraester is preferably in the range of 4.6 to 8.2 mm 2 / sec, 5.6 to 8.2 mm. More preferably, it is in the range of 2 / sec.
  • the hydroxyl value of the mixed ester is preferably 10 mgKOH / g or less, and more preferably 5 mgKOH / g or less.
  • the pentaerythritol tetraester of the present invention is used for refrigeration machine oils, engine oils, gear oils, motor oils used in hybrid cars and electric cars, grease, metal parts cleaning agents, plasticizers, etc. Can do.
  • the refrigerating machine oil using the pentaerythritol tetraester of the present invention for example, a refrigerating machine oil containing pentaerythritol tetraester and an additive for lubricating oil may be mentioned.
  • the tetraester is used as a lubricating oil base oil.
  • additives for lubricating oil include antioxidants, wear reducing agents (antiwear agents, anti-seizure agents, extreme pressure agents, etc.), friction modifiers, acid scavengers, metal deactivators, and antifoaming agents. And the like which are usually used as lubricating oil additives.
  • the content of these additives is preferably 0.001 to 5% by weight in the refrigerating machine oil.
  • the tetraester of pentaerythritol of the present invention and other lubricating base oils may be used in combination.
  • examples of other lubricating base oils include mineral oils and synthetic base oils.
  • mineral oil examples include paraffin-based crude oil, intermediate-based crude oil, and naphthenic-based crude oil. Further, refined oils obtained by refining them 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, polyhydric alcohols) other than the tetraesters of the present invention. Fatty acid ester, aliphatic polybasic acid ester, etc.), aromatic ester (aromatic monoester, aromatic ester of polyhydric alcohol, aromatic polybasic acid ester, etc.), polyalkylene glycol, polyvinyl ether, polyphenyl ether, alkylbenzene , Carbonate, synthetic naphthene and the like.
  • the tetraester of pentaerythritol of the present invention is excellent in the ability to dissolve additives for lubricating oil such as metal deactivators such as benzotriazole and silicone antifoaming agents.
  • the additive for lubricating oil is used by being dissolved in the lubricating oil, for example, in order to extend the life of the lubricating oil, equipment using the lubricating oil, and the like.
  • the additive for lubricating oil generally has low solubility in pentaerythritol ester (Japanese Patent Laid-Open No. 10-259394).
  • Benzotriazole has low solubility in mineral oil and / or synthetic oil (Japanese Patent Laid-Open No.
  • the solubility (25 ° C.) of benzotriazole in tetraester 4 (Example 4 described later), which is the tetraester of pentaerythritol of the present invention, is 0.030 g / g or more. Also exhibits high solubility of benzotriazole.
  • the solubility (25 ° C.) of benzotriazole in tetraester A (Comparative Example 1 described later) was 0.021 g / g.
  • the pentaerythritol tetraester of the present invention has excellent low-temperature fluidity and excellent wear resistance when benzotriazole is dissolved.
  • peak X corresponds to a hydrogen atom peak on the methylene group at the ⁇ -position of the carbonyl group in butyric acid
  • peak Y corresponds to a hydrogen atom on the methine group in 3,5,5-trimethylhexanoic acid
  • peak Q Corresponds to the peak of the hydrogen atom on the methylene group at the ⁇ -position of the carbonyl group in 2-methylbutyric acid.
  • Butyric acid / 3,5,5-trimethylhexanoic acid / 3-methylbutyric acid (integral value of peak X / 2) / (integral value of peak Z / 2) / (integral value of peak R / 2)
  • peak X has the same meaning as above
  • peak Z corresponds to the peak of the hydrogen atom on the methylene group at the ⁇ position of the carbonyl group in 3,5,5-trimethylhexanoic acid
  • peak R in 3-methylbutyric acid This corresponds to the peak of the hydrogen atom on the methylene group at the ⁇ -position of the carbonyl group.
  • Nuclear magnetic resonance spectra were measured for the tetraesters of pentaerythritol produced in Examples 12 to 15 below, and the molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid in the tetraester of pentaerythritol was determined. The following formula was used for calculation.
  • Butyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid (integral value of peak X / 2) / integral value of peak Y / (integral value of peak S / 2)
  • the peak X and the peak Y have the same meanings as described above
  • the peak S corresponds to a hydrogen atom peak on the methylene group at the ⁇ -position of the carbonyl group in pentanoic acid.
  • the nuclear magnetic resonance spectrum of the tetraester of pentaerythritol produced in Example 23 below was measured, and the molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid in the tetraester of pentaerythritol was determined. The following formula was used for calculation.
  • Butyric acid / 3,5,5-trimethylhexanoic acid / 2-ethylbutyric acid (integrated value of peak X / 2) / integrated value of peak Y / (integrated value of peak U / 4)
  • the peak X and the peak Y have the same meaning as described above
  • the peak U corresponds to the peak of the hydrogen atom on the ⁇ -position methylene group of the carbonyl group in 2-ethylbutyric acid.
  • a nuclear magnetic resonance spectrum was measured for the tetraester of pentaerythritol produced in Example 24 below, and the molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and hexanoic acid in the tetraester of pentaerythritol was determined as follows: Calculated by the formula.
  • Butyric acid / 3,5,5-trimethylhexanoic acid / hexanoic acid (integrated value of peak X / 2) / integrated value of peak Y / (integrated value of peak V / 4)
  • the peak X and the peak Y have the same meaning as described above
  • the peak V corresponds to the peak of the hydrogen atom on the ⁇ -position and ⁇ -position methylene group of hexanoic acid.
  • a nuclear magnetic resonance spectrum was measured for the tetraester of pentaerythritol produced in Example 25 below, and the molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and heptanoic acid in the tetraester of pentaerythritol was determined as follows: Calculated by the formula.
  • Butyric acid / 3,5,5-trimethylhexanoic acid / heptanoic acid (integrated value of peak X / 2) / integrated value of peak Y / (integrated value of peak W / 6)
  • the peak X and the peak Y have the same meaning as described above
  • the peak W corresponds to the peak of the hydrogen atom on the ⁇ -position, ⁇ -position and ⁇ -position methylene group of heptanoic acid.
  • Example 1 [Pentaerythritol with a molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) of 80/20/7 Production of tetraester (tetraester 1)]
  • tetraester 1 As an adsorbent, Kyoward 500 manufactured by Kyowa Chemical Industry Co., Ltd. was used.
  • activated carbon Shirahige P manufactured by Nippon Enviro Chemicals was used.
  • reaction product was stirred at 207 ° C. for 1 hour under a reduced pressure of 0.1 kPa to distill off unreacted carboxylic acid in the reaction product.
  • the reaction product was washed for 2 hours at 88 ° C. with 400 mL of an aqueous alkaline solution containing sodium hydroxide twice as much as the acid value of the reaction product.
  • the reaction product was then washed 3 times with 400 mL of water at 61 ° C. for 1 hour. Subsequently, the reaction product was dried at 116 ° C. for 2 hours under a reduced pressure of 0.1 kPa while performing nitrogen bubbling to dry the reaction product.
  • reaction product 8.0 g of adsorbent (corresponding to 0.7% of the reaction product) and 5.7 g of activated carbon (corresponding to 0.5% of the reaction product) are added to the reaction product, and nitrogen bubbling is performed.
  • the reaction product was stirred at 111 ° C. for 2 hours under a reduced pressure of 0.1 kPa, and then filtered using a filter aid to obtain 938 g of tetraester 1.
  • Example 2 [Pentaerythritol whose molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) is 69/31/59 Production of tetraester (tetraester 2)]
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid used is 1 /
  • the tetraester 2 was obtained in the same manner as in Example 1 except that the ratio was changed to 1.92 / 0.96 / 1.92.
  • Example 3 [Pentaerythritol with a molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid to 2-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) of 38/62/224 Production of tetraester (tetraester 3)]
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid used is 1 /
  • the tetraester 3 was obtained in the same manner as in Example 1 except that the ratio was changed to 0.38 / 0.96 / 3.46.
  • Example 4 [Pentaerythritol with a molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) of 25/75/138 Production of tetraester (tetraester 4)]
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid used is 1 /
  • the tetraester 4 was obtained in the same manner as in Example 1 except that the ratio was 0.45 / 1.35 / 3.00.
  • Example 5 [Pentaerythritol whose molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) is 46/54/33 Production of tetraester (tetraester 5)]
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid used is 1 /
  • the tetraester 5 was obtained in the same manner as in Example 1 except that the ratio was 1.44 / 1.92 / 1.44.
  • Example 6 [Pentaerythritol whose molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) is 32/68/92 Production of tetraester (tetraester 6)]
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid used is 1 /
  • the tetraester 6 was obtained in the same manner as in Example 1 except that the ratio was 0.72 / 1.68 / 2.40.
  • Example 7 [Pentaerythritol in which the molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) is 41/59/8 Production of tetraester (tetraester 7)]
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid used is 1 /
  • the tetraester 7 was obtained in the same manner as in Example 1 except that the ratio was 1.62 / 3.00 / 0.18.
  • Example 8 [Pentaerythritol whose molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) is 25/75/33 Production of tetraester (tetraester 8)] The molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid used (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) is 1 / The tetraester 8 was obtained in the same manner as in Example 1 except that the ratio was 0.90 / 3.00 / 0.90.
  • Example 9 [Pentaerythritol with a molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) of 23/77/54 Production of tetraester (tetraester 9)]
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid used is 1 /
  • the tetraester 9 was obtained in the same manner as in Example 1 except that the ratio was 0.72 / 2.40 / 1.68.
  • Example 10 [Pentaerythritol whose molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 3-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 3-methylbutyric acid ratio) is 62/38/37 Production of tetraester (tetraester 10)] Instead of 2-methylbutyric acid, 3-methylbutyric acid was used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 3-methylbutyric acid used (pentaerythritol / butyric acid / 3,5,5) The tetraester 10 was obtained in the same manner as in Example 1 except that the ratio of (trimethylhexanoic acid / 3-methylbutyric acid) was 1 / 2.16 / 1.20 / 1.44.
  • Example 11 [Pentaerythritol whose molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 3-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 3-methylbutyric acid ratio) is 36/64/76 Production of tetraester (tetraester 11)] Instead of 2-methylbutyric acid, 3-methylbutyric acid was used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 3-methylbutyric acid used (pentaerythritol / butyric acid / 3,5,5) The tetraester 11 was obtained in the same manner as in Example 1 except that the ratio (trimethylhexanoic acid / 3-methylbutyric acid ratio) was changed to 1 / 0.72 / 1.68 / 2.40.
  • Example 12 Tetraester of pentaerythritol with a molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) of 63/37/65 (tetra Production of ester 12)]
  • pentanoic acid instead of 2-methylbutyric acid
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid used pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid
  • the tetraester 12 was obtained in the same manner as in Example 1 except that the ratio (pentanoic acid ratio) was changed to 1 / 1.92 / 0.96 / 1.92.
  • Example 13 Tetraester of pentaerythritol with a molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) of 56/44/57 (tetra Production of ester 13)]
  • pentanoic acid in place of 2-methylbutyric acid, the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid used (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid)
  • the tetraester 13 was obtained in the same manner as in Example 1 except that the ratio / pentanoic acid ratio was 1 / 1.63 / 1.54 / 1.63.
  • Example 14 Tetraester of pentaerythritol having a molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid to pentanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) of 49/51/41 (tetra Production of ester 14)]
  • pentanoic acid instead of 2-methylbutyric acid
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid used pentanoic acid used (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid)
  • the tetraester 14 was obtained in the same manner as in Example 1 except that the ratio of / pentanoic acid was changed to 1 / 1.39 / 2.02 / 1.39.
  • Example 15 Tetraester of pentaerythritol with a molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) of 33/67/32 (tetra Production of ester 15)]
  • pentanoic acid in place of 2-methylbutyric acid, the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid used (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid)
  • the tetraester 15 was obtained in the same manner as in Example 1 except that the ratio (pentanoic acid ratio) was 1 / 1.08 / 2.64 / 1.08.
  • Example 16 [Pentarate having a molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid to 2-methylpentanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) of 81/19/6 Production of tetraester of erythritol (tetraester 16)] Instead of 2-methylbutyric acid, 2-methylpentanoic acid was used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid used (pentaerythritol / butyric acid / 3,5 , 5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) was changed to 1 / 3.46 / 0.96 / 0.38 to give tetraester 16 in the same manner as in Example 1.
  • Example 17 [Pentarate having a molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid to 2-methylpentanoic acid (ratio of butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylpentanoic acid) of 71/29/53 Production of tetraester of erythritol (tetraester 17)] Instead of 2-methylbutyric acid, 2-methylpentanoic acid was used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid used (pentaerythritol / butyric acid / 3,5 , 5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) was changed to 1 / 1.92 / 0.96 / 1.92 to give tetraester 17 in the same manner as in Example 1.
  • Example 18 [Pentarate having a molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid to 2-methylpentanoic acid (ratio of butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylpentanoic acid) of 33/67/237 Production of tetraester of erythritol (tetraester 18)] Instead of 2-methylbutyric acid, 2-methylpentanoic acid was used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid used (pentaerythritol / butyric acid / 3,5 , 5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) was changed to 1 / 0.38 / 0.96 / 3.46 in the same manner as in Example 1 to obtain tetraester 18.
  • Example 19 [Pentarate having a molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid to 2-methylpentanoic acid (ratio of butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylpentanoic acid) of 31/69/105 Production of tetraester of erythritol (tetraester 19)] Instead of 2-methylbutyric acid, 2-methylpentanoic acid was used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid used (pentaerythritol / butyric acid / 3,5 , 5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) was changed to 1 / 0.72 / 1.68 / 2.40 to give tetraester 19 in the same manner as in Example 1.
  • Example 20 [Pentarate having a molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid to 2-methylpentanoic acid (ratio of butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylpentanoic acid) of 43/57/32 Production of tetraester of erythritol (tetraester 20)] Instead of 2-methylbutyric acid, 2-methylpentanoic acid was used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid used (pentaerythritol / butyric acid / 3,5 , 5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) was changed to 1 / 1.44 / 1.92 / 1.44 to give tetraester 20 in the same manner as in Example 1.
  • Example 21 [Pentarate having a molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid to 2-methylpentanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) of 36/64/6 Production of tetraester of erythritol (tetraester 21)] Instead of 2-methylbutyric acid, 2-methylpentanoic acid was used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid used (pentaerythritol / butyric acid / 3,5 , 5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) was changed to 1 / 1.62 / 3.00 / 0.18 to give tetraester 21 in the same manner as in Example 1.
  • Example 22 [Pentarate in which the molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) is 26/74/19 Production of tetraester of erythritol (tetraester 22)] Instead of 2-methylbutyric acid, 2-methylpentanoic acid was used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid used (pentaerythritol / butyric acid / 3,5 , 5-trimethylhexanoic acid / 2-methylpentanoic acid ratio) was changed to 1 / 0.90 / 3.00 / 0.90 in the same manner as in Example 1 to obtain tetraester 22.
  • Example 23 [Pentaerythritol with a molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 2-ethylbutyric acid ratio) of 35/65/40 Production of tetraester (tetraester 23)] Instead of 2-methylbutyric acid, 2-ethylbutyric acid is used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid used (pentaerythritol / butyric acid / 3,5,5) The tetraester 23 was obtained in the same manner as in Example 1 except that the ratio (-trimethylhexanoic acid / 2-ethylbutyric acid) was changed to 1 / 1.20 / 2.00 / 1.60.
  • Example 24 Tetraester of pentaerythritol having a molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid to hexanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / hexanoic acid ratio) of 73/27/76 (tetra Production of ester 24)]
  • hexanoic acid instead of 2-methylbutyric acid
  • the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and hexanoic acid used penentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid
  • the tetraester 24 was obtained in the same manner as in Example 1 except that the ratio of / hexanoic acid was changed to 1 / 1.92 / 0.96 / 1.92.
  • Example 25 Tetraester of pentaerythritol with a molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and heptanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / heptanoic acid ratio) of 71/29/70 (tetra Production of ester 25)]
  • 2-methylbutyric acid heptanoic acid is used, and the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and heptanoic acid used (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid)
  • the tetraester 25 was obtained in the same manner as in Example 1 except that the ratio (1 / heptanoic acid ratio) was changed to 1 / 1.92 / 0.96 / 1.92.
  • Test Example 1 Measurement of pour point The pour points of tetraesters 1 to 25 and A were measured according to the method of JIS K2269-1987 using an automatic pour point measuring device RPC-01CML (manufactured by Rouai Co., Ltd.). The results are shown in Tables 1-5.
  • Test Example 2 Measurement of pour point of tetraester solution 1.35 g of benzotriazole was mixed with 43.65 g of each of tetraesters 1 to 25 and A, heated at 60 ° C., and 3 wt. An ester solution was prepared. In the same manner as in Test Example 1, the pour point of each 3 wt% tetraester solution was measured. The results are shown in Tables 1-5. In Tables 1 to 5, BZT represents benzotriazole.
  • Test Example 4 Measurement of two-layer separation temperature
  • the two-layer separation temperatures of tetraesters 1 to 25 and A were measured according to the method of JIS K2211: 2009. 0.4 g of tetraesters 1 to 25 and A and 3.6 g of difluoromethane refrigerant are sealed in a pressure-resistant glass tube, and the mixture is cooled from 30 ° C. at a rate of 0.5 ° C. per minute. The temperature at which white turbidity occurred was defined as the two-layer separation temperature. The results are shown in Tables 1-5.
  • Test Example 7 Measurement of weight loss temperature (evaluation of thermal stability) Using a thermogravimetric / differential calorimeter Tg-DTA6200 (manufactured by Seiko Instruments Inc.), the 5% weight loss temperature of tetraesters 1 to 25 was measured under the following conditions. The results are shown below. Measurement temperature: 40 to 420 ° C., rate of temperature increase: 10 ° C./min, atmosphere: nitrogen aeration (300 mL / min), sample container: aluminum 15 ⁇ l (open), sample amount: 3 mg
  • tetraesters 1 to 25 have a sufficient viscosity-temperature characteristic with a kinematic viscosity at 100 ° C. of 4.6 to 8.2 mm 2 / sec and a viscosity index of 83 or more, It can be seen that the point has excellent low-temperature fluidity of ⁇ 40.0 ° C. or less. In addition, it can be seen that the two-layer separation temperature is ⁇ 10 ° C. or lower and excellent compatibility with the difluoromethane refrigerant. Furthermore, the pour point of a 3% by weight tetraester solution of benzotriazole is ⁇ 32.5 ° C. or less, and it can be seen that even when benzotriazole is dissolved, it has excellent low temperature fluidity.
  • tetraesters 1 to 25 did not solidify and no precipitates were confirmed. It can be seen that the tetraester of the present invention can be preferably used even when stored or used for a long time in a low temperature range.
  • tetraesters 1 to 25 have an RBOT life of 716 minutes or longer, of which tetraester 4 is 1546 minutes, tetraester 6 is 1510 minutes, and tetraester 9 is 1440. Minutes, tetraester 10 was 996 minutes, tetraester 11 was 1355 minutes, tetraester 14 was 912 minutes, tetraester 15 was 1140 minutes, and tetraester 22 was 1500 minutes. It can be seen that the tetraester of the present invention has sufficient oxidation / hydrolysis stability.
  • the RBOT lifetime in “Condition 2” of Test Example 6 is 180 minutes for tetraester 4, 218 minutes for tetraester 6, 421 minutes for tetraester 11, 401 minutes for tetraester 12, Ester 22 was 195 minutes, tetraester 24 was 282 minutes, and tetraester 25 was 180 minutes. It can be seen that the tetraester of the present invention has sufficient oxidative stability.
  • tetraesters 1 to 25 had a 5% weight loss temperature of 209.5 ° C. or higher in the Tg-DTA measurement. It can be seen that the tetraester of the present invention has sufficient thermal stability.

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Abstract

L'invention porte sur un tétraester de pentaérythritol qui est un ester mixte de pentaérythritol et d'acide carboxylique, l'acide carboxylique contenant l'acide butyrique, l'acide 3,5,5-triméthylhexanoïque et un acide carboxylique aliphatique ayant 5-7 atomes de carbone, à utiliser dans une huile réfrigérante et similaire ayant une excellente compatibilité et similaire avec un réfrigérant difluorométhane.
PCT/JP2012/054188 2011-07-27 2012-02-22 Tétraester de pentaérythritol Ceased WO2013014959A1 (fr)

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JP2002193882A (ja) * 2000-10-16 2002-07-10 Nof Corp エステルの製造方法
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