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WO2013008487A1 - Tétraester de pentaérythritol - Google Patents

Tétraester de pentaérythritol Download PDF

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Publication number
WO2013008487A1
WO2013008487A1 PCT/JP2012/054187 JP2012054187W WO2013008487A1 WO 2013008487 A1 WO2013008487 A1 WO 2013008487A1 JP 2012054187 W JP2012054187 W JP 2012054187W WO 2013008487 A1 WO2013008487 A1 WO 2013008487A1
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WO
WIPO (PCT)
Prior art keywords
acid
pentaerythritol
tetraester
trimethylhexanoic
isobutyric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/054187
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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
Original Assignee
KH Neochem Co Ltd
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Filing date
Publication date
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Priority to CN201280034710.5A priority Critical patent/CN103649040B/zh
Priority to JP2013523842A priority patent/JP5990168B2/ja
Publication of WO2013008487A1 publication Critical patent/WO2013008487A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • 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
    • C10N2020/071—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
    • 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
    • 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
    • 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 tetraester of pentaerythritol used for industrial lubricating oil such as refrigerator oil.
  • Lubricating oils used in industrial lubricating oils such as refrigeration oils are required to have excellent low-temperature fluidity and various stability improvements for use in low-temperature environments such as winter or cold regions.
  • Examples of the stability include thermal stability, oxidation stability, oxidation / hydrolysis stability, and the like.
  • equipment using the lubricating oil is required to improve various durability such as wear resistance and fatigue resistance, and to improve energy saving performance.
  • Patent Document 1 contains an ester obtained by reacting pentaerythritol, 3,5,5-trimethylhexanoic acid, isobutyric acid and adipic acid in a molar ratio of 1: 1: 2.5: 0.25. Although the liquid composition is described as being useful as a cooling liquid for refrigerators and air conditioners, the low-temperature fluidity and stability of the ester are not satisfactory.
  • An object of the present invention is to provide a tetraester of pentaerythritol used for refrigerating machine oil or the like having a good balance of excellent low temperature fluidity and excellent stability.
  • the present invention provides the following [1] to [5].
  • [1] A mixed ester of pentaerythritol and carboxylic acid, wherein the carboxylic acid contains isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms Tetraester of pentaerythritol.
  • [2] The tetraester of pentaerythritol according to [1], wherein the carboxylic acid comprises isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms.
  • a tetraester of pentaerythritol used for refrigerating machine oil or the like having a good balance of excellent low-temperature fluidity and excellent stability can be provided.
  • the tetraester of pentaerythritol of the present invention is a mixed ester of pentaerythritol and a carboxylic acid containing isobutyric acid, 3,5,5-trimethylhexanoic acid and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms. is there.
  • 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 isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms (ii) in the same molecule Tetraesters of pentaerythritol containing two constituent carboxylic acids selected from the group consisting of isobutyric acid, 3,5,5-trimethylhexanoic acid, and linear aliphatic monocarboxylic acids having 4 to 7 carbon atoms (iii) pentaerythritol (Iv) Tetraester of carboxylic acid containing isobutyric acid (iv) Pentaerythritol and carboxylic acid containing 3,5,5-trimethylhexanoic acid (v) Linear chain of 4 to 7 carbon atom
  • the carboxylic acid constituting the mixed ester may contain other carboxylic acids other than isobutyric acid, 3,5,5-trimethylhexanoic acid, and linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms.
  • Other carboxylic acids include, for example, linear aliphatic monocarboxylic acids such as acetic acid, propionic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic 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-methyl Butyric acid, 2,2-dimethylpentanoic acid
  • the content of the other carboxylic acids in the carboxylic acid containing isobutyric acid, 3,5,5-trimethylhexanoic acid and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms is the tetraerythritol of the pentaerythritol of the present invention.
  • the ester may be in a range that does not impair excellent properties such as low-temperature fluidity, stability, or compatibility with a difluoromethane refrigerant.
  • Molar ratio of other carboxylic acids to the sum of isobutyric acid, 3,5,5-trimethylhexanoic acid and linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms is preferably in the range of 0/100 to 5/100.
  • the carboxylic acid constituting the mixed ester is more preferably composed of isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms. .
  • linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention include butyric acid, pentanoic acid, hexanoic acid and heptanoic acid. Pentanoic acid is preferred.
  • the straight-chain aliphatic monocarboxylic acid having 4 to 7 carbon atoms is butyric acid or pentanoic acid
  • the tetraester of pentaerythritol of the present invention is compatible with difluoromethane refrigerant in a wide range of concentrations, viscosity-temperature characteristics, low temperature flow Excellent properties such as stability, low temperature properties, and stability are particularly well balanced.
  • the linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention is butyric acid or pentanoic acid
  • the molar ratio of pentanoic acid is preferably in the range of 10/100 to 300/100.
  • the straight chain aliphatic monocarboxylic acid having 4 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention is heptanoic acid, heptanoic acid with respect to the sum of isobutyric acid and 3,5,5-trimethylhexanoic acid
  • the molar ratio [heptanoic acid / (isobutyric acid and 3,5,5-trimethylhexanoic acid) ratio] is preferably in the range of 20/100 to 100/100.
  • the ratio (mol%) of isobutyric acid to the sum of all carboxylic acids constituting the tetraester of pentaerythritol of the present invention is preferably in the range of 5 to 55 mol% in terms of low-temperature characteristics and stability. It is more preferably in the range of 40 mol%, and even more preferably in the range of 15 to 40 mol%.
  • the tetraesters of pentaerythritol of the present invention include, for example, pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid, a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms, and, if desired, other It can be produced by reacting with a carboxylic acid 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 molar amount is preferably 1.1 to 1.4 times the hydroxyl group of pentaerythritol.
  • a solvent may be used.
  • the solvent include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, isohexane, isooctane, isononane, decane, and the like.
  • the molar ratio of 3,5,5-trimethylhexanoic acid to a linear aliphatic monocarboxylic acid having 4 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 has excellent low temperature fluidity, excellent stability, excellent low temperature characteristics, excellent viscosity-temperature characteristics, excellent compatibility with difluoromethane solvents, excellent lubricity and the like.
  • Viscosity-temperature characteristics are changes in kinematic viscosity with respect to temperature changes in lubricants such as 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 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.
  • by using a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms as the carboxylic acid it is possible to suppress the generation of precipitates at low temperatures.
  • 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 tetraester of pentaerythritol of the present invention is excellent in compatibility with not only the conventional difluoromethane mixed solvent (R-410A, R-407C) but also the difluoromethane refrigerant alone.
  • difluoromethane refrigerant HFC-32
  • HFC-32 has attracted attention as a refrigerant for refrigerators.
  • Difluoromethane refrigerant has an ozone depletion coefficient of zero and a global warming potential (GWP) currently used refrigerant [R-410A (mixture of difluoromethane and pentafluoroethane), R-407C (difluoromethane and A mixture of pentafluoroethane and 1,1,1,2-tetrafluoroethane), etc.] and a coefficient of performance (COP) of R-410A, R-407C, etc. Therefore, it is a preferable refrigerant from the viewpoint of energy saving (“Lubrication Economy”, June 2004 (No. 460), p. 17).
  • conventional lubricating base oils are not sufficiently compatible with difluoromethane refrigerant, and lubricating base oils with excellent compatibility are demanded (Japanese Patent Laid-Open No. 2002-129177).
  • 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 compatibility of the ester with the refrigerant has a correlation with the property of the ester. In this invention, since isobutyric acid is used as carboxylic acid, the compatibility with a difluoromethane solvent is good.
  • the kinematic viscosity at 100 ° C. of the tetraester is preferably in the range of 4.6 to 8.2 mm 2 / sec, and preferably 5.0 to 7. More preferably, it is in the range of 0 mm 2 / sec. Further, the viscosity index of the ester is preferably 89 or more.
  • 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 (described later in Example 4) and tetraester 10 (described later in Example 10), which are tetraesters of pentaerythritol of the present invention, is 0.031 g / g and 0.024 g / g, which show high solubility of benzotriazole in all pentaesters of pentaerythritol.
  • the pentaerythritol tetraester of the present invention has excellent low-temperature fluidity and excellent wear resistance when benzotriazole is dissolved.
  • Isobutyric acid / 3,5,5-trimethylhexanoic acid / linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms integrated value of peak X / integrated value of peak Y / (integrated value of peak Z / 2)
  • peak X corresponds to the peak of a hydrogen atom on the methine group in isobutyric acid
  • peak Y corresponds to the hydrogen atom on the methine group in 3,5,5-trimethylhexanoic acid
  • peak Z has 4 to 4 carbon atoms.
  • 7 corresponds to the peak of the hydrogen atom on the methylene group at the ⁇ -position of the carbonyl group in the linear aliphatic monocarboxylic acid of No. 7.
  • reaction product was stirred at 218 ° C. for 1 hour under a reduced pressure of 0.7 kPa to distill off unreacted carboxylic acid in the reaction product.
  • the reaction product was washed at 85 ° C. for 1 hour with 400 mL of an alkaline aqueous 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 88 ° C. for 1 hour. Subsequently, the reaction product was dried by stirring at 106 ° C. for 1 hour under a reduced pressure of 1.1 kPa while performing nitrogen bubbling.
  • reaction product 5.0 g of adsorbent (corresponding to 0.5% by weight of the reaction product) and 9.9 g of activated carbon (corresponding to 1.0% by weight of the reaction product) are added, and nitrogen bubbling is performed.
  • the reaction product was stirred at 104 ° C. for 2 hours under a reduced pressure of 1.1 kPa, and then filtered using a filter aid to obtain 822 g of tetraester 1.
  • Example 2 Tetraester of pentaerythritol with a molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio) of 62/38/57 (tetra Production of ester 2)]
  • the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid used was set to 1 / 1.80 /
  • the tetraester 2 was obtained in the same manner as in Example 1 except that the amount was 1.20 / 1.80.
  • Example 3 [Tetraester of pentaerythritol with a molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (ratio of isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid) of 34/66/95 (tetra Production of ester 3)]
  • the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid used is 1 / 0.72 /
  • the tetraester 3 was obtained in the same manner as in Example 1 except that it was 1.68 / 2.40.
  • Example 4 Tetraester of pentaerythritol having a molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (ratio of isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid) of 34/66/41 (tetra Production of ester 4)]
  • the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid used was set to 1 / 1.20 /
  • the tetraester 4 was obtained in the same manner as in Example 1 except that the ratio was changed to 2.00 / 1.60.
  • Example 5 Tetraester of pentaerythritol having a molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio) of 24/76/42 (tetra Production of ester 5)]
  • the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid used is 1 / 0.90 /
  • the tetraester 5 was obtained in the same manner as in Example 1 except that the ratio was 3.00 / 0.90.
  • Example 7 Tetraester of pentaerythritol having a molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid to pentanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) of 69/31/74 (Production of tetraester 7)]
  • pentanoic acid instead of butyric acid
  • the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid used pentanoic acid / isobutyric acid / 3,5,5-trimethylhexanoic acid /
  • the tetraester 7 was obtained in the same manner as in Example 1 except that the ratio of pentanoic acid was changed to 1 / 1.92 / 0.96 / 1.92.
  • Example 8 [Tetraester of pentaerythritol in which the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) is 32/68/104 (Production of tetraester 8)]
  • pentanoic acid instead of butyric acid
  • the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid used pentanoic acid / isobutyric acid / 3,5,5-trimethylhexanoic acid /
  • the tetraester 8 was obtained in the same manner as in Example 1 except that the ratio of pentanoic acid was 1 / 0.72 / 1.68 / 2.40.
  • Example 9 [Tetrapentylerythritol with a molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid (ratio of isobutyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid) of 35/65/42 Production of ester (tetraester 9)]
  • pentanoic acid instead of butyric acid
  • the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid used penentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid /
  • the tetraester 9 was obtained in the same manner as in Example 1 except that the ratio of pentanoic acid was changed to 1 / 1.20 / 2.00 / 1.60.
  • Example 10 [Tetrapentylerythritol tetramole having a molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid to pentanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) of 40/60/11 Production of ester (tetraester 10)]
  • pentanoic acid instead of butyric acid
  • the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid used pentanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid /
  • the tetraester 10 was obtained in the same manner as in Example 1 except that the ratio of pentanoic acid was changed to 1 / 1.73 / 2.59 / 0.48.
  • Example 11 [Tetrapentylerythritol with a molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid to pentanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) of 26/74/22 Production of ester (tetraester 11)]
  • pentanoic acid instead of butyric acid
  • the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid used pentanoic acid / isobutyric acid / 3,5,5-trimethylhexanoic acid /
  • the tetraester 11 was obtained in the same manner as in Example 1 except that the ratio of pentanoic acid was changed to 1 / 0.90 / 3.00 / 0.90.
  • Example 12 Tetraester of pentaerythritol having a molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid to heptanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / heptanoic acid ratio) of 65/35/72 (Production of tetraester 12)] Instead of butyric acid, heptanoic acid is used, and the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and heptanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / The tetraester 12 was obtained in the same manner as in Example 1 except that the ratio of heptanoic acid was changed to 1 / 1.92 / 0.96 / 1.92.
  • Test Example 1 Measurement of pour point The pour points of tetraesters 1 to 12 and ester 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 to 3.
  • Test Example 2 Measurement of kinematic viscosity Using a Canon-Fenske viscometer, the kinematic viscosities of tetraesters 1 to 12 and ester A at 40 ° C and 100 ° C were measured according to the method of JIS K2283: 2000. The viscosity index was calculated according to the same method. The results are shown in Tables 1 to 3.
  • Test Example 3 Measurement of two-layer separation temperature
  • the two-layer separation temperatures of tetraesters 1 to 4 and 6 to 8 were measured according to the method of JIS K2211: 2009.
  • Each 0.4 g of tetraesters 1 to 4 and 6 to 8 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./min.
  • the temperature at which separation or white turbidity occurred was defined as the two-layer separation temperature. The results are shown below.
  • Test Example 6 Measurement of weight loss temperature (evaluation of thermal stability) Using a thermogravimetric / differential calorimeter Tg-DTA6200 (manufactured by Seiko Instruments Inc.), 5% weight loss temperatures of tetraesters 5, 6 and 9 to 12 were measured under the following conditions. The results are shown in Table 4. 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 12 have a kinematic viscosity at 100 ° C. of 4.6 to 8.2 mm 2 / sec, a viscosity index of 89 or more, and a pour point of ⁇ 42.5 ° C. or less. It can be seen that the RBOT life under Condition 1 is 756 minutes or longer and has excellent oxidation / hydrolysis stability.
  • tetraesters 5, 6 and 9 to 12 had a 5% weight loss temperature of 221.8 ° C. or higher in Tg-DTA measurement. It can be seen that the tetraesters of the present invention have excellent thermal stability.
  • tetraesters 1 to 4 and 6 to 8 had a two-layer separation temperature of ⁇ 32 ° C. or lower, and tetraesters 1 to 3 and 7 were ⁇ 50 ° C. or lower. It turns out that the tetraester of this invention has the outstanding compatibility with a difluoromethane refrigerant
  • Test Example 4 the tetraesters 2 to 12 were not solidified, and no precipitate was confirmed. It can be seen that the tetraesters 2 to 12 can be preferably used when stored or used for a long time in a low temperature range.
  • tetraester 3 had an RBOT life of 217 minutes, and tetraester 8 had an RBOT life of 247 minutes. It can be seen that the tetraester of the present invention has high oxidative stability.
  • a tetraester of pentaerythritol used for refrigerating machine oil or the like having a good balance of excellent low-temperature fluidity and excellent stability can be provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un tétraester de pentaérythritol, le tétraester étant un ester mixte de pentaérythritol et d'acide carboxylique, et étant utilisé dans des huiles réfrigérantes et analogues ayant une excellente fluidité à basse température, une excellente stabilité et analogues d'une manière équilibrée. L'acide carboxylique contient de l'acide isobutyrique, de l'acide 3,5,5-triméthylhexanoïque et un acide monocarboxylique aliphatique linéaire en C4-7.
PCT/JP2012/054187 2011-07-13 2012-02-22 Tétraester de pentaérythritol Ceased WO2013008487A1 (fr)

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CN116004298A (zh) * 2021-10-21 2023-04-25 联泓(江苏)新材料研究院有限公司 羧酸酯组合物及其制备方法和应用
CN116004298B (zh) * 2021-10-21 2024-05-17 联泓(江苏)新材料研究院有限公司 羧酸酯组合物及其制备方法和应用

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