WO2012026214A1 - ペンタエリスリトールのテトラエステル - Google Patents
ペンタエリスリトールのテトラエステル Download PDFInfo
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- WO2012026214A1 WO2012026214A1 PCT/JP2011/065109 JP2011065109W WO2012026214A1 WO 2012026214 A1 WO2012026214 A1 WO 2012026214A1 JP 2011065109 W JP2011065109 W JP 2011065109W WO 2012026214 A1 WO2012026214 A1 WO 2012026214A1
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- Prior art keywords
- acid
- pentaerythritol
- tetraester
- trimethylhexanoic
- isobutyric
- Prior art date
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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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
-
- 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
- C07C69/28—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 dihydroxylic compounds
-
- 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
- C07C69/30—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 trihydroxylic 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
- 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
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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
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- 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
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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
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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
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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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
- C10N2040/02—Bearings
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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
- C10N2040/25—Internal-combustion engines
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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 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.
- Patent Document 2 discloses that a mixed ester obtained by reacting pentaerythritol, i-nonanoic acid, and i-butyric anhydride in a molar ratio of 1: 3: 0.5 is used in a method for lubricating a ceramic-containing engine.
- a mixed ester obtained by reacting pentaerythritol, i-nonanoic acid, and i-butyric anhydride in a molar ratio of 1: 3: 0.5 is used in a method for lubricating a ceramic-containing engine.
- a difluoromethane refrigerant there is no description or suggestion about the compatibility of the mixed ester with a difluoromethane refrigerant.
- 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 pentaerythritol tetraesters described in the following [1] to [2].
- a mixed ester of pentaerythritol and carboxylic acid composed of isobutyric acid and 3,5,5-trimethylhexanoic acid, and the molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid in the carboxylic acid (iso A tetraester of pentaerythritol having a ratio of butyric acid / 3,5,5-trimethylhexanoic acid) in the range of 36/64 to 80/20.
- the molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) in the carboxylic acid is in the range of 36/64 to 67/33 [ The tetraester of pentaerythritol as described in 1].
- the tetraester of pentaerythritol of the present invention is a mixed ester of pentaerythritol and a carboxylic acid composed of isobutyric acid and 3,5,5-trimethylhexanoic acid.
- the molar ratio of isobutyric acid is in the range of 36/64 to 80/20, and preferably in the range of 36/64 to 67/33.
- the tetraester of pentaerythritol means a compound obtained by completely esterifying four hydroxyl groups in pentaerythritol with four molecules of carboxylic acid.
- the “mixed ester” in the present invention includes the following (i) to (iii): (I) pentaerythritol tetraester consisting of both isobutyric acid and 3,5,5-trimethylhexanoic acid as constituent carboxylic acids in the same molecule (ii) ester of pentaerythritol and isobutyric acid, and pentaerythritol and 3,5 Mixtures of esters with 5,5-trimethylhexanoic acid (iii) Embodiments of the mixtures of (i) and (ii) above are included. Further, pentaerythritol triesters and the like may be contained as impurities in the pentaerythritol tetraester of the present invention.
- the pentaerythritol tetraester of the present invention comprises reacting pentaerythritol, isobutyric acid, and 3,5,5-trimethylhexanoic acid at 120 to 250 ° C. for 5 to 60 hours in the presence of a catalyst, if desired. Can be manufactured.
- Examples of the catalyst include mineral acids, organic acids, Lewis acids, organic metals, solid acids and the like.
- Specific examples of the mineral acid include hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid and the like.
- Specific examples of 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 isobutyric acid used and the amount of 3,5,5-trimethylhexanoic acid used is preferably 1.1 to 1.4 times the mol of the hydroxyl group of pentaerythritol used.
- a rectifying column is attached to the reactor, and water produced by the reaction can be removed from the reaction mixture.
- the tetraester of pentaerythritol of the present invention is attached to a rectifying column, and when water generated by the reaction is removed from the reaction mixture, the operating conditions of the rectifying column are adjusted to change the amount of isobutyric acid cooked. The ratio of isobutyric acid constituting can be adjusted.
- 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 pentaerythritol tetraester of the present invention is usually used in synthetic organic chemistry (washing with water and / or alkaline aqueous solution, treatment with activated carbon, adsorbent, etc., various chromatographic methods, You may refine
- the tetraester of pentaerythritol of the present invention has excellent compatibility with difluoromethane refrigerant, excellent low-temperature fluidity, excellent stability against hydrolysis, excellent lubricity and the like.
- the kinematic viscosity at 40 ° C. of the tetraester is preferably in the range of 20 to 70 mm 2 / sec, and in the range of 40 to 70 mm 2 / sec. More preferably.
- the two-layer separation temperature is preferably ⁇ 15 ° C. or lower.
- the pour point is preferably ⁇ 40.0 ° C. or lower, and more preferably ⁇ 42.5 ° C. or lower.
- the tetraester of pentaerythritol of the present invention can be used not only for refrigerating machine oil but also for engine oil, gear oil, grease, plasticizer and the like.
- Examples of the refrigerating machine oil using the pentaerythritol tetraester of the present invention include a refrigerating machine oil containing the pentaerythritol tetraester of the present invention and an additive for lubricating oil.
- the refrigerating machine oil using the tetraester of pentaerythritol of the present invention the tetraester is used as a lubricating oil base oil.
- lubricant additives examples include antioxidants, wear reducers (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.
- 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.) and aliphatic esters (fatty acid monoesters, polyesters) other than the tetraesters of pentaerythritol of the present invention.
- 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 ester 1 (Example 1 described later) and ester 6 (Example 6 described later) which are tetraesters of pentaerythritol of the present invention is 0.005 g / g or more.
- high solubility of benzotriazole is exhibited.
- the pentaerythritol tetraester of the present invention has excellent low-temperature fluidity and excellent wear resistance when benzotriazole is dissolved.
- the device when cleaning the device after using the pentaerythritol tetraester of the present invention as a lubricating oil, the device can be easily cleaned with a cleaning agent such as a fluorine-based cleaning agent or an alcohol-based cleaning agent.
- a cleaning agent such as a fluorine-based cleaning agent or an alcohol-based cleaning agent.
- nuclear magnetic resonance spectra were measured, and isobutyric acid and 3,5,5-trimethylhexane in the tetraester of pentaerythritol were measured.
- the molar ratio with the acid was calculated by the following formula.
- the nuclear magnetic resonance spectrum was measured by the following measuring instrument and measuring method. Measuring instrument: GSX-400 (400 MHz) manufactured by JEOL Ltd.
- Example 1 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) of 39/61 (tetraester) 1) Production
- 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 225 ° C. for 1 hour under a reduced pressure of 1.1 kPa to distill off unreacted carboxylic acid in the reaction product.
- the reaction product was washed at 77 ° C. for 1 hour with 2 L 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 2 L of water at 68 ° C. for 1 hour. Subsequently, the reaction product was dried by stirring at 68 ° C. for 1 hour under a reduced pressure of 1.1 kPa while performing nitrogen bubbling.
- 141 g of adsorbent (corresponding to 2% by weight of the reaction product) and 141 g of activated carbon (corresponding to 2% by weight of the reaction product) are added to the reaction product, and 1.3 kPa of the reaction product is added while performing nitrogen bubbling. After stirring at 110 ° C. for 2 hours under reduced pressure, 6402 g of tetraester 1 was obtained by filtration using a filter aid.
- Example 2 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) of 36/64 (tetraester) 2) Production
- the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) to 1 / 1.73 / 3.07
- the tetraester 2 was obtained in the same manner as in Example 1 except that.
- Example 3 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (ratio of isobutyric acid / 3,5,5-trimethylhexanoic acid) of 37/63 (tetraester) 3) Production]
- the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) to 1 / 1.78 / 3.02
- the tetraester 3 was obtained in the same manner as in Example 1 except that.
- Example 4 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (ratio of isobutyric acid / 3,5,5-trimethylhexanoic acid) of 58/42 (tetraester) 4) Production]
- the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) to 1 / 2.78 / 2.02
- the tetraester 4 was obtained in the same manner as in Example 1 except that.
- Example 5 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (ratio of isobutyric acid / 3,5,5-trimethylhexanoic acid) of 67/33 (tetraester) 5) Production]
- the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) to 1 / 3.22 / 1.58
- the tetraester 5 was obtained in the same manner as in Example 1 except that.
- Example 6 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) of 76/24 (tetraester) 6) Production]
- the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) to 1 / 3.65 / 1.15
- the tetraester 6 was obtained in the same manner as in Example 1 except that.
- Example 7 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (ratio of isobutyric acid / 3,5,5-trimethylhexanoic acid) of 80/20 (tetraester) 7) Production]
- the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) to 1 / 3.84 / 0.96
- the tetraester 7 was obtained in the same manner as in Example 1 except that.
- Example 8 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) of 50/50 (tetraester) 8) Production]
- the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) to 1 / 2.40 / 2.40
- the tetraester 8 was obtained in the same manner as in Example 1 except that.
- Example 9 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) of 62/38 (tetraester) 9) Production] The molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) to 1 / 2.98 / 1.82 The tetraester 9 was obtained in the same manner as in Example 1 except that.
- Example 10 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) of 64/36 (tetraester) 10) Production
- the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) to 1 / 3.07 / 1.73
- the tetraester 10 was obtained in the same manner as in Example 1 except that.
- Example 11 Tetraester of pentaerythritol having a molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) of 37/63 (tetraester) 11) Production
- the molar ratio of pentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used was set to 1 / 1.80 / 3.00.
- the tetraester 11 was obtained in the same manner as in Example 1 except that isooctane (Kyowasol C-800; manufactured by Kyowa Hakko Chemical Co., Ltd.) was used as the solvent.
- Test Example 5 Measurement of wear scar diameter of tetraester solution
- the tetraesters 1 to 10, and 19.80 g of each of A and B were mixed with 0.20 g of benzotriazole and heated at 60 ° C. to obtain a 1 wt% tetraester solution of benzotriazole.
- Each of the obtained 1% by weight tetraester solutions was subjected to a load of 200 N, a rotation speed of 1200 rpm, a time of 30 minutes, a temperature of 75 ° C., a test material [test ball (test ball ( The test was conducted under the conditions of SUJ-2)], and the wear scar diameter after the test was measured.
- the wear scar diameter was the average value of all three fixed spheres in the vertical and horizontal directions. The results are shown in Table 2. In Table 2, the smaller the wear scar diameter value, the better the wear resistance of the tetraester solution.
- tetraesters 1 to 10 have excellent kinematic viscosity at 40 ° C. of 30.6 to 69.5 mm 2 / sec and excellent pour point of ⁇ 40.0 to ⁇ 45.0 ° C. It can be seen that the two-layer separation temperature is ⁇ 20 ° C. or lower and has excellent compatibility with the difluoromethane refrigerant. Further, it can be seen that tetraesters 1 to 5 and 8 to 10 have better low temperature fluidity with pour points of ⁇ 42.5 to ⁇ 45.0 ° C. The tetraester 11 has a kinematic viscosity of 68.3 mm 2 / sec and a two-layer separation temperature of ⁇ 20 ° C., which is almost the same as in Example 3.
- tetraesters 1 to 10 have an excellent ability to dissolve benzotriazole when the solubility of benzotriazole at 5 ° C. is 0.020 g / g or more. Tetraesters 1 to 10 have a pour point of a 3 wt% tetraester solution of benzotriazole of ⁇ 40.0 ° C. or less, and a wear scar diameter of a 1 wt% tetraester solution of benzotriazole of 0.60 mm or less. From this, it can be seen that when benzotriazole is dissolved, it has excellent low-temperature fluidity and excellent wear resistance.
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Abstract
Description
[1]ペンタエリスリトールとイソ酪酸および3,5,5-トリメチルヘキサン酸からなるカルボン酸との混合エステルであり、前記カルボン酸における3,5,5-トリメチルヘキサン酸に対するイソ酪酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が36/64~80/20の範囲にあるペンタエリスリトールのテトラエステル。
[2]前記カルボン酸における3,5,5-トリメチルヘキサン酸に対するイソ酪酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が36/64~67/33の範囲にある[1]に記載のペンタエリスリトールのテトラエステル。
(i)同一分子における構成カルボン酸が、イソ酪酸および3,5,5-トリメチルヘキサン酸の双方からなるペンタエリスリトールのテトラエステル
(ii)ペンタエリスリトールとイソ酪酸とのエステル、および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のエステルの混合物
(iii)上記(i)および(ii)の混合物
の各態様が包含される。
また、本発明のペンタエリスリトールのテトラエステル中にペンタエリスリトールのトリエステル等が不純物として含まれていてもよい。
核磁気共鳴スペクトルは、以下の測定機器、測定手法により測定した。
測定機器;日本電子社製GSX-400(400MHz)
測定手法;1H-NMR、標準物(テトラメチルシラン)、溶媒(CDCl3)
イソ酪酸/3,5,5-トリメチルヘキサン酸
=ピークXの積分値/ピークYの積分値
ここで、ピークXはイソ酪酸におけるメチン基上の水素原子のピークに相当し、ピークYは3,5,5-トリメチルヘキサン酸におけるメチン基上の水素原子のピークに相当する。
吸着剤としては、協和化学工業社製キョーワード500を用いた。
活性炭としては、日本エンバイロケミカルズ社製白鷺Pを用いた。
ディーンスタークトラップの付いた反応器にペンタエリスリトール1634g(12.0モル、広栄パーストープ社製)、イソ酪酸1979g(22.5モル、東京化成社製)および3,5,5-トリメチルヘキサン酸5560g(35.1モル、協和発酵ケミカル社製)を仕込み、混合物を攪拌しながら室温で30分間窒素バブリングを行うことにより混合物を脱気した。
次いで、窒素バブリングを行いながら混合物を155~230℃で12.5時間攪拌し、次いで、反応混合物にテトラブトキシチタン1.3gを添加し、次いで、反応混合物を230℃で12時間攪拌した。反応後、反応生成物を1.1kPaの減圧下、225℃で1時間攪拌することにより、反応生成物中の未反応のカルボン酸を留去した。反応生成物を、該反応生成物の酸価に対して2倍モルの水酸化ナトリウムを含むアルカリ水溶液2Lで、77℃で1時間洗浄した。次いで、反応生成物を、水2Lで68℃で1時間、3回洗浄した。次いで、窒素バブリングを行いながら反応生成物を1.1kPaの減圧下、68℃で1時間攪拌することにより反応生成物を乾燥した。
反応生成物に吸着剤141g(反応生成物の2重量%に相当する)および活性炭141g(反応生成物の2重量%に相当する)を添加し、窒素バブリングを行いながら反応生成物を1.3kPaの減圧下、110℃で2時間攪拌した後、濾過助剤を用いて濾過することにより、テトラエステル1を6402g得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/1.73/3.07にする以外は、実施例1と同様に操作して、テトラエステル2を得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/1.78/3.02にする以外は、実施例1と同様に操作して、テトラエステル3を得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/2.78/2.02にする以外は、実施例1と同様に操作して、テトラエステル4を得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/3.22/1.58にする以外は、実施例1と同様に操作して、テトラエステル5を得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/3.65/1.15にする以外は、実施例1と同様に操作して、テトラエステル6を得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/3.84/0.96にする以外は、実施例1と同様に操作して、テトラエステル7を得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/2.40/2.40にする以外は、実施例1と同様に操作して、テトラエステル8を得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/2.98/1.82にする以外は、実施例1と同様に操作して、テトラエステル9を得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/3.07/1.73にする以外は、実施例1と同様に操作して、テトラエステル10を得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/1.80/3.00にし、溶媒としてイソオクタン(キョーワゾールC-800;協和発酵ケミカル社製)を用いる以外は、実施例1と同様に操作して、テトラエステル11を得た。
イソ酪酸の代わりに無水イソ酪酸を用い、ペンタエリスリトール、無水イソ酪酸および3,5,5-トリメ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/無水イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.5/3にする以外は、実施例1と同様に操作して、テトラエステルAを得た。
ペンタエリスリトール、イソ酪酸および3,5,5-トリメ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/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/4.03/0.77にする以外は、実施例1と同様に操作して、テトラエステルBを得た。
自動流動点測定器RPP-01CML(離合社製)を用い、JIS K2269-1987の方法に準じてテトラエステル1~10、およびA、Bの流動点を測定した。結果を表1に示す。
キャノン-フェンスケ粘度計を用い、JIS K2283:2000の方法に準じてテトラエステル1~11、およびA、Bの40℃における動粘度を測定した。結果を表1および以下に示す。
JIS K2211:2009の方法に準じてテトラエステル1~10、およびA、Bの二層分離温度を測定した。テトラエステル1~11、およびA、Bのそれぞれ0.4gとジフルオロメタン冷媒3.6gを耐圧ガラス管に封入し、混合物を30℃から毎分0.5℃の速度で冷却し、混合物が二層分離または白濁する温度を二層分離温度とした。結果を表1および以下に示す。
テトラエステル1~10、およびA、Bのそれぞれ4.85gに、ベンゾトリアゾール0.15gを混合し、60℃で加熱して、ベンゾトリアゾールの3重量%テトラエステル溶液のそれぞれを得た。該テトラエステル溶液のそれぞれを5℃で40時間静置した後、目視により析出物の確認を行った。
析出物の見られなかった該テトラエステル溶液は、5℃におけるベンゾトリアゾールの溶解度[テトラエステル1gに対するベンゾトリアゾールの溶解量(g)]を0.030g/g以上とした。
析出物の見られた該テトラエステル溶液は、析出物を濾過(濾紙;No.5A、桐山製作所製)により除去した後に、得られた濾液を高速液体クロマトグラフィー(AGILENT社製1200SERIES、カラム:YMC Pack Ph A-414 Φ6.0×300mm、移動相:テトラヒドロフラン/0.1%リン酸水溶液=7/3、カラム温度:40℃、流速:0.7mL/分、検出:UV(220nm)、サンプル濃度:50g/L、インジェクト量:5μL)で測定し、絶対検量線法により、5℃におけるベンゾトリアゾールの溶解度[テトラエステル1gに対するベンゾトリアゾールの溶解(g)]を求めた。結果を表2に示す。
テトラエステル1~10、およびA、Bのそれぞれ19.80gに、ベンゾトリアゾール0.20gを混合し、60℃で加熱して、ベンゾトリアゾールの1重量%テトラエステル溶液のそれぞれを得た。
得られた該1重量%テトラエステル溶液のそれぞれを、シェル式四球摩擦試験機(神鋼造機社製)を用い、荷重200N、回転数1200rpm、時間30分、温度75℃、試験材[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2に示す。 表2において、摩耗痕径の値が小さいもの程、テトラエステル溶液の耐摩耗特性が優れていることを表す。
テトラエステル1~10、およびA、Bのそれぞれ43.65gに、ベンゾトリアゾール1.35gを混合し、60℃で加熱して、ベンゾトリアゾールの3重量%テトラエステル溶液のそれぞれを得た。
自動流動点測定器RPP-01CML(離合社製)を用い、JIS K2269-1987の方法に準じて、該3重量%テトラエステル溶液のそれぞれの流動点を測定した。結果を表2に示す。
表2において、BZTはベンゾトリアゾールを示す。
Claims (2)
- ペンタエリスリトールとイソ酪酸および3,5,5-トリメチルヘキサン酸からなるカルボン酸との混合エステルであり、前記カルボン酸における3,5,5-トリメチルヘキサン酸に対するイソ酪酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が36/64~80/20の範囲にあるペンタエリスリトールのテトラエステル。
- 前記カルボン酸における3,5,5-トリメチルヘキサン酸に対するイソ酪酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が36/64~67/33の範囲にある請求項1に記載のペンタエリスリトールのテトラエステル。
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CN102725259A (zh) | 2012-10-10 |
JPWO2012026214A1 (ja) | 2013-10-28 |
TW201213532A (en) | 2012-04-01 |
TWI400329B (zh) | 2013-07-01 |
JP5089826B2 (ja) | 2012-12-05 |
KR20130100100A (ko) | 2013-09-09 |
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