TW201303005A - Tetraester of pentaerythritol - Google Patents

Tetraester of pentaerythritol Download PDF

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TW201303005A
TW201303005A TW101105878A TW101105878A TW201303005A TW 201303005 A TW201303005 A TW 201303005A TW 101105878 A TW101105878 A TW 101105878A TW 101105878 A TW101105878 A TW 101105878A TW 201303005 A TW201303005 A TW 201303005A
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acid
tetraester
pentaerythritol
trimethylhexanoic
isobutyric
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TW101105878A
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TWI583783B (en
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Satoshi Hiyoshi
Takuya Nishimura
Toshihiro Inayama
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Kh Neochem Co Ltd
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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

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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

The present invention provides a tetraester of pentaerythritol, the tetraester being a mixed ester of pentaerythritol and carboxylic acid, and being used in refrigerant oils and the like having excellent low-temperature fluidity, excellent stability, and the like in a balanced manner. The carboxylic acid contains isobutyric acid, 3,5,5-trimethylhexanoic acid, and C4-7 linear aliphatic monocarboxylic acid.

Description

季戊四醇之四酯 Tetraester of pentaerythritol

本發明係關於一種用於冷凍機油等工業用潤滑油等之季戊四醇之四酯。 The present invention relates to a tetraester of pentaerythritol for use in an industrial lubricating oil such as a refrigerating machine oil.

用於冷凍機油等工業用潤滑油之潤滑油要求用以於冬季或寒冷地區等低溫環境下使用之優異之低溫流動性或各種穩定性的提高。作為該穩定性，可列舉：熱穩定性、氧化穩定性、氧化/水解穩定性等。又，對於使用該潤滑油之機器而言，要求耐磨損性、抗疲勞性等各種耐久性提高，節能性能之提高等。 Lubricating oils for industrial lubricating oils such as refrigerating machine oils are required to be used for excellent low-temperature fluidity or various stability improvements in low-temperature environments such as winter or cold regions. Examples of the stability include thermal stability, oxidation stability, and oxidation/hydrolysis stability. Further, the machine using the lubricating oil is required to have various durability such as abrasion resistance and fatigue resistance, and to improve energy-saving performance.

專利文獻1中記載：含有使季戊四醇、3,5,5-三甲基己酸、異丁酸及己二酸以1：1：2.5：0.25之莫耳比反應而獲得之酯的液狀組合物作為冰箱及空調之冷卻液體而有用，但該酯之低溫流動性及穩定性等不滿足要求。 Patent Document 1 describes a liquid combination containing an ester obtained by reacting pentaerythritol, 3,5,5-trimethylhexanoic acid, isobutyric acid, and adipic acid at a molar ratio of 1:1:2.5:0.25. The material is useful as a cooling liquid for refrigerators and air conditioners, but the low temperature fluidity and stability of the esters are not satisfactory.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平6-25690號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 6-25690

本發明之目的在於提供一種平衡良好地具有優異之低溫流動性及優異之穩定性等的用於冷凍機油等之季戊四醇之四酯。 An object of the present invention is to provide a tetraester of pentaerythritol for use in a refrigerator oil or the like which has excellent low-temperature fluidity and excellent stability.

本發明係提供以下[1]~[5]。 The present invention provides the following [1] to [5].

[1]一種季戊四醇之四酯，其係季戊四醇與羧酸之混合酯，且上述羧酸含有異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸。 [1] A tetraester of pentaerythritol which is a mixed ester of pentaerythritol and a carboxylic acid, and the above carboxylic acid contains isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear fat having a carbon number of 4 to 7. Group of monocarboxylic acids.

[2]如[1]之季戊四醇之四酯，其中上述羧酸包含異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸。 [2] The tetraester of pentaerythritol of [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.

[3]如[1]或[2]之季戊四醇之四酯，其中上述碳數4~7之直鏈脂肪族單羧酸為丁酸。 [3] The tetraester of pentaerythritol of [1] or [2], wherein the linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms is butyric acid.

[4]如[1]或[2]之季戊四醇之四酯，其中上述碳數4~7之直鏈脂肪族單羧酸為戊酸。 [4] The tetraester of pentaerythritol of [1] or [2], wherein the linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms is valeric acid.

[5]如[1]至[4]中任一項之季戊四醇之四酯，其中100℃之動黏度在4.6~8.2 mm2/秒之範圍內。 [5] The tetraester of pentaerythritol according to any one of [1] to [4], wherein the dynamic viscosity at 100 ° C is in the range of 4.6 to 8.2 mm 2 /sec.

藉由本發明，可提供一種平衡良好地具有優異之低溫流動性及優異之穩定性等的用於冷凍機油等之季戊四醇之四酯。 According to the present invention, it is possible to provide a tetraester of pentaerythritol for use in a refrigerating machine oil or the like which has excellent low-temperature fluidity and excellent stability.

本發明之季戊四醇之四酯係季戊四醇與含有異丁酸、3,5,5-三甲基己酸及碳數4~7之直鏈脂肪族單羧酸之羧酸的混合酯。此處，所謂季戊四醇之四酯，係指對季戊四醇使用複數種形成酯之羧酸進行酯化而獲得之化合物。 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. Here, the tetraester of pentaerythritol refers to a compound obtained by esterifying pentaerythritol with a plurality of carboxylic acids forming an ester.

又，本發明中所謂之「混合酯」中包含下述(i)~(vi)之各態樣： Further, the "mixed ester" as used in the present invention includes the following aspects (i) to (vi):

(i)同一分子中之構成羧酸含有異丁酸、3,5,5-三甲基 己酸、及碳數4~7之直鏈脂肪族單羧酸的季戊四醇之四酯 (i) The constituent carboxylic acid in the same molecule contains isobutyric acid, 3,5,5-trimethyl Hexanoic acid and tetraester of pentaerythritol of a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms

(ii)同一分子中之構成羧酸含有選自異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸之群中之兩者的季戊四醇之四酯 (ii) the constituent carboxylic acid in the same molecule contains two selected from the group consisting of isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms. Tetraester of pentaerythritol

(iii)季戊四醇與含有異丁酸之羧酸之四酯 (iii) pentaerythritol and a tetraester of a carboxylic acid containing isobutyric acid

(iv)季戊四醇與含有3,5,5-三甲基己酸之羧酸之四酯 (iv) pentaerythritol and a tetraester of a carboxylic acid containing 3,5,5-trimethylhexanoic acid

(v)季戊四醇與含有碳數4~7之直鏈脂肪族單羧酸之羧酸之四酯 (v) a tetraester of pentaerythritol and a carboxylic acid containing a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms

(vi)選自上述(i)~(v)之群中之兩種以上之四酯的混合物(其中，構成混合酯之羧酸含有異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸)。 (vi) a mixture of two or more kinds of tetraesters selected from the group consisting of the above (i) to (v) (wherein the carboxylic acid constituting the mixed ester contains isobutyric acid, 3,5,5-trimethylhexanoic acid And a linear aliphatic monocarboxylic acid having a carbon number of 4 to 7.

本發明之季戊四醇之四酯中亦可含有季戊四醇之三酯等作為雜質。 The tetraester of pentaerythritol of the present invention may further contain, as an impurity, a trimer of pentaerythritol or the like.

構成混合酯之羧酸中亦可含有除了異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸以外之其他羧酸。作為其他羧酸，例如可列舉：乙酸、丙酸、辛酸、壬酸、癸酸、十二酸、十四酸、十六酸、十八酸等直鏈脂肪族單羧酸；2-甲基丁酸、3-甲基丁酸、2,2-二甲基丙酸、2-乙基丁酸、2-甲基戊酸、4-甲基戊酸、2-甲基己酸、2-乙基戊酸、2-乙基-2-甲基丁酸、2,2-二甲基戊酸、2-甲基庚酸、2-乙基己酸、3-乙基己酸、2-乙基-2-甲基戊酸、2-甲基辛酸、2,2-二甲基庚酸、異十三酸、異硬脂酸等分支狀脂肪族單羧酸等。 The carboxylic acid constituting the mixed ester may further contain a carboxylic acid other than isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms. Examples of the other carboxylic acid include linear aliphatic monocarboxylic acids such as acetic acid, propionic acid, caprylic acid, capric acid, capric acid, dodecanoic acid, myristic acid, palmitic acid, and octadecanoic acid; 2-methyl group; Butyric acid, 3-methylbutyric acid, 2,2-dimethylpropionic acid, 2-ethylbutyric acid, 2-methylpentanoic acid, 4-methylpentanoic acid, 2-methylhexanoic acid, 2- Ethyl valeric acid, 2-ethyl-2-methylbutyric acid, 2,2-dimethylvaleric acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 2- a branched aliphatic monocarboxylic acid such as ethyl-2-methylpentanoic acid, 2-methyloctanoic acid, 2,2-dimethylheptanoic acid, isotridecanoic acid or isostearic acid.

關於上述含有異丁酸、3,5,5-三甲基己酸及碳數4~7之直 鏈脂肪族單羧酸之羧酸中的其他羧酸之含量，只要為不損及本發明之季戊四醇之四酯的低溫流動性、穩定性或對於二氟甲烷冷媒等之相溶性等優異特性之範圍即可。其他羧酸相對於異丁酸、3,5,5-三甲基己酸及碳數4~7之直鏈脂肪族單羧酸之和的莫耳比[其他羧酸/(異丁酸、3,5,5-三甲基己酸及碳數4~7之直鏈脂肪族單羧酸)比]較佳為在0/100~5/100之範圍內。 Regarding the above containing isobutyric acid, 3,5,5-trimethylhexanoic acid and a carbon number of 4 to 7 The content of the other carboxylic acid in the carboxylic acid of the chain aliphatic monocarboxylic acid is excellent as long as it does not impair the low-temperature fluidity, stability, compatibility with a difluoromethane refrigerant or the like of the tetraester of the pentaerythritol of the present invention. The scope is fine. Mohr ratio of other carboxylic acid relative to the sum of isobutyric acid, 3,5,5-trimethylhexanoic acid and a linear aliphatic monocarboxylic acid having 4 to 7 carbons [other carboxylic acids / (isobutyric acid, The ratio of 3,5,5-trimethylhexanoic acid and a linear aliphatic monocarboxylic acid having a carbon number of 4 to 7 is preferably in the range of from 0/100 to 5/100.

於本發明中，更佳為構成混合酯之羧酸為包含異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸者。 In the present invention, the carboxylic acid constituting the mixed ester is preferably a compound containing isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms.

作為構成本發明之季戊四醇之四酯的碳數4~7之直鏈脂肪族單羧酸，具體可列舉：丁酸、戊酸、己酸、庚酸，其中，較佳為丁酸或戊酸。於碳數4~7之直鏈脂肪族單羧酸為丁酸或戊酸時，本發明之季戊四醇之四酯尤其平衡良好地具有對於二氟甲烷冷媒之廣泛濃度下之相溶性、黏度-溫度特性、低溫流動性、低溫特性、穩定性等優異特性。 Specific examples of the linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention include butyric acid, valeric acid, caproic acid, and heptanoic acid, and among them, butyric acid or valeric acid is preferred. . When the linear aliphatic monocarboxylic acid having a carbon number of 4 to 7 is butyric acid or valeric acid, the tetraester of the pentaerythritol of the present invention has a balance, viscosity, and temperature at a wide concentration of the difluoromethane refrigerant in a particularly well-balanced manner. Excellent characteristics such as characteristics, low temperature fluidity, low temperature characteristics, and stability.

於構成本發明之季戊四醇之四酯的碳數4~7之直鏈脂肪族單羧酸為丁酸或戊酸時，丁酸或戊酸相對於異丁酸與3,5,5-三甲基己酸之和的莫耳比[(丁酸或戊酸)/(異丁酸及3,5,5-三甲基己酸)比]較佳為10/100~300/100之範圍。 When the linear aliphatic monocarboxylic acid having a carbon number of 4 to 7 constituting the tetraester of pentaerythritol of the present invention is butyric acid or valeric acid, butyric acid or valeric acid is compared with isobutyric acid and 3,5,5-trimethyl The molar ratio of [(butyric acid or valeric acid) / (isobutyric acid and 3,5,5-trimethylhexanoic acid)] is preferably in the range of 10/100 to 300/100.

於構成本發明之季戊四醇之四酯的碳數4~7之直鏈脂肪族單羧酸為庚酸時，庚酸相對於異丁酸與3,5,5-三甲基己酸之和的莫耳比[庚酸/(異丁酸及3,5,5-三甲基己酸)比]較佳為20/100~100/100之範圍。 When the linear aliphatic monocarboxylic acid having a carbon number of 4 to 7 constituting the tetraester of pentaerythritol of the present invention is heptanoic acid, the ratio of heptanoic acid 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.

於低溫特性與穩定性之方面而言，異丁酸相對於構成本 發明之季戊四醇之四酯的所有羧酸之和的比例(莫耳%)較佳為5~55莫耳%之範圍，更佳為9~40莫耳%之範圍，進而更佳為15~40莫耳%之範圍。 Isobutyric acid relative to the constituents in terms of low temperature properties and stability The ratio of the sum of all the carboxylic acids of the tetraester of pentaerythritol of the invention (% by mole) is preferably in the range of 5 to 55 mol%, more preferably in the range of 9 to 40 mol%, and still more preferably 15 to 40. The range of Moll%.

本發明之季戊四醇之四酯例如可藉由使季戊四醇、異丁酸、3,5,5-三甲基己酸、碳數4~7之直鏈脂肪族單羧酸、及視需要的其他羧酸於120~250℃下反應5~60小時而製造。 The tetraester of pentaerythritol of the present invention can be, for example, by making pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid, a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms, and optionally other carboxylic acids. The acid is produced by reacting at 120 to 250 ° C for 5 to 60 hours.

於上述反應中亦可使用觸媒，作為觸媒，例如可列舉：無機酸、有機酸、路易斯酸、有機金屬、固體酸等。作為無機酸之具體例，例如可列舉：鹽酸、氫氟酸、硫酸、磷酸、硝酸等。作為有機酸之具體例，例如可列舉：對甲苯磺酸、苯磺酸、丁磺酸、丙磺酸、乙磺酸、甲磺酸等。作為路易斯酸之具體例，例如可列舉：三氟化硼、氯化鋁、四氯化錫、四氯化鈦等。作為有機金屬之具體例，例如可列舉：四丙氧基鈦、四丁氧基鈦、四(2-乙基己氧基)鈦等。作為固體酸之具體例，例如可列舉陽離子交換樹脂等。 A catalyst may be used in the above reaction, and examples of the catalyst include inorganic acids, organic acids, Lewis acids, organic metals, and solid acids. Specific examples of the inorganic acid include hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, and nitric acid. Specific examples of the organic acid include p-toluenesulfonic acid, benzenesulfonic acid, butanesulfonic acid, propanesulfonic acid, ethanesulfonic acid, and methanesulfonic acid. Specific examples of the Lewis acid include boron trifluoride, aluminum chloride, tin tetrachloride, and titanium tetrachloride. Specific examples of the organic metal include titanium tetrapropoxide, titanium tetrabutoxide, and titanium tetrakis(2-ethylhexyloxy). Specific examples of the solid acid include a cation exchange resin and the like.

較佳為異丁酸之使用量、3,5,5-三甲基己酸之使用量、碳數4~7之直鏈脂肪族單羧酸之使用量、及其他羧酸之使用量的和相對於所使用之季戊四醇之羥基而為1.1~1.4倍莫耳。 Preferably, the amount of isobutyric acid used, the amount of 3,5,5-trimethylhexanoic acid used, the amount of the linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms, and the amount of other carboxylic acid used are preferred. And 1.1 to 1.4 times moles relative to the hydroxyl group of the pentaerythritol used.

於上述反應中亦可使用溶劑，作為溶劑，例如可列舉：苯、甲苯、二甲苯、己烷、庚烷、異己烷、異辛烷、壬烷、癸烷等烴系溶劑等。 A solvent may be used for the above reaction, and examples of the solvent include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, isohexane, isooctane, decane, and decane.

較佳為一面將由於反應而生成之水自反應混合物中去除 一面進行反應。有時於將由於反應而生成之水自反應混合物中去除時，同時將異丁酸及/或碳數4~7之直鏈脂肪族單羧酸亦自反應混合物中去除。 Preferably, the water formed by the reaction is removed from the reaction mixture on one side. The reaction is carried out on one side. Sometimes, when the water formed by the reaction is removed from the reaction mixture, isobutyric acid and/or a linear aliphatic monocarboxylic acid having a carbon number of 4 to 7 are also removed from the reaction mixture.

又，由於異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸相對於季戊四醇之反應性之差，有時構成所獲得之四酯之異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸之莫耳比與四酯之製造中所使用之量的莫耳比不同。 Further, due to the difference in reactivity between isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms relative to pentaerythritol, the obtained tetraester may be constituted. The molar ratio of the isobutyric acid, 3,5,5-trimethylhexanoic acid, and the linear aliphatic monocarboxylic acid having a carbon number of 4 to 7 is different from the molar ratio of the amount used in the production of the tetraester. .

反應後，視需要亦可利用有機合成化學中通常使用之方法(使用水及/或鹼性水溶液之清洗，利用活性碳、吸附劑等之處理，各種層析法，蒸餾法等)對本發明之季戊四醇之四酯進行純化。 After the reaction, if necessary, the method generally used in organic synthetic chemistry (cleaning with water and/or alkaline aqueous solution, treatment with activated carbon, adsorbent, etc., various chromatography methods, distillation method, etc.) may be used for the present invention. The tetraester of pentaerythritol is purified.

本發明之季戊四醇之四酯具有優異之低溫流動性、優異之穩定性、優異之低溫特性、優異之黏度-溫度特性、優異之對於二氟甲烷溶劑之相溶性、優異之潤滑性等。 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 a difluoromethane solvent, and excellent lubricity.

所謂黏度-溫度特性，係指動黏度相對於潤滑油等油劑之溫度變化的變化。所謂黏度-溫度特性良好，係指黏度變化相對於溫度變化較小，另一方面，所謂不良，係指於低溫區域中之急遽之增黏或於高溫區域中動黏度降低至預想以上者。通常，該特性係表示為黏度指數，可謂數值越高則黏度-溫度特性越良好。又，於低溫區域中之黏度特性亦被稱為低溫流動性，係以流動點或凝固點、成溝點(channel point)等表示。 The viscosity-temperature characteristic refers to a change in dynamic viscosity with respect to temperature change of an oil agent such as a lubricating oil. The viscosity-temperature characteristic is good, which means that the change in viscosity is small with respect to temperature change. On the other hand, the term "bad" refers to an increase in viscosity in a low temperature region or a decrease in dynamic viscosity in a high temperature region. Generally, this characteristic is expressed as a viscosity index, and the higher the value, the better the viscosity-temperature characteristic. Further, the viscosity characteristic in the low temperature region is also referred to as low temperature fluidity, and is expressed by a pour point, a freezing point, a channel point, and the like.

流動點係指於依據日本工業標準(JIS，Japanese Industrial Standards)K2269之方法對潤滑油等油劑進行冷卻時，油劑流動之最低溫度。流動點較低之油劑於在冬季或寒冷地區等低溫環境下使用或用作冷凍機油之情形時，即便於冷凍機內之蒸發器等成為低溫之運轉條件下，流動性亦不會惡化，因此不會產生使用油劑之機器之動作不良，就此方面而言較佳。 The pour point is based on Japanese Industrial Standards (JIS, Japanese Industrial) Standards) Method of K2269 The minimum temperature at which the oil flows when cooling oil such as lubricating oil. When the oil agent having a low flow point is used in a low-temperature environment such as winter or a cold region or used as a refrigerating machine oil, the fluidity does not deteriorate even when the evaporator in the refrigerator is operated at a low temperature. Therefore, the malfunction of the machine using the oil agent is not generated, and it is preferable in this respect.

又，於將潤滑油等油劑於溫差較大之場所中長期保管或使用之情形時，較佳為於高溫區域中無揮發性等、於低溫區域中無固化或析出等之油劑。作為溫度範圍，並無特別限制，較佳為於高溫側於150℃左右、於低溫側於-20℃左右之溫度下可穩定地使用之油劑。將於低溫區域中不產生固化或析出物之特性定義為低溫特性。於本發明中，藉由使用碳數4~7之直鏈脂肪族單羧酸作為羧酸，可抑制於低溫時產生析出物。 Further, when an oil agent such as a lubricating oil is stored or used for a long period of time in a place where the temperature difference is large, it is preferably an oil agent which does not have a volatility or the like in a high temperature region and which is not cured or precipitated in a low temperature region. The temperature range is not particularly limited, and is preferably an oil agent which can be stably used at a temperature of about 150 ° C on a high temperature side and at a temperature of about -20 ° C on a low temperature side. The property of not forming solidification or precipitates in the low temperature region is defined as low temperature characteristics. In the present invention, by using a linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms as the carboxylic acid, precipitation of precipitates at a low temperature can be suppressed.

關於穩定性，例如於潤滑油用途中可列舉熱穩定性、氧化穩定性、氧化/水解穩定性、剪切穩定性等。 Examples of the stability include thermal stability, oxidation stability, oxidation/hydrolysis stability, shear stability, and the like, for example, in the use of lubricating oil.

關於潤滑性，可列舉摩擦降低性或磨損降低性、極壓性等。 Examples of the lubricity include friction reduction, wear reduction, and extreme pressure.

又，本發明之季戊四醇之四酯不僅對於先前之二氟甲烷混合溶劑(R-410A、R-407C)、而且對於單獨之二氟甲烷冷媒之相溶性亦優異。作為冷凍機用之冷媒，近年來二氟甲烷冷媒(HFC-32)備受矚目。二氟甲烷冷媒之臭氧破壞係數為零，全球暖化係數(GWP，global warming potential)低至目前所使用之冷媒[R-410A(二氟甲烷與五氟乙烷之混合 物)、R-407C(二氟甲烷、五氟乙烷及1,1,1,2-四氟乙烷之混合物)等]之約1/3~1/4，且性能係數(COP，Coefficient of Performance)亦相對於R-410A、R-407C等而提高約5~13%，因此就節能化之觀點而言亦為較佳之冷媒(「潤滑經濟」，2004年6月號(No.460)，p.17)。然而，先前之潤滑油基礎油對於二氟甲烷冷媒之相溶性不充分，而謀求相溶性優異之潤滑油基礎油(日本專利特開2002-129177號公報)。 Further, the tetraester of pentaerythritol of the present invention is excellent not only for the previous difluoromethane mixed solvent (R-410A, R-407C) but also for the compatibility of the difluoromethane refrigerant alone. As a refrigerant for refrigerators, in recent years, difluoromethane refrigerant (HFC-32) has attracted attention. The ozone depletion coefficient of difluoromethane refrigerant is zero, and the global warming potential (GWP) is as low as the refrigerant currently used [R-410A (mixture of difluoromethane and pentafluoroethane). (), about 1/3 to 1/4 of R-407C (mixture of difluoromethane, pentafluoroethane and 1,1,1,2-tetrafluoroethane), etc., and coefficient of performance (COP, Coefficient) Of Performance is also about 5 to 13% higher than that of R-410A and R-407C. Therefore, it is also a better refrigerant in terms of energy saving ("Lubrication Economy", June 2004 (No. 460) ), p.17). However, the lubricating oil base oil of the prior art is insufficient in compatibility with the difluoromethane refrigerant, and the lubricating base oil having excellent compatibility is sought (Japanese Patent Laid-Open Publication No. 2002-129177).

對於二氟甲烷冷媒之相溶性通常係使用二層分離溫度錶示。可謂二層分離溫度越低則於低溫側之相溶性越良好。 又，酯對於冷媒之相溶性與該酯之性質有關。於本發明中，由於使用異丁酸作為羧酸，故對於二氟甲烷溶劑之相溶性良好。 The compatibility of the difluoromethane refrigerant is usually expressed using a two-layer separation temperature. It can be said that the lower the separation temperature of the two layers, the better the compatibility on the low temperature side. Further, the compatibility of the ester with the refrigerant is related to the nature of the ester. In the present invention, since isobutyric acid is used as the carboxylic acid, the compatibility with the difluoromethane solvent is good.

將本發明之季戊四醇之四酯用於冷凍機油時之該四酯的100℃下之動黏度較佳為在4.6~8.2 mm2/秒之範圍內，更佳為在5.0~7.0 mm2/秒之範圍內。 When the tetraester of pentaerythritol of the present invention is used in a refrigerator oil, the dynamic viscosity at 100 ° C of the tetraester is preferably in the range of 4.6 to 8.2 mm 2 /sec, more preferably 5.0 to 7.0 mm 2 /sec. Within the scope.

又，該酯之黏度指數較佳為89以上。 Further, the viscosity index of the ester is preferably 89 or more.

於將本發明之季戊四醇之四酯用於冷凍機油時，若該四酯之羥基之殘存量較多，則會產生冷凍機油於低溫下白濁，堵塞冷凍循環之毛細管裝置等欠佳之現象，因此該混合酯之羥值較佳為10 mg KOH/g以下，更佳為5 mg KOH/g以下。 When the tetraester of pentaerythritol of the present invention is used for a refrigerating machine oil, if the residual amount of the hydroxyl group of the tetraester is large, there is a problem that the refrigerating machine oil is turbid at a low temperature, and the capillary device that blocks the refrigeration cycle is inferior. The mixed ester preferably has a hydroxyl value of 10 mg KOH/g or less, more preferably 5 mg KOH/g or less.

本發明之季戊四醇之四酯除了用於冷凍機油以外，亦可用於發動機油(engine oil)、齒輪油、混合車或電動車中所 利用之馬達油(motor oil)、滑脂(grease)、金屬零件之清潔劑、塑化劑等。 The tetraester of pentaerythritol of the present invention can be used in engine oil, gear oil, hybrid car or electric vehicle in addition to refrigeration oil. Motor oil, grease, metal parts cleaner, plasticizer, etc.

作為使用本發明之季戊四醇之四酯的冷凍機油，例如可列舉含有季戊四醇之四酯及潤滑油用添加劑之冷凍機油等。於使用本發明之季戊四醇之四酯的冷凍機油中，該四酯係用作潤滑油基礎油。 The refrigerating machine oil to which the tetraester of pentaerythritol of the present invention is used is, for example, a refrigerating machine oil containing a tetraester of pentaerythritol and an additive for lubricating oil. In the refrigerating machine oil using the tetraester of pentaerythritol of the present invention, the tetraester is used as a lubricating base oil.

作為潤滑油用添加劑，例如可列舉：抗氧化劑、磨損降低劑(耐磨損劑、抗熔著劑、極壓劑等)、摩擦調整劑、酸捕捉劑、金屬減活劑、消泡劑等通常被用作潤滑油添加劑者。該等添加劑之含量較佳為於冷凍機油中分別為0.001~5重量%。 Examples of the lubricant additive include an antioxidant, a wear reducing agent (anti-wear agent, anti-fusing agent, extreme pressure agent, etc.), a friction modifier, an acid scavenger, a metal deactivator, an antifoaming agent, and the like. Usually used as a lubricant additive. The content of the additives is preferably 0.001 to 5% by weight in the refrigerating machine oil.

亦可將本發明之季戊四醇之四酯與其他潤滑油基礎油併用而使用。作為其他潤滑油基礎油，例如可列舉礦物油、合成基礎油等。 The tetraester of pentaerythritol of the present invention can also be used in combination with other lubricating base oils. Examples of the other lubricating base oil include mineral oil, synthetic base oil, and the like.

作為礦物油，例如可列舉：石蠟基系原油、中間基系原油、環烷基系原油等。又，亦可使用藉由蒸餾等將該等純化而成之純化油。 Examples of the mineral oil include a paraffin-based crude oil, an intermediate-based crude oil, and a cycloalkyl-based crude oil. Further, a purified oil obtained by purifying the same by distillation or the like can also be used.

作為合成基礎油，例如可列舉：聚-α-烯烴(聚丁烯、聚丙烯、碳數8~14之α-烯烴低聚物等)、本發明之四酯以外之脂肪族酯(脂肪酸單酯、多元醇之脂肪酸酯、脂肪族多元酸酯等)、芳香族酯(芳香族單酯、多元醇之芳香族酯、芳香族多元酸酯等)、聚烷二醇、聚乙烯醚、聚苯醚、烷基苯、碳酸酯、合成環烷等。 Examples of the synthetic base oil include poly-α-olefin (polybutene, polypropylene, α-olefin oligomer having 8 to 14 carbon atoms), and aliphatic esters other than the tetraester of the present invention (fatty acid single). An ester, a fatty acid ester of a polyhydric alcohol, an aliphatic polybasic acid ester, or the like, an aromatic ester (an aromatic monoester, an aromatic ester of a polyhydric alcohol, an aromatic polybasic acid ester, etc.), a polyalkylene glycol, a polyvinyl ether, Polyphenylene ether, alkylbenzene, carbonate, synthetic cycloalkane, and the like.

又，本發明之季戊四醇之四酯溶解苯并***等金屬減活 劑、聚矽氧系消泡劑等潤滑油用添加劑之能力優異。該潤滑油用添加劑例如係為了延長潤滑油、使用潤滑油之機器等之壽命而溶解於潤滑油中使用。該潤滑油用添加劑通常對於季戊四醇酯之溶解性較低(日本專利特開平10-259394號公報)。又，苯并***對於礦物油及/或合成油之溶解度較低(日本專利特開昭59-189195號公報)。然而，例如作為本發明之季戊四醇之四酯的四酯4(下述實施例4)及四酯10(下述實施例10)中的苯并***之溶解度(25℃)為0.031 g/g及0.024 g/g，於任一季戊四醇之四酯中均表現出苯并***之較高之溶解度。本發明之季戊四醇之四酯於溶解有苯并***時具有優異之低溫流動性、優異之耐磨損性。 Further, the tetraester of pentaerythritol of the present invention dissolves metal deactivation such as benzotriazole It is excellent in the ability of additives for lubricating oils such as agents and polyfluorinated defoamers. The lubricating oil additive is used, for example, in a lubricating oil for extending the life of a lubricating oil or a lubricating oil machine. The lubricating oil additive is generally low in solubility to pentaerythritol ester (Japanese Patent Laid-Open No. Hei 10-259394). Further, benzotriazole has a low solubility in mineral oil and/or synthetic oil (Japanese Patent Laid-Open Publication No. SHO 59-189195). However, for example, the solubility (25 ° C) of the benzotriazole in the tetraester 4 (the following Example 4) and the tetraester 10 (the following Example 10) as the tetraester of pentaerythritol of the present invention is 0.031 g/g. And 0.024 g / g, in the tetraester of any pentaerythritol, showed a higher solubility of benzotriazole. The tetraester of pentaerythritol of the present invention has excellent low-temperature fluidity and excellent abrasion resistance when benzotriazole is dissolved.

[實施例] [Examples]

以下，藉由實施例、比較例及試驗例進一步具體說明本發明，但並不限定於以下實施例。 Hereinafter, the present invention will be specifically described by way of Examples, Comparative Examples and Test Examples, but is not limited to the following Examples.

核磁共振波譜(nuclear magnetic resonance spectrum)係藉由以下測定裝置、測定方法測定。 The nuclear magnetic resonance spectrum is measured by the following measuring apparatus and measuring method.

測定裝置：日本電子公司製造GSX-400(400 MHz) Measuring device: GSX-400 (400 MHz) manufactured by JEOL

測定方法：1H-NMR、標準物(四甲基矽烷)、溶劑(CDCl3) Determination method: 1 H-NMR, standard (tetramethyl decane), solvent (CDCl 3 )

對以下實施例1~12中所製造之季戊四醇之四酯分別測定核磁共振波譜，藉由下式算出季戊四醇之四酯中的異丁酸、3,5,5-三甲基己酸及碳數4~7之直鏈脂肪族單羧酸之莫耳比。 The nuclear magnetic resonance spectrum of each of the pentaerythritol tetraesters produced in the following Examples 1 to 12 was measured, and isobutyric acid, 3,5,5-trimethylhexanoic acid and carbon number in the tetraester of pentaerythritol were calculated by the following formula. 4 to 7 linear aliphatic monocarboxylic acid molar ratio.

異丁酸/3,5,5-三甲基己酸/碳數4~7之直鏈脂肪族單羧酸=波峰X之積分值/波峰Y之積分值/(波峰Z之積分值/2) Isobutyric acid/3,5,5-trimethylhexanoic acid/linear aliphatic monocarboxylic acid having a carbon number of 4 to 7 = integral value of peak X / integral value of peak Y / (integral value of peak Z / 2 )

此處，波峰X相當於異丁酸中之次甲基上的氫原子之波峰，波峰Y相當於3,5,5-三甲基己酸中之次甲基上的氫原子，波峰Z相當於碳數4~7之直鏈脂肪族單羧酸中之羰基之α位之亞甲基上的氫原子之波峰。 Here, the peak X corresponds to the peak of the hydrogen atom on the methine group in the isobutyric acid, and the peak Y corresponds to the hydrogen atom on the methine group in the 3,5,5-trimethylhexanoic acid, and the peak Z is equivalent A peak of a hydrogen atom on the methylene group at the α position of the carbonyl group in the linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms.

對以下比較例1中所製造之季戊四醇之酯測定核磁共振波譜，藉由下式算出季戊四醇之酯中之異丁酸、3,5,5-三甲基己酸及己二酸之莫耳比。 The nuclear magnetic resonance spectrum of the ester of pentaerythritol produced in the following Comparative Example 1 was measured, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and adipic acid in the ester of pentaerythritol was calculated by the following formula. .

異丁酸/3,5,5-三甲基己酸/己二酸=波峰X之積分值/波峰Y之積分值/(波峰W之積分值/4) Isobutyric acid / 3,5,5-trimethylhexanoic acid / adipic acid = integral value of peak X / integral value of peak Y / (integral value of peak W / 4)

此處，波峰X及波峰Y與上述為相同含意，波峰W相當於己二酸中之羰基之α位之亞甲基上的氫原子之波峰。 Here, the peak X and the peak Y have the same meaning as described above, and the peak W corresponds to the peak of the hydrogen atom on the methylene group of the α position of the carbonyl group in the adipic acid.

[實施例1] [Example 1]

[異丁酸、3,5,5-三甲基己酸及丁酸之莫耳比(異丁酸/3,5,5-三甲基己酸/丁酸比)為71/29/33之季戊四醇之四酯(四酯1)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio) is 71/29/33 Manufacture of tetraester of pentaerythritol (tetraester 1)]

作為吸附劑，使用協和化學工業公司製造Kyowaad 500。 As the adsorbent, Kyowaad 500 was manufactured using Kyowa Chemical Industry Co., Ltd.

作為活性碳，使用Japan Enviro Chemicals公司製造白鷺P。 As the activated carbon, Egret P was manufactured using Japan Enviro Chemicals Co., Ltd.

於附有丁史塔克分水器之反應器中添加季戊四醇327 g(2.4莫耳，Koei Perstorp公司製造)、異丁酸650 g(7.4莫耳，東京化成公司製造)、3,5,5-三甲基己酸365 g(2.3莫耳，協和醱酵化學公司製造)、及丁酸162 g(1.8莫耳，和光純藥公司製造)，一面攪拌混合物一面於室溫下進行30 分鐘氮氣發泡，藉此使混合物脫氣。 Pentaerythritol 327 g (2.4 mol, manufactured by Koei Perstorp Co., Ltd.), isobutyric acid 650 g (7.4 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 3, 5, 5 were added to a reactor equipped with a DyStark water separator. - 365 g of trimethylhexanoic acid (2.3 mol, manufactured by Kyowa Essence Chemical Co., Ltd.), and 162 g of butyric acid (1.8 mol, manufactured by Wako Pure Chemical Industries, Ltd.), while stirring the mixture while stirring at room temperature 30 Nitrogen foaming was carried out for a minute to thereby degas the mixture.

繼而，一面進行氮氣發泡一面將混合物於138~230℃下攪拌30小時。反應後，將反應產物於0.7 kPa之減壓下、於218℃下攪拌1小時，藉此將反應產物中之未反應之羧酸蒸餾去除。以含有相對於該反應產物之酸值而為2倍莫耳之氫氧化鈉的鹼性水溶液400 mL於85℃下將反應產物清洗1小時。繼而，於以400 mL於88℃下用1小時將反應產物清洗3次。繼而，一面進行氮氣發泡一面將反應產物於1.1 kPa之減壓下、於106℃下攪拌1小時，藉此乾燥反應產物。 Then, while stirring nitrogen gas, the mixture was stirred at 138 to 230 ° C for 30 hours. After the reaction, the reaction product was stirred at 218 ° C for 1 hour under reduced pressure of 0.7 kPa, whereby the unreacted carboxylic acid in the reaction product was distilled off. The reaction product was washed with 400 mL of an aqueous alkaline solution containing 2 mol of sodium hydroxide relative to the acid value of the reaction product at 85 ° C for 1 hour. Then, the reaction product was washed 3 times with 400 mL at 88 ° C for 1 hour. Then, while the nitrogen gas was bubbled, the reaction product was stirred at 106 ° C for 1 hour under a reduced pressure of 1.1 kPa, whereby the reaction product was dried.

於反應產物中添加吸附劑5.0 g(相當於反應產物之重量0.5%)及活性碳9.9 g(相當於反應產物之重量1.0%)，一面進行氮氣發泡一面將反應產物於1.1 kPa之減壓下、於104℃下攪拌2小時後，使用過濾助劑進行過濾，藉此獲得822 g之四酯1。 5.0 g of the 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) were added to the reaction product, and the reaction product was depressurized at 1.1 kPa while nitrogen gas was bubbled. After stirring at 104 ° C for 2 hours, filtration was carried out using a filter aid, whereby 822 g of the tetraester 1 was obtained.

[實施例2] [Embodiment 2]

[異丁酸、3,5,5-三甲基己酸及丁酸之莫耳比(異丁酸/3,5,5-三甲基己酸/丁酸比)為62/38/57之季戊四醇之四酯(四酯2)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (isobutyric acid/3,5,5-trimethylhexanoic acid/butyric acid ratio) is 62/38/57 Manufacture of tetraester of pentaerythritol (tetraester 2)]

將季戊四醇、異丁酸、3,5,5-三甲基己酸及丁酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/丁酸比)設定為1/1.80/1.20/1.80，除此以外，以與實施例1相同之方式進行操作而獲得四酯2。 The molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio The tetraester 2 was obtained in the same manner as in Example 1 except that it was set to 1/1.80/1.20/1.80.

[實施例3] [Example 3]

[異丁酸、3,5,5-三甲基己酸及丁酸之莫耳比(異丁酸/3,5,5-三甲基己酸/丁酸比)為34/66/95之季戊四醇之四酯(四酯3)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio) is 34/66/95 Manufacture of tetraester of pentaerythritol (tetraester 3)]

將季戊四醇、異丁酸、3,5,5-三甲基己酸及丁酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/丁酸比)設定為1/0.72/1.68/2.40，除此以外，以與實施例1相同之方式進行操作而獲得四酯3。 The molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio The tetraester 3 was obtained in the same manner as in Example 1 except that it was set to 1/0.72/1.68/2.40.

[實施例4] [Example 4]

[異丁酸、3,5,5-三甲基己酸及丁酸之莫耳比(異丁酸/3,5,5-三甲基己酸/丁酸比)為34/66/41之季戊四醇之四酯(四酯4)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio) is 34/66/41 Manufacture of tetraester of pentaerythritol (tetraester 4)]

將季戊四醇、異丁酸、3,5,5-三甲基己酸及丁酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/丁酸比)設定為1/1.20/2.00/1.60，除此以外，以與實施例1相同之方式進行操作而獲得四酯4。 The molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio The tetraester 4 was obtained in the same manner as in Example 1 except that it was set to 1/1.20/2.00/1.60.

[實施例5] [Example 5]

[異丁酸、3,5,5-三甲基己酸及丁酸之莫耳比(異丁酸/3,5,5-三甲基己酸/丁酸比)為24/76/42之季戊四醇之四酯(四酯5)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio) is 24/76/42 Manufacture of tetraester of pentaerythritol (tetraester 5)]

將季戊四醇、異丁酸、3,5,5-三甲基己酸及丁酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/丁酸比)設定為1/0.90/3.00/0.90，除此以外，以與實施例1相同之方式進行操作而獲得四酯5。 The molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (pentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio The tetraester 5 was obtained in the same manner as in Example 1 except that it was set to 1/0.90/3.00/0.90.

[實施例6] [Embodiment 6]

[異丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(異丁酸/3,5,5-三甲基己酸/戊酸比)為30/70/259之季戊四醇之四酯(四酯6)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 30/70/259 Manufacture of tetraester of pentaerythritol (tetraester 6)]

使用戊酸代替丁酸，並將季戊四醇、異丁酸、3,5,5-三甲基己酸及戊酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/戊酸比)設定為1/0.38/0.96/3.46，除此以外，以與實施例1相同之方式進行操作而獲得四酯6。 Use valeric acid instead of butyric acid, and use the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / isobutyric acid / 3,5,5-three The tetraester 6 was obtained in the same manner as in Example 1 except that the methylhexanoic acid/pentanoic acid ratio was set to 1/0.38/0.96/3.46.

[實施例7] [Embodiment 7]

[異丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(異丁酸/3,5,5-三甲基己酸/戊酸比)為69/31/74之季戊四醇之四酯(四酯7)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 69/31/74 Manufacture of tetraester of pentaerythritol (tetraester 7)]

使用戊酸代替丁酸，並將季戊四醇、異丁酸、3,5,5-三甲基己酸及戊酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/戊酸比)設定為1/1.92/0.96/1.92，除此以外，以與實施例1相同之方式進行操作而獲得四酯7。 Use valeric acid instead of butyric acid, and use the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / isobutyric acid / 3,5,5-three The tetraester 7 was obtained in the same manner as in Example 1 except that the methylhexanoic acid/pentanoic acid ratio was set to 1/1.92/0.96/1.92.

[實施例8] [Embodiment 8]

[異丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(異丁酸/3,5,5-三甲基己酸/戊酸比)為32/68/104之季戊四醇之四酯(四酯8)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 32/68/104 Manufacture of tetraester of pentaerythritol (tetraester 8)]

使用戊酸代替丁酸，並將季戊四醇、異丁酸、3,5,5-三甲基己酸及戊酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/戊酸比)設定為1/0.72/1.68/2.40，除此以外，以與實施例1相同之方式進行操作而獲得四酯8。 Use valeric acid instead of butyric acid, and use the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / isobutyric acid / 3,5,5-three The tetraester 8 was obtained in the same manner as in Example 1 except that the methylhexanoic acid/pentanoic acid ratio was set to 1/0.72/1.68/2.40.

[實施例9] [Embodiment 9]

[異丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(異丁酸/3,5,5-三甲基己酸/戊酸比)為35/65/42之季戊四醇之四酯(四酯9)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 35/65/42 Manufacture of tetraester of pentaerythritol (tetraester 9)]

使用戊酸代替丁酸，並將季戊四醇、異丁酸、3,5,5-三甲基己酸及戊酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/戊酸比)設定為1/1.20/2.00/1.60，除此以外，以與實施例1相同之方式進行操作而獲得四酯9。 Use valeric acid instead of butyric acid, and use the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / isobutyric acid / 3,5,5-three The tetraester 9 was obtained in the same manner as in Example 1 except that the methylhexanoic acid/pentanoic acid ratio was set to 1/1.20/2.00/1.60.

[實施例10] [Embodiment 10]

[異丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(異丁酸/3,5,5-三甲基己酸/戊酸比)為40/60/11之季戊四醇之四酯(四酯10)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 40/60/11 Manufacture of tetraester of pentaerythritol (tetraester 10)]

使用戊酸代替丁酸，並將季戊四醇、異丁酸、3,5,5-三甲基己酸及戊酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/戊酸比)設定為1/1.73/2.59/0.48，除此以外，以與實施例1相同之方式進行操作而獲得四酯10。 Use valeric acid instead of butyric acid, and use the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / isobutyric acid / 3,5,5-three The tetraester 10 was obtained in the same manner as in Example 1 except that the methylhexanoic acid/pentanoic acid ratio was set to 1/1.73/2.59/0.48.

[實施例11] [Example 11]

[異丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(異丁酸/3,5,5-三甲基己酸/戊酸比)為26/74/22之季戊四醇之四酯(四酯11)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 26/74/22 Manufacture of tetraester of pentaerythritol (tetraester 11)]

使用戊酸代替丁酸，並將季戊四醇、異丁酸、3,5,5-三甲基己酸及戊酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/戊酸比)設定為1/0.90/3.00/0.90，除此以外，以與實施例1相同之方式進行操作而獲得四酯11。 Use valeric acid instead of butyric acid, and use the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / isobutyric acid / 3,5,5-three The tetraester 11 was obtained in the same manner as in Example 1 except that the methylhexanoic acid/pentanoic acid ratio was set to 1/0.90/3.00/0.90.

[實施例12] [Embodiment 12]

[異丁酸、3,5,5-三甲基己酸及庚酸之莫耳比(異丁酸/3,5,5-三甲基己酸/庚酸比)為65/35/72之季戊四醇之四酯(四酯12)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and heptanoic acid (isobutyric acid/3,5,5-trimethylhexanoic acid/heptanoic acid ratio) is 65/35/72 Manufacture of tetraester of pentaerythritol (tetraester 12)]

使用庚酸代替丁酸，並將季戊四醇、異丁酸、3,5,5-三甲基己酸及庚酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/庚酸比)設定為1/1.92/0.96/1.92，除此以外，以與實施例1相同之方式進行操作而獲得四酯12。 Use heptanoic acid instead of butyric acid, and use molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and heptanoic acid (pentaerythritol / isobutyric acid / 3, 5, 5 - three The tetraester 12 was obtained in the same manner as in Example 1 except that the methylhexanoic acid/heptanoic acid ratio was set to 1/1.92/0.96/1.92.

[比較例1] [Comparative Example 1]

[異丁酸、3,5,5-三甲基己酸、及己二酸之莫耳比(異丁酸/3,5,5-三甲基己酸/己二酸比)為69/31/7之季戊四醇之酯(酯A)之製造] [Mole ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid, and adipic acid (isobutyric acid / 3,5,5-trimethylhexanoic acid / adipic acid ratio) is 69/ Production of 31/7 pentaerythritol ester (ester A)

使用己二酸代替丁酸，並將季戊四醇、異丁酸、3,5,5-三甲基己酸及己二酸之使用量之莫耳比(季戊四醇/異丁酸/3,5,5-三甲基己酸/己二酸比)設定為1/2.50/1.00/0.25，除此以外，以與實施例1相同之方式進行操作而獲得酯A。 Use adipic acid instead of butyric acid, and use the molar ratio of pentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and adipic acid (pentaerythritol / isobutyric acid / 3, 5, 5 The ester A was obtained in the same manner as in Example 1 except that the ratio of -trimethylhexanoic acid / adipic acid was set to 1/2.50 / 1.00 / 0.25.

(試驗例1)流動點之測定 (Test Example 1) Measurement of the flow point

使用自動流動點測定器RPC-01CML(離合(RIGO)公司製造)，依據JIS K2269-1987之方法測定四酯1~12及酯A之流動點。將結果示於表1~3。 The flow point of the tetraesters 1 to 12 and the ester A was measured in accordance with the method of JIS K2269-1987 using an automatic flow point measuring device RPC-01CML (manufactured by RIGO). The results are shown in Tables 1 to 3.

(試驗例2)動黏度之測定 (Test Example 2) Measurement of dynamic viscosity

使用坎農-芬斯克黏度計(Cannon-Fenske viscometer)，依據JIS K2283：2000之方法測定四酯1~12及酯A的40℃及100℃下之動黏度。又，依據相同方法算出黏度指數。將結果示於表1~3。 The dynamic viscosity at 40 ° C and 100 ° C of tetraesters 1 to 12 and ester A was measured according to the method of JIS K2283:2000 using a Cannon-Fenske viscometer. Further, the viscosity index was calculated in accordance with the same method. The results are shown in Tables 1 to 3.

(試驗例3)二層分離溫度之測定 (Test Example 3) Determination of the separation temperature of the two layers

依據JIS K2211：2009之方法測定四酯1~4及6~8之二層分離溫度。將四酯1~4及6~8各0.4 g與二氟甲烷冷媒3.6 g封入至耐壓玻璃管中，將混合物自30℃起以每分鐘0.5℃之速度冷卻，將混合物二層分離或白濁之溫度作為二層分離溫度。將結果示於以下。 The separation temperature of the two layers of tetraesters 1 to 4 and 6 to 8 was measured according to the method of JIS K2211:2009. 0.4 g of tetraesters 1~4 and 6~8 and 3.6 g of difluoromethane refrigerant were sealed into a pressure-resistant glass tube, and the mixture was cooled at a rate of 0.5 ° C per minute from 30 ° C. The mixture was separated or white turbid. The temperature is taken as the two-layer separation temperature. The results are shown below.

(試驗例4)-20℃下之固化、析出物有無之確認(低溫特性之評價) (Test Example 4) Confirmation of solidification at -20 ° C and presence or absence of precipitates (evaluation of low temperature characteristics)

將四酯2~12各1.0 g加入至玻璃容器中，於設定為-20℃之恆溫器中靜置96小時。目測確認靜置後之固化、析出物有無。將結果示於以下。 1.0 g of each of the tetraesters 2 to 12 was placed in a glass vessel, and allowed to stand in a thermostat set at -20 ° C for 96 hours. The solidification after standing and the presence or absence of precipitates were visually confirmed. The results are shown below.

(試驗例5)RBOT(Rotating Bomb Oxidation Test，旋轉氧彈試驗)壽命之測定(氧化/水解穩定性、氧化穩定性之評價) (Test Example 5) Measurement of the life of RBOT (Rotating Bomb Oxidation Test) (evaluation of oxidation/hydrolysis stability and oxidation stability) 「條件1」 "Condition 1"

使用旋轉彈式氧化穩定度試驗器RBOT-02(離合公司製造)，依據JIS K2514-1996之方法進行氧化穩定度試驗。將四酯1~12及酯A各49.50 g、4,4'-亞甲基雙(2,6-二-第三丁基苯酚)(東京化成工業公司製造)0.25 g、IRGANOX L57(汽巴精化公司製造)0.25 g、水5 mL、及經紙銼刀#400磨擦之電解銅線(直徑1.6 mm，長度3 m)加入至耐壓容器中。繼而，向該耐壓容器中壓入氧氣直至620 kPa為止，將該耐壓容器放入至150℃之恆溫槽中，以每分鐘100轉進行旋轉。測定自該耐壓容器之壓力達到最高時起直至下降175 kPa之壓力為止所需之時間(RBOT壽命)。將結果示於表1~3。 The oxidation stability test was carried out in accordance with the method of JIS K2514-1996 using a rotary elastic oxidation stability tester RBOT-02 (manufactured by Seiko Co., Ltd.). 49.50 g of tetraester 1~12 and ester A, 4,4'-methylenebis(2,6-di-t-butylphenol) (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.25 g, IRGANOX L57 (Ciba Electrolytic copper wire (diameter 1.6 mm, length 3 m), which was manufactured by Jinghua Co., Ltd., 0.25 g, water 5 mL, and paper trowel #400 was added to a pressure-resistant container. Then, oxygen gas was injected into the pressure-resistant container up to 620 kPa, and the pressure-resistant container was placed in a thermostatic chamber at 150 ° C and rotated at 100 rpm. Measured from the time when the pressure of the pressure vessel reached the highest until it dropped 175 Time required for kPa pressure (RBOT life). The results are shown in Tables 1 to 3.

於表1~3中表示RBOT壽命越長則四酯之氧化/水解穩定性越優異。 Tables 1-3 show that the longer the RBOT life, the more excellent the oxidation/hydrolysis stability of the tetraester.

「條件2」 "Condition 2"

不將4,4'-亞甲基雙(2,6-二-第三丁基苯酚)、IRGANOX L57及水加入至耐壓容器中，除此以外，進行與條件1相同之操作，對於四酯3及8，測定自該耐壓容器之壓力達到最高時起直至下降175 kPa之壓力為止所需之時間(RBOT壽命)。此處表示RBOT壽命越長則四酯之氧化穩定性越優異。 The same operation as in Condition 1 was carried out except that 4,4'-methylenebis(2,6-di-t-butylphenol), IRGANOX L57 and water were not added to the pressure vessel. The esters 3 and 8 were measured for the time (RBOT life) required from the time when the pressure of the pressure-resistant container reached the maximum until the pressure of 175 kPa was lowered. Here, the longer the RBOT life is, the more excellent the oxidation stability of the tetraester is.

(試驗例6)重量減少溫度之測定(熱穩定性之評價) (Test Example 6) Measurement of weight reduction temperature (evaluation of thermal stability)

使用熱重量/示差熱量計Tg-DTA6200(Seiko Instruments公司製造)，於以下之條件下測定四酯5、6及9~12之5%重量減少溫度。將結果示於表4。 The 5% weight loss temperature of the tetraesters 5, 6, and 9 to 12 was measured under the following conditions using a thermogravimetric/differential calorimeter Tg-DTA6200 (manufactured by Seiko Instruments Co., Ltd.). The results are shown in Table 4.

測定溫度：40~420℃，升溫速度：10℃/分鐘，環境：氮氣流通(300 mL/分鐘)，試樣容器：鋁製15 μl(開放)，樣品量：3 mg Measurement temperature: 40~420°C, heating rate: 10°C/min, environment: nitrogen flow (300 mL/min), sample container: aluminum 15 μl (open), sample amount: 3 mg

根據表1~3可知，四酯1~12係100℃下之動黏度為4.6~8.2 mm2/秒，且黏度指數為89以上，具有流動點為-42.5℃以下之優異之低溫流動性，具有條件1下之RBOT壽命為756分鐘以上之優異之氧化/水解穩定性。 According to Tables 1-3, the tetraester 1~12 has an kinetic viscosity of 4.6 to 8.2 mm 2 /sec at 100 ° C and a viscosity index of 89 or more, and has excellent low temperature fluidity of a flow point of -42.5 ° C or less. It has excellent oxidative/hydrolytical stability with an RBOT lifetime of 756 minutes or more under Condition 1.

根據表4，四酯5、6及9~12於Tg-DTA之測定中，5%重量減少溫度為221.8℃以上。可知本發明之四酯具有優異之熱穩定性。 According to Table 4, in the measurement of Tg-DTA of tetraesters 5, 6, and 9 to 12, the 5% weight loss temperature was 221.8 ° C or more. It is understood that the tetraester of the present invention has excellent thermal stability.

於試驗例3中，四酯1~4及6~8係二層分離溫度為-32℃以下，其中，四酯1~3及7為-50℃以下。可知本發明之四酯具有對於二氟甲烷冷媒之優異之相溶性。 In Test Example 3, the separation temperature of the tetraesters 1 to 4 and 6 to 8 was -32 ° C or lower, and the tetraesters 1 to 3 and 7 were -50 ° C or lower. It is understood that the tetraester of the present invention has excellent compatibility with a difluoromethane refrigerant.

於試驗例4中，四酯2~12未固化，且亦未確認到析出物。可知四酯2~12即便於在低溫區域中長期保管或使用之情形時，亦可較佳地使用。 In Test Example 4, the tetraester 2 to 12 was not cured, and no precipitate was observed. It is understood that the tetraesters 2 to 12 can be preferably used even when they are stored or used for a long period of time in a low temperature region.

於試驗例5之「條件2」下，四酯3係RBOT壽命為217分鐘，四酯8係RBOT壽命為247分鐘。可知本發明之四酯具有較高之氧化穩定性。 Under the "Condition 2" of Test Example 5, the tetraester 3 system RBOT lifetime was 217 minutes, and the tetraester 8 system RBOT lifetime was 247 minutes. It is known that the tetraester of the present invention has high oxidative stability.

[產業上之可利用性] [Industrial availability]

藉由本發明，可提供一種平衡良好地具有優異之低溫流動性及優異之穩定性等的用於冷凍機油等之季戊四醇之四酯。 According to the present invention, it is possible to provide a tetraester of pentaerythritol for use in a refrigerating machine oil or the like which has excellent low-temperature fluidity and excellent stability.

Claims (5)

一種季戊四醇之四酯，其係季戊四醇與羧酸之混合酯，且上述羧酸含有異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸。 a tetraester of pentaerythritol, which is a mixed ester of pentaerythritol and a carboxylic acid, and the above carboxylic acid contains isobutyric acid, 3,5,5-trimethylhexanoic acid, and a linear aliphatic monocarboxylic acid having a carbon number of 4-7. acid. 如請求項1之季戊四醇之四酯，其中上述羧酸包含異丁酸、3,5,5-三甲基己酸、及碳數4~7之直鏈脂肪族單羧酸。 The tetraester of pentaerythritol of claim 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. 如請求項1或2之季戊四醇之四酯，其中上述碳數4~7之直鏈脂肪族單羧酸為丁酸。 The tetraester of pentaerythritol of claim 1 or 2, wherein the linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms is butyric acid. 如請求項1或2之季戊四醇之四酯，其中上述碳數4~7之直鏈脂肪族單羧酸為戊酸。 The tetraester of pentaerythritol of claim 1 or 2, wherein the linear aliphatic monocarboxylic acid having 4 to 7 carbon atoms is valeric acid. 如請求項1或2之季戊四醇之四酯，其中100℃之動黏度在4.6~8.2 mm2/秒之範圍內。 A tetraester of pentaerythritol as claimed in claim 1 or 2, wherein the dynamic viscosity at 100 ° C is in the range of 4.6 to 8.2 mm 2 /sec.
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Family Cites Families (16)

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US5698502A (en) * 1996-09-11 1997-12-16 Exxon Chemical Patents Inc Polyol ester compositions with unconverted hydroxyl groups for use as lubricant base stocks
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US8518295B2 (en) * 2009-10-07 2013-08-27 Chemtura Corporation Lubricants for refrigeration systems
KR101705935B1 (en) * 2010-08-24 2017-02-10 케이에이치 네오켐 가부시키가이샤 Pentaerythritol tetraester
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