TW201305323A - Tetraester of pentaerythritol - Google Patents

Tetraester of pentaerythritol Download PDF

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TW201305323A
TW201305323A TW101105877A TW101105877A TW201305323A TW 201305323 A TW201305323 A TW 201305323A TW 101105877 A TW101105877 A TW 101105877A TW 101105877 A TW101105877 A TW 101105877A TW 201305323 A TW201305323 A TW 201305323A
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acid
tetraester
pentaerythritol
trimethylhexanoic
butyric
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TWI600754B (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
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/101—Containing Hydrofluorocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

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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

Provided is a tetraester of pentaerythritol that is a mixed ester of pentaerythritol and carboxylic acid, the carboxylic acid containing butyric acid, 3,5,5-trimethylhexanoic acid, and aliphatic carboxylic acid having 5-7 carbon atoms, to be used in refrigerant oil and the like having excellent compatibility and the like with difluoromethane refrigerant.

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.

近年來，使用臭氧破壞係數為零、全球暖化係數(GWP，global warming potential)更低之氫氟碳(HFC，hydrofluorocarbon)作為冷凍機用之冷媒。二氟甲烷冷媒(HFC-32)係GWP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為較佳之冷媒(非專利文獻1)。 In recent years, hydrofluorocarbon (HFC) having a zero ozone destruction coefficient and a lower global warming potential (GWP) has been used as a refrigerant for a refrigerator. The difluoromethane refrigerant (HFC-32) is a low-GWP refrigerant [R-410A (mixture of difluoromethane and pentafluoroethane), R-407C (difluoromethane, pentafluoroethane and 1, Approximately 1/3 to 1/4 of a mixture of 1,1,2-tetrafluoroethane, etc., and a coefficient of performance (COP, Coefficient of Performance) is also increased by about 5 with respect to R-410A, R-407C, and the like. Since it is ~13%, it is a refrigerant which is preferable from the viewpoint of energy saving (Non-Patent Document 1).

專利文獻1中揭示有用於二氟甲烷冷媒用冷凍機油的季戊四醇與脂肪酸之酯，但該酯之對於二氟甲烷冷媒之相溶性等不充分。 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 a difluoromethane refrigerant is insufficient.

[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2002-129177號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-129177

[非專利文獻] [Non-patent literature]

[非專利文獻1]「潤滑經濟」，2004年6月號(No.460)，p.17 [Non-Patent Document 1] "Lubrication Economy", June 2004 (No. 460), p. 17

本發明之目的在於提供一種具有對於二氟甲烷冷媒之優異之相溶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 compatibility with a difluoromethane refrigerant.

本發明係提供以下[1]~[9]。 The present invention provides the following [1] to [9].

[1]一種季戊四醇之四酯，其係季戊四醇與羧酸之混合酯，且上述羧酸含有丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族羧酸。 [1] A tetraester of pentaerythritol which is a mixed ester of pentaerythritol and a carboxylic acid, and the above carboxylic acid contains butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms. .

[2]如[1]之季戊四醇之四酯，其中上述羧酸包含丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族羧酸。 [2] The tetraester of pentaerythritol of [1], wherein the carboxylic acid comprises butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms.

[3]如[1]或[2]之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為碳數5或6之分支脂肪族羧酸。 [3] The tetraester of pentaerythritol of [1] or [2], wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is a branched aliphatic carboxylic acid having 5 or 6 carbon atoms.

[4]如[1]至[3]中任一項之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為2-甲基丁酸。 [4] The tetraester of pentaerythritol according to any one of [1] to [3] wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is 2-methylbutyric acid.

[5]如[1]至[3]中任一項之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為3-甲基丁酸。 [5] The tetraester of pentaerythritol according to any one of [1] to [3] wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is 3-methylbutyric acid.

[6]如[1]至[3]中任一項之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為2-甲基戊酸。 [6] The tetraester of pentaerythritol according to any one of [1] to [3] wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is 2-methylvaleric acid.

[7]如[1]或[2]之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為碳數5~7之直鏈脂肪族羧酸。 [7] The tetraester of pentaerythritol of [1] or [2], wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is a linear aliphatic carboxylic acid having 5 to 7 carbon atoms.

[8]如[1]、[2]及[7]中任一項之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為戊酸。 [8] The tetraester of pentaerythritol according to any one of [1], [2], and [7], wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is valeric acid.

[9]如[1]至[8]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。 [9] The tetraester of pentaerythritol according to any one of [1] to [8], 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，可提供一種具有對於二氟甲烷冷媒之優異之相溶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 refrigerator oil or the like having excellent compatibility with a difluoromethane refrigerant.

本發明之季戊四醇之四酯係季戊四醇與含有丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族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 butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 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丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族羧酸的季戊四醇之四酯 (i) a tetraester of pentaerythritol constituting a carboxylic acid containing butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms in the same molecule

(ii)同一分子中之構成羧酸含有選自丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族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 a tetraester of pentaerythritol selected from the group consisting of butyric acid, 3,5,5-trimethylhexanoic acid, and a group of aliphatic carboxylic acids having 5 to 7 carbon atoms.

(iii)季戊四醇與含有丁酸之羧酸之四酯 (iii) pentaerythritol and a tetraester of a carboxylic acid containing butyric 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5~7之脂肪族羧酸之羧酸之四酯 (v) tetraester of pentaerythritol and a carboxylic acid containing an aliphatic carboxylic acid having 5 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 (vi) a mixture of two or more tetraesters selected from the group consisting of (i) to (v) above

(其中，構成混合酯之羧酸含有丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族羧酸)。 (The carboxylic acid constituting the mixed ester contains butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms).

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.

於本發明中，藉由使用丁酸、3,5,5-三甲基己酸及碳數5~7之脂肪族羧酸作為羧酸，可提高對於二氟甲烷冷媒之 相溶性，又，可縮小廣泛之溫度範圍內之黏度變化。 In the present invention, by using butyric acid, 3,5,5-trimethylhexanoic acid and an aliphatic carboxylic acid having 5 to 7 carbon atoms as a carboxylic acid, the refrigerant for difluoromethane can be improved. Compatibility, in turn, can reduce viscosity changes over a wide range of temperatures.

構成混合酯之羧酸中亦可含有除了丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族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羧酸；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、異癸酸、異十三酸、異硬脂酸等分支狀脂肪族羧酸等。 The carboxylic acid constituting the mixed ester may further contain a carboxylic acid other than butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms. Examples of the other carboxylic acid include linear aliphatic carboxylic acids such as acetic acid, propionic acid, caprylic acid, capric acid, capric acid, dodecanoic acid, myristic acid, palmitic acid, and octadecanoic acid; 2-methylglycol Acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 2-ethyl-2-methylpentanoic acid, 2-methyloctanoic acid, 2,2-dimethylheptanoic acid, isodecanoic acid, isotactic A branched aliphatic carboxylic acid such as triacid or isostearic acid.

關於上述含有丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族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、對於二氟甲烷冷媒等之相溶性等優異特性之範圍即可。其他羧酸相對於丁酸、3,5,5-三甲基己酸及碳數5~7之脂肪族羧酸之和的莫耳比[其他羧酸/(丁酸、3,5,5-三甲基己酸及碳數5~7之脂肪族羧酸)比]較佳為在0/100~5/100之範圍內。 The content of the other carboxylic acid in the carboxylic acid containing butyric acid, 3,5,5-trimethylhexanoic acid, and the aliphatic carboxylic acid having 5 to 7 carbon atoms is not impaired by the pentaerythritol of the present invention. The range of excellent properties such as the low-temperature fluidity of the tetraester and the compatibility with the difluoromethane refrigerant or the like may be sufficient. Mohr ratio of the sum of other carboxylic acids relative to butyric acid, 3,5,5-trimethylhexanoic acid and aliphatic carboxylic acids having 5 to 7 carbons [other carboxylic acids / (butyric acid, 3, 5, 5) The ratio of -trimethylhexanoic acid and aliphatic carboxylic acid having 5 to 7 carbon atoms 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丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族羧酸者。 In the present invention, it is more preferred that the carboxylic acid constituting the mixed ester is an aliphatic carboxylic acid containing butyric acid, 3,5,5-trimethylhexanoic acid, and a carbon number of 5 to 7.

作為構成本發明之季戊四醇之四酯的碳數5~7之脂肪族羧酸，可列舉碳數5~7之直鏈脂肪族羧酸或碳數5~7之分支脂肪族羧酸。作為碳數5~7之直鏈脂肪族羧酸，具體可列舉戊酸、己酸及庚酸，其中，較佳為戊酸或己酸，更佳為戊酸。作為碳數5~7之分支脂肪族羧酸，可列舉：2-甲基丁酸、3-甲基丁酸、2-甲基丁酸與3-甲基丁酸之混合物、2,2-二甲基丙酸、2-甲基戊酸、2-乙基丁酸、2-甲基己 酸、3-甲基己酸、新庚酸等，其中，較佳為2-甲基丁酸、3-甲基丁酸、2-甲基丁酸與3-甲基丁酸之混合物或2-甲基戊酸，更佳為2-甲基丁酸或3-甲基丁酸。 Examples of the aliphatic carboxylic acid having 5 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention include a linear aliphatic carboxylic acid having 5 to 7 carbon atoms or a branched aliphatic carboxylic acid having 5 to 7 carbon atoms. Specific examples of the linear aliphatic carboxylic acid having 5 to 7 carbon atoms include valeric acid, caproic acid and heptanoic acid. Among them, valeric acid or hexanoic acid is preferred, and valeric acid is more preferred. Examples of the branched aliphatic carboxylic acid having 5 to 7 carbon atoms include 2-methylbutyric acid, 3-methylbutyric acid, a mixture of 2-methylbutyric acid and 3-methylbutyric acid, and 2,2- Dimethylpropionic acid, 2-methylpentanoic acid, 2-ethylbutyric acid, 2-methylhexyl An acid, 3-methylhexanoic acid, neoheptanoic acid or the like, wherein a mixture of 2-methylbutyric acid, 3-methylbutyric acid, 2-methylbutyric acid and 3-methylbutyric acid or 2 is preferred. Methyl valeric acid, more preferably 2-methylbutyric acid or 3-methylbutyric acid.

作為構成本發明之季戊四醇之四酯的碳數5~7之脂肪族羧酸，為選自碳數5~7之脂肪族羧酸中之一種脂肪族羧酸、或選自碳數5~7之脂肪族羧酸中之兩種以上之羧酸之混合物，其中，較佳為選自碳數5~7之脂肪族羧酸中之一種脂肪族羧酸。 The aliphatic carboxylic acid having 5 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention is an aliphatic carboxylic acid selected from aliphatic carboxylic acids having 5 to 7 carbon atoms, or is selected from carbon numbers 5 to 7. A mixture of two or more kinds of carboxylic acids in the aliphatic carboxylic acid, preferably an aliphatic carboxylic acid selected from the group consisting of aliphatic carboxylic acids having 5 to 7 carbon atoms.

作為碳數5~7之脂肪族羧酸，亦可為碳數5或6之分支脂肪族羧酸。作為碳數5或6之分支脂肪族羧酸，可列舉上述碳數5~7之分支脂肪族羧酸中碳數5或6之分支脂肪族羧酸。 The aliphatic carboxylic acid having 5 to 7 carbon atoms may be a branched aliphatic carboxylic acid having 5 or 6 carbon atoms. The branched aliphatic carboxylic acid having a carbon number of 5 or 6 may be a branched aliphatic carboxylic acid having 5 or 6 carbon atoms in the branched aliphatic carboxylic acid having 5 to 7 carbon atoms.

於碳數5~7之脂肪族羧酸為戊酸、己酸、庚酸、2-甲基丁酸、3-甲基丁酸、2-甲基戊酸或2-乙基丁酸時，本發明之季戊四醇之四酯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、低溫特性等優異特性及充分之穩定性。 When the aliphatic carboxylic acid having 5 to 7 carbon atoms is valeric acid, caproic acid, heptanoic acid, 2-methylbutyric acid, 3-methylbutyric acid, 2-methylpentanoic acid or 2-ethylbutyric acid, The tetraester of pentaerythritol of the present invention has excellent balance characteristics such as compatibility, viscosity-temperature characteristics, low-temperature fluidity, and low-temperature characteristics at a wide concentration of a difluoromethane refrigerant, and sufficient stability.

於構成本發明之季戊四醇之四酯之碳數5~7之脂肪族羧酸為戊酸、2-甲基丁酸、3-甲基丁酸或2-甲基戊酸時，戊酸、2-甲基丁酸、3-甲基丁酸或2-甲基戊酸相對於丁酸與3,5,5-三甲基己酸之和的莫耳比[(戊酸、2-甲基丁酸、3-甲基丁酸或2-甲基戊酸)/(丁酸及3,5,5-三甲基己酸)比]較佳為5/100~250/100之範圍。 When the aliphatic carboxylic acid having 5 to 7 carbon atoms constituting the tetraester of pentaerythritol of the present invention is valeric acid, 2-methylbutyric acid, 3-methylbutyric acid or 2-methylpentanoic acid, valeric acid, 2 - molar ratio of methylbutyric acid, 3-methylbutyric acid or 2-methylpentanoic acid to the sum of butyric acid and 3,5,5-trimethylhexanoic acid [(pentanoic acid, 2-methyl group) Butyric acid, 3-methylbutyric acid or 2-methylpentanoic acid) / (butyric acid and 3,5,5-trimethylhexanoic acid) ratio is preferably in the range of 5/100 to 250/100.

於將本發明之四酯用作潤滑油之情形時，若該四酯之黏 度過低，則存在磨損增大而使用潤滑油之機器等之壽命縮短之傾向，另一方面，若該四酯之黏度過高，則存在摩擦係數增大而能量效率降低之傾向，因此該四酯要求適當之黏度範圍。本發明之四酯就適當之黏度範圍之觀點而言，3,5,5-三甲基己酸相對於丁酸、3,5,5-三甲基己酸及碳數5~7之脂肪族羧酸之和的莫耳比[3,5,5-三甲基己酸/(丁酸、3,5,5-三甲基己酸及碳數5~7之脂肪族羧酸)比]較佳為15/100~65/100之範圍。 When the tetraester of the present invention is used as a lubricating oil, if the tetraester is sticky When the degree is too low, there is a tendency that the wear of the lubricating oil is increased, and the life of the machine using the lubricating oil is shortened. On the other hand, if the viscosity of the tetraester is too high, the friction coefficient increases and the energy efficiency tends to decrease. Tetraesters require a suitable viscosity range. The tetraester of the present invention has 3,5,5-trimethylhexanoic acid relative to butyric acid, 3,5,5-trimethylhexanoic acid and a carbon number of 5 to 7 in terms of a suitable viscosity range. The ratio of the molar ratio of the carboxylic acid to the [3,5,5-trimethylhexanoic acid / (butyric acid, 3,5,5-trimethylhexanoic acid and aliphatic carboxylic acid having a carbon number of 5 to 7) ] preferably in the range of 15/100 to 65/100.

本發明之季戊四醇之四酯例如可藉由使季戊四醇、丁酸、3,5,5-三甲基己酸、碳數5~7之脂肪族羧酸、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, made of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid, an aliphatic carboxylic acid having 5 to 7 carbon atoms, and optionally other carboxylic acids in 120~ Manufactured at 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.

較佳為丁酸之使用量、3,5,5-三甲基己酸之使用量、碳數5~7之脂肪族羧酸之使用量、及其他羧酸之使用量之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 butyric acid used, the amount of 3,5,5-trimethylhexanoic acid used, the amount of the aliphatic carboxylic acid having 5 to 7 carbon atoms, and the amount of other carboxylic acid used are relative to The hydroxyl group of pentaerythritol is used to be 1.1 to 1.4 times mole.

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，同時將丁酸及/或碳數5~7之脂肪族羧酸亦自反應混合物中去除。 It is preferred to carry out the reaction while removing water formed by the reaction from the reaction mixture. Sometimes, when the water formed by the reaction is removed from the reaction mixture, butyric acid and/or an aliphatic carboxylic acid having 5 to 7 carbon atoms are also removed from the reaction mixture.

又，由於丁酸、3,5,5-三甲基己酸及碳數5~7之脂肪族羧酸相對於季戊四醇的反應性之差，有時構成所獲得之四酯之丁酸、3,5,5-三甲基己酸及碳數5~7之脂肪族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 butyric acid, 3,5,5-trimethylhexanoic acid and an aliphatic carboxylic acid having 5 to 7 carbon atoms relative to pentaerythritol, it may constitute the butyric acid of the obtained tetraester, 3 The molar ratio of 5,5-trimethylhexanoic acid and the aliphatic carboxylic acid having 5 to 7 carbon atoms 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。又，具有優異之低溫流動性、優異之低溫特性、充分之黏度-溫度特性、優異之潤滑性、充分之穩定性等。 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 difluoromethane refrigerant alone. Further, it has excellent low-temperature fluidity, excellent low-temperature characteristics, sufficient viscosity-temperature characteristics, excellent lubricity, and sufficient stability.

又，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。於將該四酯用於冷凍機油之情形時，例如較佳為相對於冷媒添加10%之該四酯之情形的二層分離溫度為-10℃以 下，更佳為-20℃以下。又，酯對於冷媒之相溶性與該酯之性質有關。 Further, the compatibility with the difluoromethane refrigerant is usually expressed by 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. When the tetraester is used in the case of a refrigerating machine oil, for example, it is preferred to add a 10% of the tetraester to the refrigerant to have a two-layer separation temperature of -10 ° C. Next, more preferably -20 ° C or less. Further, the compatibility of the ester with the refrigerant is related to the nature of the ester.

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。於用於潤滑油等油劑之情形時，黏度指數較佳為80以上，更佳為90以上。 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. Usually, this characteristic is expressed as a viscosity index, and the higher the value, the better the viscosity-temperature characteristic. In the case of using an oil agent such as a lubricating oil, the viscosity index is preferably 80 or more, more preferably 90 or more.

又，於低溫區域中之黏度特性亦被稱為低溫流動性，以流動點或凝固點、成溝點(channel point)等表示。 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，即便在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 refers to the lowest temperature at which the oil flows when the oil agent such as lubricating oil is cooled according to the method of Japanese Industrial Standards (JIS) K2269. When the oil agent having a low flow point is used in a low-temperature environment such as winter or a cold area 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。 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.

對於穩定性，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, for example, thermal stability, oxidative stability, oxidation/hydrolytic stability, shear stability, and the like.

對於潤滑性，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.

將本發明之季戊四醇之四酯用於冷凍機油時的該四酯之100℃下之動黏度較佳為在4.6~8.2 mm2/秒之範圍內，更佳為在5.6~8.2 mm2/秒之範圍內。 The dynamic viscosity at 100 ° C of the tetraester of the pentaerythritol of the present invention when used in a refrigerating machine oil is preferably in the range of 4.6 to 8.2 mm 2 /sec, more preferably 5.6 to 8.2 mm 2 /sec. Within the scope.

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 for motor oil, grease, metal used in engine oil, gear oil, hybrid car or electric vehicle, in addition to refrigeration oil. Parts of detergents, plasticizers, 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 in the refrigerating machine oil 0.001 to 5% by weight.

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)中之苯并***之溶解度(25℃)為0.030 g/g以上，於季戊四醇之四酯中亦表現出苯并***之較高之溶解度。另一方面，四酯A(下述比較例1)中之苯并***之溶解度(25℃)為0.021 g/g。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 is excellent in the ability to dissolve an additive for lubricating oil such as a metal deactivator such as benzotriazole or a polyfluorene-based antifoaming agent. 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) of the tetraester of pentaerythritol of the present invention is 0.030 g/g or more, and is also exhibited in the tetraester of pentaerythritol. Higher solubility of benzotriazole. On the other hand, the solubility (25 ° C) of the benzotriazole in the tetraester A (Comparative Example 1 below) was 0.021. g/g. 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1~9及比較例1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丁酸、3,5,5-三甲基己酸及2-甲基丁酸之莫耳比。 The nuclear magnetic resonance spectrum of each of the tetraesters of pentaerythritol produced in the following Examples 1 to 9 and Comparative Example 1 was measured, and butyric acid and 3,5,5-trimethylhexanoic acid in the tetraester of pentaerythritol were calculated by the following formula. And the molar ratio of 2-methylbutyric acid.

丁酸/3,5,5-三甲基己酸/2-甲基丁酸=(波峰X之積分值/2)/波峰Y之積分值/(波峰Q之積分值/2) Butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid=(integral value of peak X/2)/integral value of peak Y/(integral value of peak Q/2)

此處，波峰X相當於丁酸中之羰基之β位之亞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Q相當於2-甲基丁酸中之羰基之β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 methylene group at the β position of the carbonyl group in the butyric acid, and the peak Y corresponds to the hydrogen atom on the methine group in the 3,5,5-trimethylhexanoic acid. The peak Q corresponds to the peak of a hydrogen atom on the methylene group at the β position of the carbonyl group in 2-methylbutyric acid.

對以下實施例10及11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丁酸、3,5,5-三甲基己酸及3-甲基丁酸之莫耳比。 The nuclear magnetic resonance spectrum of each of the tetraesters of pentaerythritol produced in the following Examples 10 and 11 was measured, and butyric acid, 3,5,5-trimethylhexanoic acid and 3-methyl in the tetraester of pentaerythritol were calculated by the following formula: Moth ratio of butyl butyrate.

丁酸/3,5,5-三甲基己酸/3-甲基丁酸=(波峰X之積分值/2)/(波峰Z之積分值/2)/(波峰R之積分值/2) Butyric acid/3,5,5-trimethylhexanoic acid/3-methylbutyric acid=(integral value of peak X/2)/(integral value of peak Z/2)/(integral value of peak R/2 )

此處，波峰X與上述為相同含意，波峰Z相當於3,5,5-三 甲基己酸中之羰基之γ位之亞甲基上的氫原子之波峰，波峰R相當於3-甲基丁酸中之羰基之α位之亞甲基上的氫原子之波峰。 Here, the peak X has the same meaning as the above, and the peak Z is equivalent to 3, 5, 5 - three. The peak of the hydrogen atom on the methylene group at the γ position of the carbonyl group in methylhexanoic acid, and the peak R corresponds to the peak of the hydrogen atom on the methylene group at the α position of the carbonyl group in the 3-methylbutyric acid.

對以下實施例12~15中所製造之季戊四醇之四酯測定核磁共振波譜，藉由下式算出季戊四醇之四酯中的丁酸、3,5,5-三甲基己酸及戊酸之莫耳比。 The nuclear magnetic resonance spectrum of the tetraester of pentaerythritol produced in the following Examples 12 to 15 was measured, and butyric acid, 3,5,5-trimethylhexanoic acid and valeric acid in the tetraester of pentaerythritol were calculated by the following formula. Ear ratio.

丁酸/3,5,5-三甲基己酸/戊酸=(波峰X之積分值/2)/波峰Y之積分值/(波峰S之積分值/2) Butyric acid / 3,5,5-trimethylhexanoic acid / valeric acid = (integral value of peak X / 2) / integral value of peak Y / (integral value of peak S / 2)

此處，波峰X及波峰Y與上述為相同含意，波峰S相當於戊酸中之羰基之γ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 S corresponds to the peak of the hydrogen atom on the methylene group of the γ position of the carbonyl group in the valeric acid.

對以下實施例16~22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丁酸、3,5,5-三甲基己酸及2-甲基戊酸之莫耳比。 The nuclear magnetic resonance spectrum of the tetraester of pentaerythritol produced in the following Examples 16 to 22 was measured, and butyric acid, 3,5,5-trimethylhexanoic acid and 2-methyl in the tetraester of pentaerythritol were calculated by the following formula: The molar ratio of valeric acid.

丁酸/3,5,5-三甲基己酸/2-甲基戊酸=(波峰X之積分值/2)/波峰Y之積分值/波峰T之積分值 Butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid=(integral value of peak X/2)/integral value of peak Y/integral value of peak T

此處，波峰X及波峰Y與上述為相同含意，波峰T相當於2-甲基戊酸中之次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 T corresponds to the peak of a hydrogen atom on the methine group in 2-methylvaleric acid.

對以下實施例23中所製造之季戊四醇之四酯測定核磁共振波譜，藉由下式算出季戊四醇之四酯中的丁酸、3,5,5-三甲基己酸、及2-乙基丁酸之莫耳比。 The nuclear magnetic resonance spectrum of the tetraester of pentaerythritol produced in the following Example 23 was measured, and butyric acid, 3,5,5-trimethylhexanoic acid, and 2-ethylbutyl group in the tetraester of pentaerythritol were calculated by the following formula: Moth ratio of acid.

丁酸/3,5,5-三甲基己酸/2-乙基丁酸=(波峰X之積分值/2)/波峰Y之積分值/(波峰U之積分值/4) Butyric acid/3,5,5-trimethylhexanoic acid/2-ethylbutyric acid=(integral value of peak X/2)/integral value of peak Y/(integral value of peak U/4)

此處，波峰X及波峰Y與上述為相同含意，波峰U相當於2-乙基丁酸中之羰基之β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 U corresponds to a peak of a hydrogen atom on the methylene group at the β position of the carbonyl group in 2-ethylbutyric acid.

對以下實施例24中所製造之季戊四醇之四酯測定核磁共振波譜，藉由下式算出季戊四醇之四酯中的丁酸、3,5,5-三甲基己酸及己酸之莫耳比。 The nuclear magnetic resonance spectrum of the tetraester of pentaerythritol produced in the following Example 24 was measured, and the molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and caproic acid in the tetraester of pentaerythritol was calculated by the following formula. .

丁酸/3,5,5-三甲基己酸/己酸=(波峰X之積分值/2)/波峰Y之積分值/(波峰V之積分值/4) Butyric acid / 3,5,5-trimethylhexanoic acid / caproic acid = (integral value of peak X / 2) / integral value of peak Y / (integral value of peak V / 4)

此處，波峰X及波峰Y與上述為相同含意，波峰V相當於己酸中之羰基之γ位及δ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 V corresponds to the peak of the γ position of the carbonyl group in the hexanoic acid and the hydrogen atom on the methylene group of the δ position.

對以下實施例25中所製造之季戊四醇之四酯測定核磁共振波譜，藉由下式算出季戊四醇之四酯中之丁酸、3,5,5-三甲基己酸及庚酸之莫耳比。丁酸/3,5,5-三甲基己酸/庚酸=(波峰X之積分值/2)/波峰Y之積分值/(波峰W之積分值/6) The nuclear magnetic resonance spectrum of the tetraester of pentaerythritol produced in the following Example 25 was measured, and the molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and heptanoic acid in the tetraester of pentaerythritol was calculated by the following formula. . Butyric acid/3,5,5-trimethylhexanoic acid/heptanoic acid=(integral value of peak X/2)/integral value of peak Y/(integral value of peak W/6)

此處，波峰X及波峰Y與上述為相同含意，波峰W相當於庚酸中之羰基之γ位、δ位及ε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 γ position of the carbonyl group in the heptanoic acid, the δ position, and the hydrogen atom on the methylene group of the ε position.

[實施例1] [Example 1] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)為80/20/7之季戊四醇之四酯(四酯1)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid ratio) Manufacture of 80/20/7 pentaerythritol tetraester (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325 g(2.4莫耳，Koei Perstorp公司製造)、丁酸727 g(8.3莫耳，東京化成公司製造)、3,5,5-三甲基己酸362 g(2.3莫耳，協和醱酵化學公司製造)、及2-甲基丁酸94 g(0.9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 325 g (2.4 mol, manufactured by Koei Perstorp Co., Ltd.), butyric acid 727 g (8.3 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 3, 5, 5- was added to the reactor with the DyStark water separator. Trimethylhexanoic acid 362 g (2.3 mol, manufactured by Kyowa Chemical Co., Ltd.), and 2-methylbutyric acid 94 g (0.9 m, and light) The product was degassed by stirring nitrogen gas at room temperature for 30 minutes while stirring the mixture.

繼而，一面進行氮氣發泡一面將混合物於151~225℃下攪拌23小時。反應後，將反應產物於0.1 kPa之減壓下、於207℃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倍莫耳之氫氧化鈉之鹼性水溶液400 mL於88℃下將反應產物清洗2小時。繼而，以水400m L於61℃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0.1 kPa之減壓下、於116℃下攪拌2小時，藉此乾燥反應產物。 Then, while stirring nitrogen gas, the mixture was stirred at 151 to 225 ° C for 23 hours. After the reaction, the reaction product was stirred at 207 ° C for 1 hour under reduced pressure of 0.1 kPa, whereby the unreacted carboxylic acid in the reaction product was distilled off. The reaction product was washed at 400 ° C for 2 hours at 400 ° C in an alkaline aqueous solution containing 2 mol of sodium hydroxide relative to the acid value of the reaction product. Then, the reaction product was washed 3 times with water of 400 m L at 61 ° C for 1 hour. Then, while the nitrogen gas was foamed, the reaction product was stirred at 116 ° C for 2 hours under reduced pressure of 0.1 kPa, whereby the reaction product was dried.

於反應產物中添加吸附劑8.0 g(相當於反應產物之重量0.7%)及活性碳5.7 g(相當於反應產物之重量0.5%)，一面進行氮氣發泡一面將反應產物於0.1 kPa之減壓下、於111℃下攪拌2小時後，使用過濾助劑進行過濾，藉此獲得938 g之四酯1。 8.0 g of an adsorbent (corresponding to 0.7% by weight of the reaction product) and 5.7 g of activated carbon (corresponding to 0.5% by weight of the reaction product) were added to the reaction product, and the reaction product was decompressed at 0.1 kPa while nitrogen gas was bubbled. After stirring at 111 ° C for 2 hours, it was filtered using a filter aid, whereby 938 g of the tetraester 1 was obtained.

[實施例2] [Embodiment 2] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)為69/31/59之季戊四醇之四酯(四酯2)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid ratio) Manufacture of 69/31/59 pentaerythritol tetraester (tetraester 2)]

將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)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2。 The molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2 The tetraester 2 was obtained in the same manner as in Example 1 except that the ratio of -methylbutyric acid was changed to 1/1.92/0.96/1.92.

[實施例3] [Example 3] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)為38/62/224之季戊四醇之四酯(四酯3)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid ratio) Manufacture of tetraester (tetraester 3) of pentaerythritol of 38/62/224]

將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)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3。 The molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2 The tetraester 3 was obtained in the same manner as in Example 1 except that the ratio of -methylbutyric acid was changed to 1/0.38/0.96/3.46.

[實施例4] [Example 4] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)為25/75/138之季戊四醇之四酯(四酯4)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid ratio) Manufacture of 25/75/138 pentaerythritol tetraester (tetraester 4)]

將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)設定為1/0.45/1.35/3.00，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, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2 The tetraester 4 was obtained in the same manner as in Example 1 except that the ratio of -methylbutyric acid was changed to 1/0.45/1.35/3.00.

[實施例5] [Example 5] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)為46/54/33之季戊四醇之四酯(四酯5)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid ratio) Manufacture of 46/54/33 pentaerythritol tetraester (tetraester 5)]

將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)設定為1/1.44/1.92/1.44，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, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2 The tetraester 5 was obtained in the same manner as in Example 1 except that the ratio of -methylbutyric acid was set to 1/1.44/1.92/1.44.

[實施例6] [Embodiment 6] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)為32/68/92之季戊四醇之四酯(四酯6)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid ratio) Manufacture of 32/68/92 pentaerythritol tetraester (tetraester 6)]

將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)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6。 The molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2 The tetraester 6 was obtained in the same manner as in Example 1 except that the ratio of -methylbutyric acid was changed to 1/0.72/1.68/2.40.

[實施例7] [Embodiment 7] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)為41/59/8之季戊四醇之四酯(四酯7)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid ratio) Manufacture of tetraester (tetraester 7) of pentaerythritol of 41/59/8]

將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)設定為1/1.62/3.00/0.18，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。 The molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2 The tetraester 7 was obtained in the same manner as in Example 1 except that the ratio of -methylbutyric acid was changed to 1/1.62/3.00/0.18.

[實施例8] [Embodiment 8] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)為25/75/33之季戊四醇之四酯(四酯8)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid ratio) Manufacture of 25/75/33 pentaerythritol tetraester (tetraester 8)]

將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)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8。 The molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2 The tetraester 8 was obtained in the same manner as in Example 1 except that the ratio of -methylbutyric acid was changed to 1/0.90/3.00/0.90.

[實施例9] [Embodiment 9] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)為23/77/54之季戊四醇之四酯(四酯9)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylbutyric acid ratio) Manufacture of 23/77/54 pentaerythritol tetraester (tetraester 9)]

將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)設定為1/0.72/2.40/1.68，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。 The molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2 The tetraester 9 was obtained in the same manner as in Example 1 except that the ratio of -methylbutyric acid was changed to 1/0.72/2.40/1.68.

[實施例10] [Embodiment 10] [丁酸、3,5,5-三甲基己酸及3-甲基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/3-甲基丁酸比)為62/38/37之季戊四醇之四酯(四酯10)之製造] [Merce ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 3-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 3-methylbutyric acid ratio) Manufacture of tetraester (tetraester 10) of pentaerythritol of 62/38/37]

使用3-甲基丁酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及3-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/3-甲基丁酸比)設定為1/2.16/1.20/1.44，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 3-methylbutyric acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 3-methylbutyric acid (pentaerythritol / In the same manner as in Example 1, except that the ratio of butyric acid/3,5,5-trimethylhexanoic acid/3-methylbutyric acid was set to 1/2.16/1.20/1.44, four were obtained in the same manner as in Example 1. Ester 10.

[實施例11] [Example 11] [丁酸、3,5,5-三甲基己酸及3-甲基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/3-甲基丁酸比)為36/64/76之季戊四醇之四酯(四酯11)之製造] [Merce ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 3-methylbutyric acid (butyric acid / 3,5,5-trimethylhexanoic acid / 3-methylbutyric acid ratio) Manufacture of 36/64/76 pentaerythritol tetraester (tetraester 11)]

使用3-甲基丁酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及3-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/3-甲基丁酸比)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11。 Use 3-methylbutyric acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 3-methylbutyric acid (pentaerythritol / Butyric acid / 3,5,5-trimethylhexanoic acid / 3-methylbutyric acid ratio) is set to A tetraester 11 was obtained in the same manner as in Example 1 except that 1/0.72/1.68/2.40 was used.

[實施例12] [Embodiment 12] [丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/戊酸比)為63/37/65之季戊四醇之四酯(四酯12)之製造] [The molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (butyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 63/37/65 pentaerythritol Manufacture of tetraester (tetraester 12)]

使用戊酸代替2-甲基丁酸，並將季戊四醇、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/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12。 Use valeric acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / butyric acid / 3, 5, 5 The tetraester 12 was obtained in the same manner as in Example 1 except that the trimethylhexanoic acid/pentanoic acid ratio was set to 1/1.92/0.96/1.92.

[實施例13] [Example 13] [丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/戊酸比)為56/44/57之季戊四醇之四酯(四酯13)之製造] [The molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (butyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 56/44/57 pentaerythritol Manufacture of tetraester (tetraester 13)]

使用戊酸代替2-甲基丁酸，並將季戊四醇、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/丁酸/3,5,5-三甲基己酸/戊酸比)設定為1/1.63/1.54/1.63，除此以外，以與實施例1相同之方式進行操作而獲得四酯13。 Use valeric acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / butyric acid / 3, 5, 5 The tetraester 13 was obtained in the same manner as in Example 1 except that the trimethylhexanoic acid/pentanoic acid ratio was set to 1/1.63/1.54/1.63.

[實施例14] [Embodiment 14] [丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/戊酸比)為49/51/41之季戊四醇之四酯(四酯14)之製造] [The molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (butyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 49/51/41 of pentaerythritol Manufacture of tetraester (tetraester 14)]

使用戊酸代替2-甲基丁酸，並將季戊四醇、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/丁酸/ 3,5,5-三甲基己酸/戊酸比)設定為1/1.39/2.02/1.39，除此以外，以與實施例1相同之方式進行操作而獲得四酯14。 Use valeric acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / butyric acid / The tetraester 14 was obtained in the same manner as in Example 1 except that the ratio of 3,5,5-trimethylhexanoic acid/pentanoic acid was set to 1/1.39/2.02/1.39.

[實施例15] [Example 15] [丁酸、3,5,5-三甲基己酸及戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/戊酸比)為33/67/32之季戊四醇之四酯(四酯15)之製造] [The molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (butyric acid / 3,5,5-trimethylhexanoic acid / valeric acid ratio) is 33/67/32 pentaerythritol Manufacture of tetraester (tetraester 15)]

使用戊酸代替2-甲基丁酸，並將季戊四醇、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/丁酸/3,5,5-三甲基己酸/戊酸比)設定為1/1.08/2.64/1.08，除此以外，以與實施例1相同之方式進行操作而獲得四酯15。 Use valeric acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and valeric acid (pentaerythritol / butyric acid / 3, 5, 5 The tetraester 15 was obtained in the same manner as in Example 1 except that the trimethylhexanoic acid/pentanoic acid ratio was set to 1/1.08/2.64/1.08.

[實施例16] [Example 16] [丁酸、3,5,5-三甲基己酸及2-甲基戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)為81/19/6之季戊四醇之四酯(四酯16)之製造] [Merce ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid ratio) Manufacture of tetraester (tetraester 16) of pentaerythritol of 81/19/6]

使用2-甲基戊酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基戊酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)設定為1/3.46/0.96/0.38，除此以外，以與實施例1相同之方式進行操作而獲得四酯16。 Use 2-methylpentanoic acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (pentaerythritol / In the same manner as in Example 1, except that the ratio of butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid was set to 1/3.46/0.96/0.38, four were obtained in the same manner as in Example 1. Ester 16.

[實施例17] [Example 17] [丁酸、3,5,5-三甲基己酸及2-甲基戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)為71/29/53之季戊四醇之四酯(四酯17)之製造] [Merce ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid ratio) Manufacture of tetraester (tetraester 17) of pentaerythritol of 71/29/53]

使用2-甲基戊酸代替2-甲基丁酸，並將季戊四醇、丁 酸、3,5,5-三甲基己酸及2-甲基戊酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)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17。 Use 2-methylpentanoic acid instead of 2-methylbutyric acid, and pentaerythritol, butyl Mohr ratio of acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (pentaerythritol/butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentidine) The tetraester 17 was obtained in the same manner as in Example 1 except that the acid ratio was set to 1/1.92/0.96/1.92.

[實施例18] [Embodiment 18] [丁酸、3,5,5-三甲基己酸及2-甲基戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)為33/67/237之季戊四醇之四酯(四酯18)之製造] [Merce ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid ratio) Manufacture of tetraester (tetraester 18) of pentaerythritol of 33/67/237]

使用2-甲基戊酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基戊酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)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18。 Use 2-methylpentanoic acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (pentaerythritol / In the same manner as in Example 1, except that the ratio of butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid was set to 1/0.38/0.96/3.46, four were obtained in the same manner as in Example 1. Ester 18.

[實施例19] [Embodiment 19] [丁酸、3,5,5-三甲基己酸及2-甲基戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)為31/69/105之季戊四醇之四酯(四酯19)之製造] [Merce ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid ratio) Manufacture of tetraester (tetraester 19) of pentaerythritol of 31/69/105]

使用2-甲基戊酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基戊酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)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19。 Use 2-methylpentanoic acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (pentaerythritol / In the same manner as in Example 1, except that the ratio of butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid was set to 1/0.72/1.68/2.40, four operations were carried out in the same manner as in Example 1. Ester 19.

[實施例20] [Example 20] [丁酸、3,5,5-三甲基己酸及2-甲基戊酸之莫耳比(丁酸/ 3,5,5-三甲基己酸/2-甲基戊酸比)為43/57/32之季戊四醇之四酯(四酯20)之製造] [Molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid/2-methylpentanoic acid ratio) is a 43/57/32 pentaerythritol tetraester (tetraester 20)]

使用2-甲基戊酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基戊酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)設定為1/1.44/1.92/1.44，除此以外，以與實施例1相同之方式進行操作而獲得四酯20。 Use 2-methylpentanoic acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (pentaerythritol / In the same manner as in Example 1, except that the ratio of butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid was set to 1/1.44/1.92/1.44, four were obtained in the same manner as in Example 1. Ester 20.

[實施例21] [Example 21] [丁酸、3,5,5-三甲基己酸及2-甲基戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)為36/64/6之季戊四醇之四酯(四酯21)之製造] [Merce ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid ratio) Manufacture of 36/64/6 pentaerythritol tetraester (tetraester 21)]

使用2-甲基戊酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基戊酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)設定為1/1.62/3.00/0.18，除此以外，以與實施例1相同之方式進行操作而獲得四酯21。 Use 2-methylpentanoic acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (pentaerythritol / In the same manner as in Example 1, except that the ratio of butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid was set to 1/1.62/3.00/0.18, four were obtained in the same manner as in Example 1. Ester 21.

[實施例22] [Example 22] [丁酸、3,5,5-三甲基己酸及2-甲基戊酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)為26/74/19之季戊四醇之四酯(四酯22)之製造] [Merce ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid ratio) Manufacture of tetraester (tetraester 22) of pentaerythritol of 26/74/19]

使用2-甲基戊酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基戊酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基戊酸比)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22。 Use 2-methylpentanoic acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylpentanoic acid (pentaerythritol / In the same manner as in Example 1, except that the ratio of butyric acid/3,5,5-trimethylhexanoic acid/2-methylpentanoic acid was set to 1/0.90/3.00/0.90. The tetraester 22 is obtained by a row operation.

[實施例23] [Example 23] [丁酸、3,5,5-三甲基己酸及2-乙基丁酸之莫耳比(丁酸/3,5,5-三甲基己酸/2-乙基丁酸比)為35/65/40之季戊四醇之四酯(四酯23)之製造] [Merh ratio of butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (butyric acid/3,5,5-trimethylhexanoic acid/2-ethylbutyric acid ratio) Manufacture of 35/65/40 pentaerythritol tetraester (tetraester 23)]

使用2-乙基丁酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及2-乙基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-乙基丁酸比)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23。 Use 2-ethylbutyric acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylbutyric acid (pentaerythritol / In the same manner as in Example 1, except that the ratio of butyric acid/3,5,5-trimethylhexanoic acid/2-ethylbutyric acid was set to 1/1.20/2.00/1.60, four operations were carried out in the same manner as in Example 1. Ester 23.

[實施例24] [Example 24] [丁酸、3,5,5-三甲基己酸及己酸之莫耳比(丁酸/3,5,5-三甲基己酸/己酸比)為73/27/76之季戊四醇之四酯(四酯24)之製造] [The molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and caproic acid (butyric acid/3,5,5-trimethylhexanoic acid/hexanoic acid ratio) is 73/27/76 pentaerythritol. Manufacture of tetraester (tetraester 24)]

使用己酸代替2-甲基丁酸，並將季戊四醇、丁酸、3,5,5-三甲基己酸及己酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/己酸比)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24。 Use hexanoic acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and caproic acid (pentaerythritol / butyric acid / 3, 5, 5 The tetraester 24 was obtained in the same manner as in Example 1 except that the ratio of -trimethylhexanoic acid/hexanoic acid was changed to 1/1.92/0.96/1.92.

[實施例25] [Example 25] [丁酸、3,5,5-三甲基己酸及庚酸之莫耳比(丁酸/3,5,5-三甲基己酸/庚酸比)為71/29/70之季戊四醇之四酯(四酯25)之製造] [The molar ratio of butyric acid, 3,5,5-trimethylhexanoic acid and heptanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid / heptanoic acid ratio) is 71/29/70 pentaerythritol Manufacture of tetraester (tetraester 25)]

使用庚酸代替2-甲基丁酸，並將季戊四醇、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/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25。 Use heptanoic acid instead of 2-methylbutyric acid, and use the molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and heptanoic acid (pentaerythritol / butyric acid / The tetraester 25 was obtained in the same manner as in Example 1 except that the ratio of 3,5,5-trimethylhexanoic acid/heptanoic acid was changed to 1/1.92/0.96/1.92.

[比較例1] [Comparative Example 1] [丁酸與3,5,5-三甲基己酸之莫耳比(丁酸/3,5,5-三甲基己酸比)為25/75之季戊四醇之四酯(四酯A)之製造] [The molar ratio of butyric acid to 3,5,5-trimethylhexanoic acid (butyric acid / 3,5,5-trimethylhexanoic acid ratio) is a tetraester of 25/75 pentaerythritol (tetraester A) Manufacturing]

將季戊四醇、丁酸、3,5,5-三甲基己酸及2-甲基丁酸之使用量之莫耳比(季戊四醇/丁酸/3,5,5-三甲基己酸/2-甲基丁酸比)設定為1/1.20/3.60/0，除此以外，以與實施例1相同之方式進行操作而獲得四酯A。 The molar ratio of pentaerythritol, butyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (pentaerythritol / butyric acid / 3,5,5-trimethylhexanoic acid / 2 The tetraester A was obtained in the same manner as in Example 1 except that the ratio of -methylbutyric acid was changed to 1/1.20/3.60/0.

(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1~25及A之流動點。將結果示於表1~5。 The flow point of the tetraesters 1 to 25 and 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 5.

(試驗例2)四酯溶液之流動點之測定 (Test Example 2) Measurement of the flow point of the tetraester solution

於四酯1~25及A各43.65 g中混合苯并***1.35 g，於60℃下進行加熱而製備苯并***之3重量%四酯溶液。以與試驗例1相同之方式測定該3重量%四酯溶液各自之流動點。將結果示於表1~5。於表1~5中，BZT係表示苯并***。 A benzotriazole 1.35 g was mixed with tetraesters 1 to 25 and 43.65 g of each of A, and heated at 60 ° C to prepare a 3% by weight tetraester solution of benzotriazole. The respective flow points of the 3% by weight tetraester solution were measured in the same manner as in Test Example 1. The results are shown in Tables 1 to 5. In Tables 1 to 5, the BZT system represents benzotriazole.

(試驗例3)動黏度之測定 (Test Example 3) 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1~25及A之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1~5。 The dynamic viscosity at 40 ° C and 100 ° C of tetraesters 1 to 25 and 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 5.

(試驗例4)二層分離溫度之測定 (Test Example 4) Determination of the separation temperature of the two layers

依據JIS K2211：2009之方法測定四酯1~25及A之二層分離溫度。將四酯1~25及A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。將結果示於表1~5。 The separation temperature of the two layers of the tetraesters 1 to 25 and A was measured in accordance with the method of JIS K2211:2009. The tetraesters 1 to 25 and A 0.4 g each and the difluoromethane refrigerant 3.6 g were sealed in a pressure-resistant glass tube, and the mixture was cooled at a rate of 0.5 ° C per minute from 30 ° C to separate the mixture into two layers or the temperature of white turbidity. As a two layer separation temperature. The results are shown in Tables 1 to 5.

(試驗例5)-20℃下之固化、析出物有無之確認(低溫特性之評價) (Test Example 5) Confirmation of solidification at -20 ° C and presence or absence of precipitates (evaluation of low-temperature characteristics)

將四酯1~25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 1 to 25 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6)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 6) 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1~25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)。此處表示RBOT 壽命越長則四酯之氧化/水解穩定性越優異。將結果示於以下。 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 1~25, 4,4'-methylenebis(2,6-di-t-butylphenol) (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.25 g, IRGANOX L57 (Ciba Specialty Chemicals Co., Ltd. Manufactured) 0.25 g, 5 mL of water, and a copper wire (diameter 1.6 mm, length 3 m) rubbed by a paper rake #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. The time (RBOT life) required from the time when the pressure of the pressure-resistant container reached the highest pressure until the pressure of 175 kPa was lowered was measured. Here RBOT The longer the life, the more excellent the oxidation/hydrolysis stability of the tetraester. The results are shown below.

「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，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。將結果示於以下。 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 time required for the pressure of the pressure vessel to reach the pressure of 175 kPa (RBOT life). Here, the longer the RBOT life is, the more excellent the oxidation stability of the tetraester is. The results are shown below.

(試驗例7)重量減少溫度之測定(熱穩定性之評價) (Test Example 7) 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1~25之5%重量減少溫度。將結果示於以下。 The 5% weight loss temperature of the tetraester 1 to 25 was measured under the following conditions using a thermogravimetric/differential calorimeter Tg-DTA6200 (manufactured by Seiko Instruments Co., Ltd.). The results are shown below.

測定溫度：40~420℃，升溫速度：10℃/分鐘，環境：氮氣流通(300 mL/分)，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1~5可知，四酯1~25係100℃下之動黏度為4.6~8.2 mm2/秒，且具有黏度指數為83以上之充分之黏度-溫度特性，具有流動點為-40.0℃以下之優異之低溫流動性。又可知，具有二層分離溫度為-10℃以下之對於二氟甲烷冷媒之優異之相溶性。進而可知，苯并***之3重量%四酯溶液之流動點為-32.5℃以下，於溶解有苯并***時亦具有優異之低溫流動性。 According to Tables 1 to 5, the tetraester 1~25 system has a dynamic viscosity of 4.6 to 8.2 mm 2 /sec at 100 ° C and a viscosity-temperature characteristic with a viscosity index of 83 or more, and a flow point of -40.0 ° C. The following excellent low temperature fluidity. It is also known that the two-layer separation temperature is -10 ° C or less and excellent compatibility with a difluoromethane refrigerant. Further, it is understood that the 3% by weight of the tetraester solution of benzotriazole has a pour point of -32.5 ° C or less, and also has excellent low-temperature fluidity when benzotriazole is dissolved.

於試驗例5中，四酯1~25未固化，又，亦未確認到析出物。可知本發明之四酯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 5, the tetraester 1 to 25 was not cured, and no precipitate was observed. It is understood that the tetraester of the present invention can be preferably used even when it is stored or used for a long period of time in a low temperature region.

於試驗例6之「條件1」下，四酯1~25係RBOT壽命為716分鐘以上，其中四酯4為1546分鐘，四酯6為1510分鐘，四酯9為1440分鐘，四酯10為996分鐘，四酯11為1355分鐘，四酯14為912分鐘，四酯15為1140分鐘，四酯22為1500分鐘。可知本發明之四酯具有充分之氧化/水解穩定性。 Under the "Condition 1" of Test Example 6, the lifetime of the tetraester 1~25 series RBOT was 716 minutes or more, wherein the tetraester 4 was 1546 minutes, the tetraester 6 was 1510 minutes, the tetraester 9 was 1440 minutes, and the tetraester 10 was At 996 minutes, tetraester 11 was 1355 minutes, tetraester 14 was 912 minutes, tetraester 15 was 1140 minutes, and tetraester 22 was 1500 minutes. It is understood that the tetraester of the present invention has sufficient oxidation/hydrolysis stability.

試驗例6之「條件2」下之RBOT壽命係四酯4為180分鐘，四酯6為218分鐘，四酯11為421分鐘，四酯12為401分鐘，四酯22為195分鐘，四酯24為282分鐘，四酯25為180分鐘。可知本發明之四酯具有充分之氧化穩定性。 The RBOT lifetime under "Condition 2" of Test Example 6 was 180 minutes for tetraester 4, 218 minutes for tetraester 6, 421 minutes for tetraester 11, 401 minutes for tetraester 12, and 195 minutes for tetraester 22, tetraester. 24 is 282 minutes and tetraester 25 is 180 minutes. It is understood that the tetraester of the present invention has sufficient oxidative stability.

於試驗例7中，四酯1~25之Tg-DTA之測定中之5%重量減少溫度為209.5℃以上。可知本發明之四酯具有充分之熱穩定性。 In Test Example 7, the 5% weight loss temperature in the measurement of the Tg-DTA of the tetraester 1 to 25 was 209.5 ° C or higher. It is understood that the tetraester of the present invention has sufficient thermal stability.

[產業上之可利用性] [Industrial availability]

藉由本發明，可提供一種具有對於二氟甲烷冷媒之優異之相溶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 refrigerator oil or the like having excellent compatibility with a difluoromethane refrigerant.

Claims (9)

一種季戊四醇之四酯，其係季戊四醇與羧酸之混合酯，且上述羧酸含有丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族羧酸。 A tetraester of pentaerythritol which is a mixed ester of pentaerythritol and a carboxylic acid, and the carboxylic acid contains butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 to 7 carbon atoms. 如請求項1之季戊四醇之四酯，其中上述羧酸包含丁酸、3,5,5-三甲基己酸、及碳數5~7之脂肪族羧酸。 The tetraester of pentaerythritol of claim 1, wherein the carboxylic acid comprises butyric acid, 3,5,5-trimethylhexanoic acid, and an aliphatic carboxylic acid having 5 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5~7之脂肪族羧酸為碳數5或6之分支脂肪族羧酸。 The tetraester of pentaerythritol of claim 1 or 2, wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is a branched aliphatic carboxylic acid having 5 or 6 carbon atoms. 如請求項1或2之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為2-甲基丁酸。 The tetraester of pentaerythritol of claim 1 or 2, wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is 2-methylbutyric acid. 如請求項1或2之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為3-甲基丁酸。 The tetraester of pentaerythritol of claim 1 or 2, wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is 3-methylbutyric acid. 如請求項1或2之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為2-甲基戊酸。 The tetraester of pentaerythritol of claim 1 or 2, wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is 2-methylvaleric acid. 如請求項1或2之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為碳數5~7之直鏈脂肪族羧酸。 The tetraester of pentaerythritol of claim 1 or 2, wherein the aliphatic carboxylic acid having 5 to 7 carbon atoms is a linear aliphatic carboxylic acid having 5 to 7 carbon atoms. 如請求項1或2之季戊四醇之四酯，其中上述碳數5~7之脂肪族羧酸為戊酸。 The tetraester of pentaerythritol of claim 1 or 2, wherein the aliphatic carboxylic acid having 5 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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TWI600754B (en) 2017-10-01
JP2017019868A (en) 2017-01-26
JP6035240B2 (en) 2016-11-30
WO2013014959A1 (en) 2013-01-31

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