WO2013115160A1 - Mixed ester of mixed polyhydric alcohol and carboxylic acid - Google Patents
Mixed ester of mixed polyhydric alcohol and carboxylic acid Download PDFInfo
- Publication number
- WO2013115160A1 WO2013115160A1 PCT/JP2013/051848 JP2013051848W WO2013115160A1 WO 2013115160 A1 WO2013115160 A1 WO 2013115160A1 JP 2013051848 W JP2013051848 W JP 2013051848W WO 2013115160 A1 WO2013115160 A1 WO 2013115160A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- mixed ester
- pentaerythritol
- dipentaerythritol
- mixed
- Prior art date
Links
Classifications
-
- 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
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/011—Cloud point
-
- 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
- C10N2020/09—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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- Patent Document 1 Patent Document 2
- Patent Document 3 Patent Document 3
- Example 15 The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 60/40, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 15) having a trimethylhexanoic acid ratio) of 82/18]
- the molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used is 1 /
- a mixed ester 15 was obtained in the same manner as in Example 1 except that 0.67 / 7.68 / 1.92.
- Example 18 The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid and 2-ethylhexanoic acid (isobutyric acid / 2-ethylhexanoic acid ratio) is 47.
- the mixed esters 1 to 24 had a kinematic viscosity at 40 ° C. of 31.2 to 93.6 mm 2 / sec and a two-layer separation temperature of ⁇ 22 ° C. or lower. It can be seen that the mixed esters 1 to 24 have excellent compatibility with the difluoromethane refrigerant while ensuring the viscosity range necessary for the refrigerator oil.
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
Description
[1]ペンタエリスリトールおよび式(I)
で表されるジペンタエリスリトールからなる混合多価アルコールとイソ酪酸を含有するカルボン酸との混合エステルであって、前記混合多価アルコールにおけるペンタエリスリトールとジペンタエリスリトールのモル比[ペンタエリスリトール/ジペンタエリスリトール]が98/2~40/60の範囲であり、前記カルボン酸にしめるイソ酪酸の割合が35~85モル%の範囲である混合エステル。
[2]前記カルボン酸がイソ酪酸と3,5,5-トリメチルヘキサン酸および/または2-エチルヘキサン酸とを含有する[1]に記載の混合エステル。
[3]前記カルボン酸がイソ酪酸と3,5,5-トリメチルヘキサン酸とからなる[1]に記載の混合エステル。
[4]前記カルボン酸がイソ酪酸と2-エチルヘキサン酸とからなる[1]に記載の混合エステル。 The present invention provides the following [1] to [4].
[1] Pentaerythritol and formula (I)
A mixed ester of a mixed polyhydric alcohol composed of dipentaerythritol and a carboxylic acid containing isobutyric acid represented by the formula: wherein the molar ratio of pentaerythritol and dipentaerythritol in the mixed polyhydric alcohol [pentaerythritol / dipenta Erythritol] is in the range of 98/2 to 40/60, and the mixed ester has a ratio of isobutyric acid to the carboxylic acid in the range of 35 to 85 mol%.
[2] The mixed ester according to [1], wherein the carboxylic acid contains isobutyric acid and 3,5,5-trimethylhexanoic acid and / or 2-ethylhexanoic acid.
[3] The mixed ester according to [1], wherein the carboxylic acid comprises isobutyric acid and 3,5,5-trimethylhexanoic acid.
[4] The mixed ester according to [1], wherein the carboxylic acid comprises isobutyric acid and 2-ethylhexanoic acid.
で表されるジペンタエリスリトールからなる混合多価アルコールと、イソ酪酸を含有するカルボン酸との混合エステルであって、前記混合多価アルコールにおけるペンタエリスリトールとジペンタエリスリトールのモル比[ペンタエリスリトール/ジペンタエリスリトール]が98/2~40/60の範囲であり、前記カルボン酸にしめるイソ酪酸の割合が35~85モル%の範囲である混合エステルである。ここで、混合エステルとは、多価アルコールを複数種用いてエステル化して得られる化合物を意味する。
以下、前記式(I)で表されるジペンタエリスリトールを、ジペンタエリスリトールという。 The mixed esters of the present invention are pentaerythritol and formula (I)
A mixed ester of a mixed polyhydric alcohol composed of dipentaerythritol and a carboxylic acid containing isobutyric acid, the molar ratio of pentaerythritol and dipentaerythritol in the mixed polyhydric alcohol [pentaerythritol / di Pentaerythritol] is in the range of 98/2 to 40/60, and the ratio of isobutyric acid to the carboxylic acid is in the range of 35 to 85 mol%. Here, the mixed ester means a compound obtained by esterification using a plurality of polyhydric alcohols.
Hereinafter, dipentaerythritol represented by the formula (I) is referred to as dipentaerythritol.
(i)同一分子における構成カルボン酸がイソ酪酸およびイソ酪酸以外のその他のカルボン酸の双方を含むペンタエリスリトールのエステルと、同一分子における構成カルボン酸がイソ酪酸およびイソ酪酸以外のその他のカルボン酸の双方を含むジペンタエリスリトールのエステル、との混合物
(ii)ペンタエリスリトールとイソ酪酸を含有するカルボン酸とのエステル、ペンタエリスリトールとイソ酪酸以外のその他のカルボン酸とからなるエステル、ジペンタエリスリトールとイソ酪酸を含有するカルボン酸とのエステル、およびジペンタエリスリトールとイソ酪酸以外のその他のカルボン酸とからなるエステル、との混合物
(iii)上記(i)および(ii)の混合物
の各態様が包含される。
なお、本発明の混合エステルには混合多価アルコールの水酸基の一部がエステル化されずに水酸基のまま残っている部分エステル等が不純物として含まれていてもよい。 The “mixed ester” in the present invention includes the following (i) to (iii):
(I) an ester of pentaerythritol in which the constituent carboxylic acid in the same molecule includes both isobutyric acid and other carboxylic acids other than isobutyric acid; and the constituent carboxylic acid in the same molecule of other carboxylic acids other than isobutyric acid and isobutyric acid (Ii) ester of pentaerythritol and carboxylic acid containing isobutyric acid, ester of pentaerythritol and other carboxylic acid other than isobutyric acid, dipentaerythritol and isobutane Mixtures of esters with carboxylic acids containing butyric acid and esters of dipentaerythritol with other carboxylic acids other than isobutyric acid (iii) The embodiments of the mixtures of (i) and (ii) above are included The
Note that the mixed ester of the present invention may contain, as impurities, a partial ester in which a part of the hydroxyl group of the mixed polyhydric alcohol is not esterified and remains as a hydroxyl group.
本発明の混合エステルを構成するカルボン酸にしめるイソ酪酸の割合は35~85モル%の範囲であり、40~80モル%の範囲であるのがより好ましく、60~80モル%の範囲であるのがさらに好ましい。混合エステルを構成するカルボン酸にしめるイソ酪酸の該割合は35~85モル%の範囲を外れると上記特性が得られない。イソ酪酸の該割合が85モル%超であると、混合エステルの低温特性が悪くなる。 Since the carboxylic acid constituting the mixed ester of the present invention contains isobutyric acid, the mixed ester of the present invention has excellent compatibility with difluoromethane refrigerant, excellent lubricity, sufficient viscosity-temperature characteristics, sufficient Good balance of properties such as low-temperature properties.
The proportion of isobutyric acid included in the carboxylic acid constituting the mixed ester of the present invention is in the range of 35 to 85 mol%, more preferably in the range of 40 to 80 mol%, and in the range of 60 to 80 mol%. Is more preferable. If the proportion of isobutyric acid included in the carboxylic acid constituting the mixed ester is outside the range of 35 to 85 mol%, the above characteristics cannot be obtained. When the proportion of isobutyric acid is more than 85 mol%, the low temperature characteristics of the mixed ester are deteriorated.
イソ酪酸と3,5,5-トリメチルヘキサン酸および/または2-エチルヘキサン酸の和に対するその他のカルボン酸のモル比[その他のカルボン酸/(イソ酪酸と3,5,5-トリメチルヘキサン酸および/または2-エチルヘキサン酸)比]は、0/100~50/50の範囲であるのが好ましく、0/100であるのがさらに好ましい。 When the carboxylic acid constituting the mixed ester of the present invention is a carboxylic acid containing isobutyric acid and 3,5,5-trimethylhexanoic acid and / or 2-ethylhexanoic acid, the mixed ester of the present invention is a difluoromethane refrigerant. Other carboxylic acids can be contained in a content that does not impair excellent properties such as compatibility with the other.
Molar ratio of other carboxylic acids to the sum of isobutyric acid and 3,5,5-trimethylhexanoic acid and / or 2-ethylhexanoic acid [other carboxylic acids / (isobutyric acid and 3,5,5-trimethylhexanoic acid and // 2-ethylhexanoic acid) ratio] is preferably in the range of 0/100 to 50/50, more preferably 0/100.
本発明の混合エステルを構成するカルボン酸がイソ酪酸と2-エチルヘキサン酸とからなるカルボン酸であるとき、イソ酪酸と2-エチルヘキサン酸のモル比[イソ酪酸/2-エチルヘキサン酸比]は、35/65~85/15の範囲にある。 When the carboxylic acid constituting the mixed ester of the present invention is a carboxylic acid composed of isobutyric acid and 3,5,5-trimethylhexanoic acid, the molar ratio of isobutyric acid to 3,5,5-trimethylhexanoic acid [iso Butyric acid / 3,5,5-trimethylhexanoic acid ratio] is in the range of 35/65 to 85/15.
When the carboxylic acid constituting the mixed ester of the present invention is a carboxylic acid composed of isobutyric acid and 2-ethylhexanoic acid, the molar ratio of isobutyric acid to 2-ethylhexanoic acid [ratio of isobutyric acid / 2-ethylhexanoic acid] Is in the range of 35/65 to 85/15.
核磁気共鳴スペクトルは、以下の測定機器、測定手法により測定した。
測定機器;日本電子社製GSX-400(400MHz)
測定手法;1H-NMR、標準物(テトラメチルシラン)、溶媒(CDCl3) EXAMPLES Hereinafter, although an Example, a comparative example, a reference example, and a test example demonstrate this invention further more concretely, it is not limited to a following example.
The nuclear magnetic resonance spectrum was measured by the following measuring instrument and measuring method.
Measuring instrument: GSX-400 (400 MHz) manufactured by JEOL Ltd.
Measurement method: 1 H-NMR, standard (tetramethylsilane), solvent (CDCl 3 )
ペンタエリスリトール/ジペンタエリスリトール=(ピークRの積分値/8)/(ピークSの積分値/4)
ここでピークRはペンタエリスリトールにおけるメチレン基上の水素原子のピークに相当し、ピークSはジペンタエリスリトールにおけるエーテル酸素と結合しているメチレン基上の水素原子に相当する。 Nuclear magnetic resonance spectra were measured for each of the mixed esters produced in Examples 1 to 24, Comparative Example 1 and Reference Examples 1 and 2 below, and the molar ratio of pentaerythritol and dipentaerythritol in the mixed ester was Calculated by the formula.
Pentaerythritol / dipentaerythritol = (integral value of peak R / 8) / (integral value of peak S / 4)
Here, the peak R corresponds to the peak of the hydrogen atom on the methylene group in pentaerythritol, and the peak S corresponds to the hydrogen atom on the methylene group bonded to the ether oxygen in dipentaerythritol.
イソ酪酸/3,5,5-トリメチルヘキサン酸=ピークTの積分値/ピークUの積分値
ここでピークTはイソ酪酸におけるメチン基上の水素原子のピークに相当し、ピークUは3,5,5-トリメチルヘキサン酸におけるメチン基上の水素原子に相当する。 For each of the mixed esters produced in the following Examples 1 to 16, Comparative Example 1 and Reference Examples 1 and 2, nuclear magnetic resonance spectra were measured, and isobutyric acid and 3,5,5-trimethylhexanoic acid in the mixed ester were measured. Was calculated by the following formula.
Isobutyric acid / 3,5,5-trimethylhexanoic acid = integrated value of peak T / integrated value of peak U Here, peak T corresponds to the peak of the hydrogen atom on the methine group in isobutyric acid, and peak U is 3,5 , Corresponds to a hydrogen atom on the methine group in 5-trimethylhexanoic acid.
イソ酪酸/2-エチルヘキサン酸=ピークTの積分値/ピークVの積分値
ここでピークTは前記と同義であり、ピークVは2-エチルヘキサン酸におけるメチン基上の水素原子のピークに相当する。 Nuclear magnetic resonance spectra were measured for each of the mixed esters produced in Examples 17 to 19 below, and the molar ratio of isobutyric acid to 2-ethylhexanoic acid in the mixed ester was calculated by the following formula.
Isobutyric acid / 2-ethylhexanoic acid = integrated value of peak T / integrated value of peak V Here, peak T has the same meaning as above, and peak V corresponds to the peak of the hydrogen atom on the methine group in 2-ethylhexanoic acid. To do.
イソ酪酸/3,5,5-トリメチルヘキサン酸/2-エチルヘキサン酸=ピークTの積分値/ピークUの積分値/ピークVの積分値
ここでピークT、ピークUおよびピークVは前記と同義である。 For the mixed ester produced in Example 20 below, a nuclear magnetic resonance spectrum was measured, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid in the mixed ester was determined by the following formula. Calculated.
Isobutyric acid / 3,5,5-trimethylhexanoic acid / 2-ethylhexanoic acid = integrated value of peak T / integrated value of peak U / integrated value of peak V Here, peak T, peak U and peak V are as defined above. It is.
イソ酪酸/3,5,5-トリメチルヘキサン酸/酪酸=ピークTの積分値/ピークUの積分値/(ピークWの積分値/2)
ここでピークTおよびピークUは前記と同義であり、ピークWは酪酸におけるカルボニル基のα位のメチレン基上の水素原子のピークに相当する。 The nuclear magnetic resonance spectrum of the mixed ester produced in Example 21 below was measured, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid in the mixed ester was calculated according to the following formula.
Isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid = integrated value of peak T / integrated value of peak U / (integrated value of peak W / 2)
Here, the peak T and the peak U have the same meaning as described above, and the peak W corresponds to the peak of a hydrogen atom on the methylene group at the α-position of the carbonyl group in butyric acid.
イソ酪酸/3,5,5-トリメチルヘキサン酸/ペンタン酸=ピークTの積分値/ピークUの積分値/(ピークXの積分値/2)
ここでピークTおよびピークUは前記と同義であり、ピークXはペンタン酸におけるカルボニル基のα位のメチレン基上の水素原子のピークに相当する。 For each of the mixed esters produced in Examples 22 and 23 below, a nuclear magnetic resonance spectrum was measured, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid in the mixed ester was expressed by the following formula: Calculated by
Isobutyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid = integrated value of peak T / integrated value of peak U / (integrated value of peak X / 2)
Here, the peak T and the peak U have the same meaning as described above, and the peak X corresponds to the peak of a hydrogen atom on the α-position methylene group of the carbonyl group in pentanoic acid.
イソ酪酸/3,5,5-トリメチルヘキサン酸/2-メチル酪酸=ピークTの積分値/ピークUの積分値/ピークYの積分値
ここでピークTおよびピークUは前記と同義であり、ピークYは2-メチル酪酸におけるメチン基上の水素原子のピークに相当する。 For the mixed ester produced in Example 24 below, the nuclear magnetic resonance spectrum was measured, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid in the mixed ester was calculated by the following formula: did.
Isobutyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid = integrated value of peak T / integrated value of peak U / integrated value of peak Y Here, peak T and peak U are as defined above, and peak Y corresponds to the peak of the hydrogen atom on the methine group in 2-methylbutyric acid.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が97/3であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が81/19である混合エステル(混合エステル1)の製造]
吸着剤としては、協和化学工業社製キョーワード500を用いた。
活性炭としては、日本エンバイロケミカルズ社製白鷺Pを用いた。
ディーンスタークトラップの付いた反応器にペンタエリスリトール153g(1.1モル、広栄パーストープ社製)、ジペンタエリスリトール9g(0.04モル、広栄パーストープ社製)、イソ酪酸398g(4.5モル、東京化成社製)および3,5,5-トリメチルヘキサン酸177g(1.1モル、協和発酵ケミカル社製)を仕込み、混合物を攪拌しながら室温で30分間窒素バブリングを行うことにより混合物を脱気した。
次いで、窒素バブリングを行いながら混合物を155~232℃で23時間攪拌した。反応後、反応生成物を0.7kPaの減圧下、210℃で1時間攪拌することにより、反応生成物中の未反応のカルボン酸を留去した。反応生成物を、該反応生成物の酸価に対して2倍モルの水酸化ナトリウムを含むアルカリ水溶液300mLで、90℃で1時間洗浄した。次いで、反応生成物を、水300mLで90℃で1時間、3回洗浄した。次いで、窒素バブリングを行いながら反応生成物を0.7kPaの減圧下、110℃で1時間攪拌することにより反応生成物を乾燥した。
反応生成物に吸着剤5.5g(反応生成物の重量1.0%に相当する)および活性炭5.5g(反応生成物の重量1.0%に相当する)を添加し、窒素バブリングを行いながら反応生成物を0.7kPaの減圧下、110℃で2時間攪拌した後、濾過助剤を用いて濾過することにより、混合エステル1を370g得た。 [Example 1]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 97/3, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 1) having a trimethylhexanoic acid ratio) of 81/19]
As an adsorbent, Kyoward 500 manufactured by Kyowa Chemical Industry Co., Ltd. was used.
As activated carbon, Shirahige P manufactured by Nippon Enviro Chemicals was used.
In a reactor equipped with a Dean-Stark trap, 153 g of pentaerythritol (1.1 mol, manufactured by Guangei Perstorp), 9 g of dipentaerythritol (0.04 mol, manufactured by Guangei Perstorp), 398 g (4.5 mol, Tokyo) Kasei Co., Ltd.) and 3,5,5-trimethylhexanoic acid 177 g (1.1 mol, manufactured by Kyowa Hakko Chemical Co., Ltd.) were added, and the mixture was degassed by bubbling nitrogen at room temperature for 30 minutes while stirring the mixture. .
The mixture was then stirred at 155-232 ° C. for 23 hours with nitrogen bubbling. After the reaction, the reaction product was stirred at 210 ° C. for 1 hour under a reduced pressure of 0.7 kPa to distill off unreacted carboxylic acid in the reaction product. The reaction product was washed at 90 ° C. for 1 hour with 300 mL of an alkaline aqueous solution containing sodium hydroxide twice as much as the acid value of the reaction product. The reaction product was then washed 3 times with 300 mL of water at 90 ° C. for 1 hour. Subsequently, the reaction product was dried at 110 ° C. for 1 hour under a reduced pressure of 0.7 kPa while performing nitrogen bubbling.
To the reaction product, 5.5 g of adsorbent (corresponding to 1.0% by weight of the reaction product) and 5.5 g of activated carbon (corresponding to 1.0% of the weight of the reaction product) are added, and nitrogen bubbling is performed. Then, the reaction product was stirred at 110 ° C. for 2 hours under a reduced pressure of 0.7 kPa, and then filtered using a filter aid to obtain 370 g of mixed ester 1.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が97/3であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が64/36である混合エステル(混合エステル2)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.03/3.01/2.01にする以外は、実施例1と同様に操作して、混合エステル2を得た。 [Example 2]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 97/3, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 2) having a trimethylhexanoic acid ratio) of 64/36]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 2 was obtained in the same manner as in Example 1 except that 0.03 / 3.01 / 2.01.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が97/3であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が40/60である混合エステル(混合エステル3)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.03/2.01/3.01にする以外は、実施例1と同様に操作して、混合エステル3を得た。 [Example 3]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 97/3, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 3) having a trimethylhexanoic acid ratio) of 40/60]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 3 was obtained in the same manner as in Example 1 except that the ratio was 0.03 / 2.01 / 3.01.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が90/10であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が82/18である混合エステル(混合エステル4)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.11/4.48/1.12にする以外は、実施例1と同様に操作して、混合エステル4を得た。 [Example 4]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 90/10, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 4) having a trimethylhexanoic acid ratio) of 82/18]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 4 was obtained in the same manner as in Example 1 except that the ratio was 0.11 / 4.48 / 1.12.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が90/10であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が72/28である混合エステル(混合エステル5)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.11/3.92/1.68にする以外は、実施例1と同様に操作して、混合エステル5を得た。 [Example 5]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 90/10, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 5) having a trimethylhexanoic acid ratio) of 72/28]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 5 was obtained in the same manner as in Example 1 except that 0.11 / 3.92 / 1.68 was used.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が90/10であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が51/49である混合エステル(混合エステル6)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.11/2.80/2.80にする以外は、実施例1と同様に操作して、混合エステル6を得た。 [Example 6]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 90/10, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 6) having a trimethylhexanoic acid ratio) of 51/49]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 6 was obtained in the same manner as in Example 1 except that 0.11 / 2.80 / 2.80.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が81/19である混合エステル(混合エステル7)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.18/4.86/1.21にする以外は、実施例1と同様に操作して、混合エステル7を得た。 [Example 7]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 7) having a trimethylhexanoic acid ratio) of 81/19]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 7 was obtained in the same manner as in Example 1 except that the ratio was 0.18 / 4.86 / 1.21.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が58/42である混合エステル(混合エステル8)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.18/3.49/2.58にする以外は、実施例1と同様に操作して、混合エステル8を得た。 [Example 8]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 8) having a trimethylhexanoic acid ratio) of 58/42]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 8 was obtained in the same manner as in Example 1 except that 0.18 / 3.49 / 2.58 was used.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が50/50である混合エステル(混合エステル9)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.18/3.04/3.04にする以外は、実施例1と同様に操作して、混合エステル9を得た。 [Example 9]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 9) having a trimethylhexanoic acid ratio) of 50/50]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 9 was obtained in the same manner as in Example 1 except that 0.18 / 3.04 / 3.04.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が40/60である混合エステル(混合エステル10)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.18/2.43/3.64にする以外は、実施例1と同様に操作して、混合エステル10を得た。 [Example 10]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 10) having a trimethylhexanoic acid ratio) of 40/60]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 10 was obtained in the same manner as in Example 1 except that 0.18 / 2.43 / 3.64.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が80/20であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が82/18である混合エステル(混合エステル11)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.25/5.28/1.32にする以外は、実施例1と同様に操作して、混合エステル11を得た。 [Example 11]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 80/20, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 11) having a trimethylhexanoic acid ratio) of 82/18]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 11 was obtained in the same manner as in Example 1 except that 0.25 / 5.28 / 1.32.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が80/20であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が72/28である混合エステル(混合エステル12)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.25/4.62/1.98にする以外は、実施例1と同様に操作して、混合エステル12を得た。 [Example 12]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 80/20, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 12) having a trimethylhexanoic acid ratio) of 72/28]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 12 was obtained in the same manner as in Example 1 except that the ratio was changed to 0.25 / 4.62 / 1.98.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が70/30であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が82/18である混合エステル(混合エステル13)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.43/6.31/1.58にする以外は、実施例1と同様に操作して、混合エステル13を得た。 [Example 13]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 70/30, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 13) having a trimethylhexanoic acid ratio) of 82/18]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 13 was obtained in the same manner as in Example 1 except that the ratio was 0.43 / 6.31 / 1.58.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が70/30であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が60/40である混合エステル(混合エステル14)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,・BR>T,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.43/4.73/3.15にする以外は、実施例1と同様に操作して、混合エステル14を得た。 [Example 14]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 70/30, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 14) having a trimethylhexanoic acid ratio) of 60/40]
Molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3, · BR> T, 5-trimethylhexanoic acid used (ratio of pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid) The mixed ester 14 was obtained in the same manner as in Example 1 except that the ratio was changed to 1 / 0.43 / 4.73 / 3.15.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が60/40であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が82/18である混合エステル(混合エステル15)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.67/7.68/1.92にする以外は、実施例1と同様に操作して、混合エステル15を得た。 [Example 15]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 60/40, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 15) having a trimethylhexanoic acid ratio) of 82/18]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester 15 was obtained in the same manner as in Example 1 except that 0.67 / 7.68 / 1.92.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が50/50であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が81/19である混合エステル(混合エステル16)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/1.00/9.60/2.40にする以外は、実施例1と同様に操作して、混合エステル16を得た。 [Example 16]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 50/50, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester 16) having a trimethylhexanoic acid ratio) of 81/19]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / The mixed ester 16 was obtained in the same manner as in Example 1 except that the ratio was changed to 1.00 / 9.60 / 2.40.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と2-エチルヘキサン酸のモル比(イソ酪酸/2-エチルヘキサン酸比)が64/36である混合エステル(混合エステル17)の製造]
3,5,5-トリメチルヘキサン酸の代わりに2-エチルヘキサン酸を用い、ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および2-エチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/2-エチルヘキサン酸比)を1/0.18/3.64/2.43にする以外は、実施例1と同様に操作して、混合エステル17を得た。 [Example 17]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid to 2-ethylhexanoic acid (ratio of isobutyric acid / 2-ethylhexanoic acid) is 64 / 36 Production of mixed ester (mixed ester 17)]
Instead of 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid is used, and the molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 2-ethylhexanoic acid used (pentaerythritol / dipentaerythritol / iso The mixed ester 17 was obtained in the same manner as in Example 1 except that the ratio of butyric acid / 2-ethylhexanoic acid was changed to 1 / 0.18 / 3.64 / 2.43.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と2-エチルヘキサン酸のモル比(イソ酪酸/2-エチルヘキサン酸比)が47/53である混合エステル(混合エステル18)の製造]
3,5,5-トリメチルヘキサン酸の代わりに2-エチルヘキサン酸を用い、ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および2-エチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/2-エチルヘキサン酸比)を1/0.18/2.43/3.64にする以外は、実施例1と同様に操作して、混合エステル18を得た。 [Example 18]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid and 2-ethylhexanoic acid (isobutyric acid / 2-ethylhexanoic acid ratio) is 47. / 53 Production of mixed ester (mixed ester 18)]
Instead of 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid is used, and the molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 2-ethylhexanoic acid used (pentaerythritol / dipentaerythritol / iso The mixed ester 18 was obtained in the same manner as in Example 1 except that the ratio of butyric acid / 2-ethylhexanoic acid was changed to 1 / 0.18 / 2.43 / 3.64.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が70/30であり、イソ酪酸と2-エチルヘキサン酸のモル比(イソ酪酸/2-エチルヘキサン酸比)が62/38である混合エステル(混合エステル19)の製造]
3,5,5-トリメチルヘキサン酸の代わりに2-エチルヘキサン酸を用い、ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および2-エチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/2-エチルヘキサン酸比)を1/0.43/4.73/3.15にする以外は、実施例1と同様に操作して、混合エステル19を得た。 [Example 19]
[The molar ratio of pentaerythritol to dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 70/30, and the molar ratio of isobutyric acid to 2-ethylhexanoic acid (ratio of isobutyric acid / 2-ethylhexanoic acid) is 62 / 38 Production of mixed ester (mixed ester 19)]
Instead of 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid is used, and the molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 2-ethylhexanoic acid used (pentaerythritol / dipentaerythritol / iso A mixed ester 19 was obtained in the same manner as in Example 1 except that the ratio of butyric acid / 2-ethylhexanoic acid was changed to 1 / 0.43 / 4.73 / 3.15.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸/2-エチルヘキサン酸比)が61/19/20である混合エステル(混合エステル20)の製造]
3,5,5-トリメチルヘキサン酸の代わりに3,5,5-トリメチルヘキサン酸と2-エチルヘキサン酸の混合カルボン酸を用い、ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸、3,5,5-トリメチルヘキサン酸および2-エチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸/2-エチルヘキサン酸比)を1/0.18/3.64/1.21/1.21にする以外は、実施例1と同様に操作して、混合エステル20を得た。 [Example 20]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid (isobutyric acid Of 3,5,5-trimethylhexanoic acid / 2-ethylhexanoic acid ratio) of 61/19/20 (mixed ester 20)]
Instead of 3,5,5-trimethylhexanoic acid, a mixed carboxylic acid of 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid is used, pentaerythritol, dipentaerythritol, isobutyric acid, 3,5,5- The molar ratio of trimethylhexanoic acid and 2-ethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / 2-ethylhexanoic acid ratio) was set to 1 / 0.18 / A mixed ester 20 was obtained in the same manner as in Example 1 except that the ratio was changed to 3.64 / 1.21 / 1.21.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸と酪酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸/酪酸比)が39/18/43である混合エステル(混合エステル21)の製造]
3,5,5-トリメチルヘキサン酸の代わりに3,5,5-トリメチルヘキサン酸と酪酸の混合カルボン酸を用い、ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸、3,5,5-トリメチルヘキサン酸および酪酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸/酪酸比)を1/0.18/2.43/1.21/2.43にする以外は、実施例1と同様に操作して、混合エステル21を得た。 [Example 21]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and butyric acid (isobutyric acid / 3,5 , 5-Trimethylhexanoic acid / butyric acid ratio) is 39/18/43 to produce a mixed ester (mixed ester 21)]
Instead of 3,5,5-trimethylhexanoic acid, a mixed carboxylic acid of 3,5,5-trimethylhexanoic acid and butyric acid is used, pentaerythritol, dipentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid and The molar ratio of butyric acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / butyric acid ratio) to 1 / 0.18 / 2.43 / 1.21 / 2.43 A mixed ester 21 was obtained in the same manner as in Example 1 except that.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸とペンタン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸/ペンタン酸比)が40/17/43である混合エステル(混合エステル22)の製造]
3,5,5-トリメチルヘキサン酸の代わりに3,5,5-トリメチルヘキサン酸とペンタン酸の混合カルボン酸を用い、ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸、3,5,5-トリメチルヘキサン酸およびペンタン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸/ペンタン酸比)を1/0.18/2.43/1.21/2.43にする以外は、実施例1と同様に操作して、混合エステル22を得た。 [Example 22]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid (isobutyric acid / 3, Production of mixed ester (mixed ester 22) having a ratio of 5,5-trimethylhexanoic acid / pentanoic acid) of 40/17/43]
A mixed carboxylic acid of 3,5,5-trimethylhexanoic acid and pentanoic acid is used in place of 3,5,5-trimethylhexanoic acid, pentaerythritol, dipentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid And the molar ratio of the amount of pentanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) of 1 / 0.18 / 2.43 / 1.21 / 2 The mixed ester 22 was obtained in the same manner as in Example 1 except that the ratio was changed to .43.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸とペンタン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸/ペンタン酸比)が38/39/23である混合エステル(混合エステル23)の製造]
3,5,5-トリメチルヘキサン酸の代わりに3,5,5-トリメチルヘキサン酸とペンタン酸の混合カルボン酸を用い、ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸、3,5,5-トリメチルヘキサン酸およびペンタン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸/ペンタン酸比)を1/0.18/2.43/2.43/1.21にする以外は、実施例1と同様に操作して、混合エステル23を得た。 [Example 23]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and pentanoic acid (isobutyric acid / 3, Production of mixed ester (mixed ester 23) having a 5,5-trimethylhexanoic acid / pentanoic acid ratio) of 38/39/23]
A mixed carboxylic acid of 3,5,5-trimethylhexanoic acid and pentanoic acid is used in place of 3,5,5-trimethylhexanoic acid, pentaerythritol, dipentaerythritol, isobutyric acid, 3,5,5-trimethylhexanoic acid And the molar ratio of the amount of pentanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / pentanoic acid ratio) is 1 / 0.18 / 2.43 / 2.43 / 1 The mixed ester 23 was obtained in the same manner as in Example 1 except that it was changed to .21.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸と2-メチル酪酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸/2-メチル酪酸比)が43/20/37である混合エステル(混合エステル24)の製造]
3,5,5-トリメチルヘキサン酸の代わりに3,5,5-トリメチルヘキサン酸と2-メチル酪酸の混合カルボン酸を用い、ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸、3,5,5-トリメチルヘキサン酸および2-メチル酪酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸/2-メチル酪酸比)を1/0.18/2.43/1.21/2.43にする以外は、実施例1と同様に操作して、混合エステル24を得た。 [Example 24]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid, 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid (isobutyric acid / Production of mixed ester (mixed ester 24) having 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) of 43/20/37]
A mixed carboxylic acid of 3,5,5-trimethylhexanoic acid and 2-methylbutyric acid is used in place of 3,5,5-trimethylhexanoic acid, pentaerythritol, dipentaerythritol, isobutyric acid, 3,5,5-trimethyl The molar ratio of the amounts of hexanoic acid and 2-methylbutyric acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid / 2-methylbutyric acid ratio) was set to 1 / 0.18 / 2.43. The mixed ester 24 was obtained in the same manner as in Example 1 except that the ratio was changed to /1.21/2.43.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が60/40であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が12.5/87.5である混合エステル(混合エステルA)の製造]
イソ酪酸の代わりにイソ酪酸無水物を用い、ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸無水物および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸無水物/3,5,5-トリメチルヘキサン酸比)を1/0.67/0.60/8.40にする以外は、実施例1と同様に操作して、混合エステルAを得た。 [Comparative Example 1]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 60/40, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester A) having a trimethylhexanoic acid ratio) of 12.5 / 87.5]
Isobutyric anhydride is used instead of isobutyric acid, and the molar ratio of pentaerythritol, dipentaerythritol, isobutyric anhydride and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric anhydride) Product / 3,5,5-trimethylhexanoic acid ratio) was changed to 1 / 0.67 / 0.60 / 8.40 in the same manner as in Example 1 to obtain mixed ester A.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が85/15であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が86/14である混合エステル(混合エステルB)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/0.18/5.30/0.79にする以外は、実施例1と同様に操作して、混合エステルBを得た。混合エステルBは室温では固体であったため、冷凍機油のように幅広い温度範囲で使用される用途には不適切である。 [Reference Example 1]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 85/15, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester B) having a trimethylhexanoic acid ratio) of 86/14]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester B was obtained in the same manner as in Example 1 except that 0.18 / 5.30 / 0.79. Since the mixed ester B was a solid at room temperature, it is unsuitable for applications that are used in a wide temperature range such as refrigerator oil.
[ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が35/65であり、イソ酪酸と3,5,5-トリメチルヘキサン酸のモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸)が81/19である混合エステル(混合エステルC)の製造]
ペンタエリスリトール、ジペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸比)を1/1.87/14.62/3.65にする以外は、実施例1と同様に操作して、混合エステルCを得た。混合エステルCは室温では固体であったため、冷凍機油のように幅広い温度範囲で使用される用途には不適切である。 [Reference Example 2]
[The molar ratio of pentaerythritol and dipentaerythritol (pentaerythritol / dipentaerythritol ratio) is 35/65, and the molar ratio of isobutyric acid and 3,5,5-trimethylhexanoic acid (isobutyric acid / 3,5,5 -Production of mixed ester (mixed ester C) wherein trimethylhexanoic acid) is 81/19]
The molar ratio of pentaerythritol, dipentaerythritol, isobutyric acid and 3,5,5-trimethylhexanoic acid used (pentaerythritol / dipentaerythritol / isobutyric acid / 3,5,5-trimethylhexanoic acid ratio) is 1 / A mixed ester C was obtained in the same manner as in Example 1 except that 1.87 / 14.62 / 3.65. Since the mixed ester C was solid at room temperature, it is unsuitable for applications that are used in a wide temperature range, such as refrigerator oil.
キャノン-フェンスケ粘度計を用い、JIS K2283:2000の方法に準じて混合エステル1~24および混合エステルAの40℃および100℃における動粘度を測定した。また、同方法に準じて粘度指数を算出した。結果を表1~6に示す。 Test Example 1 Measurement of Kinematic Viscosity Using a Canon-Fenske viscometer, the kinematic viscosities of mixed esters 1 to 24 and mixed ester A at 40 ° C. and 100 ° C. were measured according to the method of JIS K2283: 2000. The viscosity index was calculated according to the same method. The results are shown in Tables 1-6.
JIS K-2501の方法に準じて混合エステル1~24および混合エステルA~Cの水酸基価を測定した。結果を表1~6に示す。 (Test Example 2) Measurement of hydroxyl value The hydroxyl values of mixed esters 1 to 24 and mixed esters A to C were measured according to the method of JIS K-2501. The results are shown in Tables 1-6.
自動流動点測定器RPC-01CML(離合社製)を用い、JIS K2269-1987の方法に準じて混合エステル1~24および混合エステルAの流動点を測定した。結果を表1~6に示す。 (Test Example 3) Measurement of pour point The pour point of mixed ester 1 to 24 and mixed ester A was measured according to the method of JIS K2269-1987 using an automatic pour point measuring device RPC-01CML (manufactured by Rouai Co., Ltd.). The results are shown in Tables 1-6.
JIS K2211:2009の方法に準じて混合エステル1~24および混合エステルAの二層分離温度を測定した。混合エステル1~24および混合エステルAのそれぞれ0.4gとジフルオロメタン冷媒3.6gを耐圧ガラス管に封入し、混合物を30℃から毎分0.5℃の速度で冷却し、混合物が二層分離または白濁する温度を二層分離温度とした。結果を表1~6に示す。ただし、30℃ですでに混合物が二層分離または白濁している場合は「分離」と表記する。 (Test Example 4) Measurement of two-layer separation temperature The two-layer separation temperatures of mixed ester 1 to 24 and mixed ester A were measured according to the method of JIS K2211: 2009. Each 0.4 g of mixed ester 1 to 24 and mixed ester A and 3.6 g of difluoromethane refrigerant are sealed in a pressure-resistant glass tube, and the mixture is cooled from 30 ° C. at a rate of 0.5 ° C. per minute. The temperature at which separation or white turbidity occurred was defined as the two-layer separation temperature. The results are shown in Tables 1-6. However, when the mixture is already separated into two layers or clouded at 30 ° C., it is expressed as “separation”.
シェル式四球摩擦試験機(神鋼造機社製)を用いて、荷重100N、回転数300rpm、温度25℃、試験材[試験球(SUJ-2)]の条件で試験を行い、混合エステル1~24および混合エステルAの摩擦係数を測定した。摩擦係数は上記条件で、なじみ運転を20分間行った後の10分間の摩擦係数の平均とした。結果を表1~6に示す。 (Test Example 5) Measurement of friction coefficient Using a shell-type four-ball friction tester (manufactured by Shinko Engineering Co., Ltd.) under the conditions of a load of 100 N, a rotation speed of 300 rpm, a temperature of 25 ° C., and a test material [test ball (SUJ-2)] Tests were performed and the friction coefficients of mixed esters 1-24 and mixed ester A were measured. The coefficient of friction was the average of the coefficient of friction for 10 minutes after the familiar operation for 20 minutes under the above conditions. The results are shown in Tables 1-6.
混合エステル1~24のそれぞれ10gをガラス容器に入れ、-20℃に設定した恒温器中で10時間静置した。10時間静置後の固化、析出物の有無を目視にて確認した。結果を以下に示す。 (Test Example 6) Solidification at −20 ° C., confirmation of presence of precipitates (evaluation of low temperature characteristics)
10 g of each of the mixed esters 1 to 24 was put in a glass container, and allowed to stand for 10 hours in a thermostat set to −20 ° C. The solidification after standing for 10 hours and the presence or absence of precipitates were confirmed visually. The results are shown below.
混合エステル7~10、13、15および混合エステルAのそれぞれ4.85gに、ベンゾトリアゾール0.15gを混合し、60℃で加熱して、ベンゾトリアゾールの3重量%混合エステル溶液のそれぞれを得た。該混合エステル溶液のそれぞれを5℃で40時間放置した後、目視により析出物の確認を行った。
析出物の見られなかった該混合エステル溶液は、5℃におけるベンゾトリアゾールの溶解度[混合エステル1gに対するベンゾトリアゾールの溶解量(g)]を0.030g/g以上とした。析出物の見られた該混合エステル溶液は、析出物を濾過(濾紙;No.5A、桐山製作所製)により除去した後に、得られた濾液を高速液体クロマトグラフィー(AGILENT社製1200SERIES、カラム:YMC Pack Ph A-414 φ6.0×300mm、移動相:テトラヒドロフラン/0.1%リン酸水溶液=7/3、カラム温度:40℃、流速:0.7mL/分、検出:UV(220nm)、サンプル濃度:50g/L、インジェクト量:5μL)で測定し、絶対検量線法により、5℃におけるベンゾトリアゾールの溶解度[混合エステル1gに対するベンゾトリアゾールの溶解量(g)]を求めた。結果を表7および8に示す。 (Test Example 7) Measurement of solubility of benzotriazole at 5 ° C. Each of the mixed esters 7 to 10, 13, 15 and 4.85 g of the mixed ester A was mixed with 0.15 g of benzotriazole and heated at 60 ° C. Each of the 3 wt% mixed ester solutions of benzotriazole was obtained. Each of the mixed ester solutions was allowed to stand at 5 ° C. for 40 hours, and then the precipitate was visually confirmed.
In the mixed ester solution in which no precipitate was observed, the solubility of benzotriazole at 5 ° C. [the amount of benzotriazole dissolved in 1 g of mixed ester (g)] was set to 0.030 g / g or more. The mixed ester solution in which precipitates were observed was removed by filtration (filter paper; No. 5A, manufactured by Kiriyama Seisakusho), and the obtained filtrate was subjected to high performance liquid chromatography (AGILENT 1200SERIES, column: YMC). Pack Ph A-414 φ6.0 × 300 mm, mobile phase: tetrahydrofuran / 0.1% aqueous phosphoric acid solution = 7/3, column temperature: 40 ° C., flow rate: 0.7 mL / min, detection: UV (220 nm), sample Concentration: 50 g / L, injection amount: 5 μL), and the solubility of benzotriazole at 5 ° C. [dissolution amount of benzotriazole in 1 g of mixed ester (g)] was determined by an absolute calibration curve method. The results are shown in Tables 7 and 8.
混合エステル7~10、13、15および混合エステルAのそれぞれ43.65gに、ベンゾトリアゾール1.35gを混合し、60℃で加熱して、ベンゾトリアゾールの3重量%混合エステル溶液のそれぞれを得た。自動流動点測定器RPP-01CML(離合社製)を用い、JIS K2269-1987の方法に準じて、該3重量%混合エステル溶液のそれぞれの流動点を測定した。結果を表7および8に示す。表7および8において、BZTはベンゾトリアゾールを示す。 (Test Example 8) Measurement of pour point of mixed ester solution Each of mixed esters 7 to 10, 13, 15 and 43.65 g of mixed ester A was mixed with 1.35 g of benzotriazole and heated at 60 ° C. Each of the 3 wt% mixed ester solutions of triazole was obtained. Each pour point of the 3 wt% mixed ester solution was measured using an automatic pour point measuring device RPP-01CML (manufactured by Hosei Co., Ltd.) according to the method of JIS K2269-1987. The results are shown in Tables 7 and 8. In Tables 7 and 8, BZT represents benzotriazole.
混合エステル7~10、13および15のそれぞれ19.80gに、ベンゾトリアゾール0.20gを混合し、60℃で加熱して、ベンゾトリアゾールの1重量%混合エステル溶液のそれぞれを得た。得られた該1重量%混合エステル溶液のそれぞれを、シェル式四球摩擦試験機(神鋼造機社製)を用い、荷重200N、回転数1200rpm、時間30分間、温度75℃、試験材[試験球(SUJ-2)]の条件で試験を行い、試験後の摩耗痕径を測定した。摩耗痕径は3つの固定球の垂直方向、水平方向全ての平均値とした。結果を以下に示す。混合エステル溶液の耐摩耗性は、摩耗痕径の値が小さいもの程優れていることを表す。 (Test Example 9) Measurement of wear scar diameter of mixed ester solution Each of mixed esters 7 to 10, 13 and 15 was mixed with 19.80 g of benzotriazole 0.20 g and heated at 60 ° C. Each of the weight percent mixed ester solutions was obtained. Each of the obtained 1% by weight mixed ester solution was subjected to a load of 200 N, a rotation speed of 1200 rpm, a time of 30 minutes, a temperature of 75 ° C., a test material [test ball (test ball ( The test was conducted under the conditions of SUJ-2)], and the wear scar diameter after the test was measured. The wear scar diameter was the average value of all three fixed spheres in the vertical and horizontal directions. The results are shown below. The wear resistance of the mixed ester solution indicates that the smaller the wear scar diameter, the better.
Claims (4)
- ペンタエリスリトールおよび式(I)
で表されるジペンタエリスリトールからなる混合多価アルコールとイソ酪酸を含有するカルボン酸との混合エステルであって、前記混合多価アルコールにおけるペンタエリスリトールとジペンタエリスリトールのモル比[ペンタエリスリトール/ジペンタエリスリトール]が98/2~40/60の範囲であり、前記カルボン酸にしめるイソ酪酸の割合が35~85モル%の範囲である混合エステル。 Pentaerythritol and formula (I)
A mixed ester of a mixed polyhydric alcohol composed of dipentaerythritol and a carboxylic acid containing isobutyric acid represented by the formula: wherein the molar ratio of pentaerythritol and dipentaerythritol in the mixed polyhydric alcohol [pentaerythritol / dipenta Erythritol] is in the range of 98/2 to 40/60, and the mixed ester has a ratio of isobutyric acid to the carboxylic acid in the range of 35 to 85 mol%. - 前記カルボン酸がイソ酪酸と3,5,5-トリメチルヘキサン酸および/または2-エチルヘキサン酸とを含有する請求項1に記載の混合エステル。 The mixed ester according to claim 1, wherein the carboxylic acid contains isobutyric acid and 3,5,5-trimethylhexanoic acid and / or 2-ethylhexanoic acid.
- 前記カルボン酸がイソ酪酸と3,5,5-トリメチルヘキサン酸とからなる請求項1に記載の混合エステル。 The mixed ester according to claim 1, wherein the carboxylic acid comprises isobutyric acid and 3,5,5-trimethylhexanoic acid.
- 前記カルボン酸がイソ酪酸と2-エチルヘキサン酸とからなる請求項1に記載の混合エステル。
The mixed ester according to claim 1, wherein the carboxylic acid comprises isobutyric acid and 2-ethylhexanoic acid.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013556398A JP6083873B2 (en) | 2012-02-01 | 2013-01-29 | Mixed ester of mixed polyhydric alcohol and carboxylic acid |
CN201380007825.XA CN104093694B (en) | 2012-02-01 | 2013-01-29 | The mixed ester of polyol blend and carboxylic acid |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012019801 | 2012-02-01 | ||
JP2012-019801 | 2012-02-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013115160A1 true WO2013115160A1 (en) | 2013-08-08 |
Family
ID=48905197
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/051848 WO2013115160A1 (en) | 2012-02-01 | 2013-01-29 | Mixed ester of mixed polyhydric alcohol and carboxylic acid |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP6083873B2 (en) |
CN (1) | CN104093694B (en) |
WO (1) | WO2013115160A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015140352A (en) * | 2014-01-27 | 2015-08-03 | 日油株式会社 | Ester for refrigeration oil |
WO2015125883A1 (en) * | 2014-02-20 | 2015-08-27 | 旭硝子株式会社 | Composition for heat cycle system, and heat cycle system |
WO2015125881A1 (en) * | 2014-02-20 | 2015-08-27 | 旭硝子株式会社 | Composition for heat cycle system, and heat cycle system |
WO2015125884A1 (en) * | 2014-02-20 | 2015-08-27 | 旭硝子株式会社 | Composition for heat cycle system, and heat cycle system |
JP2016023902A (en) * | 2014-07-24 | 2016-02-08 | 日立アプライアンス株式会社 | Air conditioner |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114657010B (en) * | 2022-03-17 | 2023-06-27 | 苏州铱诺化学材料有限公司 | Lubricating oil for refrigerator and preparation method and application thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03227397A (en) * | 1989-11-29 | 1991-10-08 | Asahi Denka Kogyo Kk | Lubricant for freezer |
JPH0641575A (en) * | 1992-04-28 | 1994-02-15 | Lubrizol Corp:The | Liquid composition containing carboxylic acid ester mixture |
JPH0770577A (en) * | 1993-06-30 | 1995-03-14 | Nippon Oil & Fats Co Ltd | Synthetic lubricant, and working fluid composition for refrigerator |
WO1997011933A1 (en) * | 1995-09-25 | 1997-04-03 | Kao Corporation | Ester compounds and lubricating oil composition |
JP2002356694A (en) * | 2001-05-29 | 2002-12-13 | Nof Corp | Lubricating oil composition for operating fluid composition refrigerator and |
JP2005171233A (en) * | 2003-11-21 | 2005-06-30 | Nof Corp | Lubricant oil composition for refrigerating machine |
WO2012026212A1 (en) * | 2010-08-24 | 2012-03-01 | 協和発酵ケミカル株式会社 | Tetraester of pentaerythritol |
WO2012026214A1 (en) * | 2010-08-24 | 2012-03-01 | 協和発酵ケミカル株式会社 | Tetraester of pentaerythritol |
WO2012026303A1 (en) * | 2010-08-24 | 2012-03-01 | Jx日鉱日石エネルギー株式会社 | Refrigerating machine oil and working fluid composition for refrigerating machines |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0430657A1 (en) * | 1989-11-29 | 1991-06-05 | Asahi Denka Kogyo Kabushiki Kaisha | Lubricant for refrigerators |
CA2487587C (en) * | 2003-11-21 | 2012-04-24 | Nof Corporation | A polyol ester for use within a refrigeration lubricant composition compatible with chlorine-free hydrofluorocarbon refrigerants |
WO2010029704A1 (en) * | 2008-09-09 | 2010-03-18 | 株式会社ジャパンエナジー | Refrigerator oil for refrigerant 2,3,3,3-tetrafluoro-1-propene |
-
2013
- 2013-01-29 WO PCT/JP2013/051848 patent/WO2013115160A1/en active Application Filing
- 2013-01-29 JP JP2013556398A patent/JP6083873B2/en active Active
- 2013-01-29 CN CN201380007825.XA patent/CN104093694B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03227397A (en) * | 1989-11-29 | 1991-10-08 | Asahi Denka Kogyo Kk | Lubricant for freezer |
JPH0641575A (en) * | 1992-04-28 | 1994-02-15 | Lubrizol Corp:The | Liquid composition containing carboxylic acid ester mixture |
JPH0770577A (en) * | 1993-06-30 | 1995-03-14 | Nippon Oil & Fats Co Ltd | Synthetic lubricant, and working fluid composition for refrigerator |
WO1997011933A1 (en) * | 1995-09-25 | 1997-04-03 | Kao Corporation | Ester compounds and lubricating oil composition |
JP2002356694A (en) * | 2001-05-29 | 2002-12-13 | Nof Corp | Lubricating oil composition for operating fluid composition refrigerator and |
JP2005171233A (en) * | 2003-11-21 | 2005-06-30 | Nof Corp | Lubricant oil composition for refrigerating machine |
WO2012026212A1 (en) * | 2010-08-24 | 2012-03-01 | 協和発酵ケミカル株式会社 | Tetraester of pentaerythritol |
WO2012026214A1 (en) * | 2010-08-24 | 2012-03-01 | 協和発酵ケミカル株式会社 | Tetraester of pentaerythritol |
WO2012026303A1 (en) * | 2010-08-24 | 2012-03-01 | Jx日鉱日石エネルギー株式会社 | Refrigerating machine oil and working fluid composition for refrigerating machines |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015140352A (en) * | 2014-01-27 | 2015-08-03 | 日油株式会社 | Ester for refrigeration oil |
US9957429B2 (en) | 2014-02-20 | 2018-05-01 | Asahi Glass Company, Limited | Composition for heat cycle system, and heat cycle system |
WO2015125881A1 (en) * | 2014-02-20 | 2015-08-27 | 旭硝子株式会社 | Composition for heat cycle system, and heat cycle system |
WO2015125884A1 (en) * | 2014-02-20 | 2015-08-27 | 旭硝子株式会社 | Composition for heat cycle system, and heat cycle system |
JPWO2015125883A1 (en) * | 2014-02-20 | 2017-03-30 | 旭硝子株式会社 | Composition for thermal cycle system and thermal cycle system |
WO2015125883A1 (en) * | 2014-02-20 | 2015-08-27 | 旭硝子株式会社 | Composition for heat cycle system, and heat cycle system |
US9957430B2 (en) | 2014-02-20 | 2018-05-01 | Asahi Glass Company, Limited | Composition for heat cycle system, and heat cycle system |
US9976067B2 (en) | 2014-02-20 | 2018-05-22 | Asahi Glass Company, Limited | Composition for heat cycle system, and heat cycle system |
US10233371B2 (en) | 2014-02-20 | 2019-03-19 | AGC Inc. | Composition for heat cycle system, and heat cycle system |
US10392546B2 (en) | 2014-02-20 | 2019-08-27 | AGC Inc. | Composition for heat cycle system, and heat cycle system |
JP2020041149A (en) * | 2014-02-20 | 2020-03-19 | Agc株式会社 | Heat cycle system composition and heat cycle system |
US11072734B2 (en) | 2014-02-20 | 2021-07-27 | AGC Inc. | Composition for heat cycle system, and heat cycle system |
JP2016023902A (en) * | 2014-07-24 | 2016-02-08 | 日立アプライアンス株式会社 | Air conditioner |
Also Published As
Publication number | Publication date |
---|---|
CN104093694A (en) | 2014-10-08 |
JP6083873B2 (en) | 2017-02-22 |
CN104093694B (en) | 2016-03-23 |
JPWO2013115160A1 (en) | 2015-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5150790B2 (en) | Pentaerythritol tetraester | |
JP5089826B2 (en) | Pentaerythritol tetraester | |
JP6135017B2 (en) | Mixed ester | |
JP6083873B2 (en) | Mixed ester of mixed polyhydric alcohol and carboxylic acid | |
JP6115565B2 (en) | Mixed ester | |
JP5150791B2 (en) | Diester of neopentyl glycol | |
JP5572273B1 (en) | Hexaester of bispentaerythritol monoformal | |
JP2017019868A (en) | Tetraester of pentaerythritol | |
WO2012026213A1 (en) | Composition containing tetraester of pentaerythritol and diester of neopentyl glycol | |
JP2016193938A (en) | Tetraester of pentaerythritol | |
JP5979764B2 (en) | Pentaerythritol tetraester | |
JP5538636B1 (en) | Hexaester of bispentaerythritol monoformal | |
JP2015096470A (en) | Mixed ester |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201380007825.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13743116 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013556398 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13743116 Country of ref document: EP Kind code of ref document: A1 |