JP2016084286A - Ester compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ester compound that can be synthesized easily from a variety of carboxylic acid compounds, is hard to crystallize and volatilize, and has an excellent viscosity index.SOLUTION: The present invention provides an ester compound represented by general formula (1) where Rs independently represent C1-C25 aliphatic groups, aralkyl groups or aryl groups, R, Rand Rindependently represent C1-C10 alkyl groups.SELECTED DRAWING: None

Description

  The present invention relates to an ester compound and a method for producing the ester compound.

Ester-based synthetic oils such as polyol esters have a high balance of properties, such as viscosity characteristics, thermal stability, oxidation stability, lubricity, volatility, and low-temperature characteristics, compared to mineral oils. Synthetic oil widely used in the necessary lubrication field.
Among them, hindered polyol esters that do not have a hydrogen atom at the β-position of the ester carbonyl group are less susceptible to low activation energy type low-temperature decomposition via a quasi-cyclic intermediate and greatly improve thermal stability.

  For example, in the field of heat resistance applications, esters of hindered carboxylic acids and hindered polyols have been studied for further improvement of heat resistance. In order to increase the heat resistance, a combination with a tertiary carboxylic acid is preferable, but it is generally known that the viscosity index of the ester decreases as the carboxylic acid is changed to primary, secondary, or tertiary. Yes. The viscosity index is an important index as one of the characteristics of the lubricating oil, and in order to give a good viscosity index with an ester with a tertiary carboxylic acid, a long chain alkyl group is required (for example, Patent Document 1). Hindered polyols that give a better viscosity index).

  On the other hand, in a refrigeration cycle such as a car air conditioner, a building air conditioner, a freezer warehouse, and a refrigerator, a refrigerator oil composition in which a refrigerant is dissolved in refrigerator oil is used as a working fluid. Particularly in these areas, CFC (chlorofluorocarbon) and HCFC (hydrochlorofluorocarbon) are subject to regulation due to the problem of ozone layer destruction, and hydrofluorocarbon refrigerants are being used instead of these, and these refrigerants are dissolved. Polyol ester is used for refrigerating machine oil (for example, refer patent document 2). The specification of Patent Document 3 describes that a polyol ester oil consisting of one kind of alcohol and one kind of fatty acid is usually easily crystallized or solidified from room temperature to low temperature for use in a polyol ester for low temperature applications. In general, the use of polyol esters for low-temperature applications is known to be used by mixing various fatty acids in order to avoid crystallization.

  The problem of crystallization of polyol esters is well known not only in the fields of lubricating oils, greases and refrigerator base oils but also in the field of cosmetic raw materials. Patent Document 4 demands a polyol ester compound that is difficult to crystallize at room temperature, and describes that the amount of benzoic acid is limited due to crystallization.

JP 09-301919 A Japanese Patent Laid-Open No. 06-017073 JP 2013-133443 A International Publication No. 2006-033231

  In various fields such as jet engine oil, automobile engine oil, air compressor oil, and flame retardant hydraulic oil, thermal stability and oxidation stability are further improved due to recent demands for higher performance, more severe use environment, longer life, etc. An excellent lubricating oil is desired. Also in fields where low temperature characteristics are required, refrigerating machine oils with new characteristics are required due to environmental demands such as ozone depletion, and the development of polyol esters with further characteristics in various fields is desired. Has been done.

  Although hindered polyol esters having excellent heat resistance and viscosity characteristics in various fields, difficult crystallinity, and lower melting point are desired, hindered polyols actually used are neopentyl. Glycol (2,2-dimethylpropane-1,3-diol), trimethylolpropane (2-ethyl-2-hydroxymethylpropane-1,3-diol), pentaerythritol (2,2-bis (hydroxymethyl) propane -1,3-diol), ditrimethylolpropane (2,6-diethyl-2,6-bis (hydroxymethyl) -4-oxaheptane-1,7-diol), dipentaerythritol (2,2,6, 6-tetrakis (hydroxymethyl) -4-oxa-1,7-heptanediol), these Polyol skeleton capable of providing the applicable novel hindered polyol ester to the request has been widely desired.

  In view of these backgrounds, an object of the present invention is to provide an ester compound that can be easily synthesized from various carboxylic acid compounds, is hardly crystalline, hardly volatile, and has an excellent viscosity index.

  As a result of intensive investigations to achieve the above object, the present inventors have obtained an ester compound that is excellent in viscosity index and hardly crystalline and hardly volatile by using a triol compound having a specific structure. Has been found and has led to the present invention. That is, this invention is as follows and includes the following aspects.

[1] An ester compound represented by the following general formula (1).

In the formula, each R ¹ independently represents an aliphatic group having 1 to 25 carbon atoms, an aralkyl group, or an aryl group. R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group having 1 to 10 carbon atoms.
[2] In General Formula (1), R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, and R ¹¹ , R ^12, and R ¹³ each independently represents an alkyl group having 1 to 6 carbon atoms [ 1].
[3] The ester compound according to [1] or [2], wherein R ¹¹ and R ^{12 in the} general formula (1) are methyl groups.
[4] In the general formula (1), ^{R 1} is each independently represent an alkyl group having 1 to 12 carbon atoms [1] to ester compound according to any one of [3].
[5] In General Formula (1), each R ¹ independently represents a secondary alkyl group, a tertiary alkyl group, or a primary alkyl group containing a branched chain, described in any one of [1] to [4] The ester compound.
[6] A lubricating oil comprising the ester compound according to any one of [1] to [5].
[7] A cosmetic raw material containing the ester compound according to any one of [1] to [5].
[8] A cosmetic comprising the cosmetic material according to [7].
[9] An ester represented by the general formula (1), comprising a dehydration condensation reaction of a triol compound represented by the following general formula (2) and at least one carboxylic acid compound represented by the general formula (3) It is a manufacturing method of a compound.

In the formula, each R ¹ independently represents an aliphatic group having 1 to 25 carbon atoms, an aralkyl group, or an aryl group. R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group having 1 to 10 carbon atoms.
[10] The dehydration condensation reaction is performed in the presence of a catalyst, and the catalyst contains methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, sulfuric acid, and a sulfonic acid group. [9] which is at least one selected from the group consisting of a solid acid catalyst, hydrochloric acid, phosphoric acid, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, dioctyltin oxide and dibutyltin oxide It is a manufacturing method of the ester compound of description.
[11] It is represented by the general formula (1), comprising transesterifying the triol compound represented by the following general formula (2) and at least one carboxylic acid ester compound represented by the general formula (3a). It is a manufacturing method of an ester compound.

In the formula, each R ¹ independently represents an aliphatic group having 1 to 25 carbon atoms, an aralkyl group, or an aryl group. Z represents an aliphatic group having 1 to 3 carbon atoms. R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group having 1 to 10 carbon atoms.
[12] The transesterification reaction is performed in the presence of a catalyst, and the catalyst is sulfuric acid, p-toluenesulfonic acid, titanate, acetylacetone zinc, dibutyltin oxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, [11] The method for producing an ester compound according to [11], which is at least one selected from the group consisting of potassium hydroxide and sodium methoxide.

  According to the present invention, it is possible to provide an ester compound that can be easily synthesized from various carboxylic acid compounds and that is hardly crystalline, hardly volatile, and has an excellent viscosity index.

¹ H-NMR spectrum of tris (3,5,5-trimethylhexanoic acid) 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7-diyl obtained in Example 1 It is. It is the elements on larger scale of FIG. 2 is a ¹ H-NMR spectrum of tris (2-ethylhexanoic acid) 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7-diyl obtained in Example 2. FIG. 4 is a partially enlarged view of FIG. 3. 2 is a ¹ H-NMR spectrum of tris (2,2-dimethylbutanoic acid) 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7-diyl obtained in Example 3. It is the elements on larger scale of FIG. 2 is a ¹ H-NMR spectrum of 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7-diyl tribenzoate obtained in Example 4.

In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Moreover, content of each component in a composition means the total amount of the said some substance which exists in a composition, unless there is particular notice, when the substance applicable to each component exists in a composition in multiple numbers.
Hereinafter, embodiments according to the present invention will be described in detail.

  The ester compound according to this embodiment is represented by the following general formula (1). The ester compound represented by the following general formula (1) has a low melting point and is hardly crystalline, has a high viscosity index, and is suitable for use in a wide temperature range. Furthermore, it is excellent in heat resistance.

In the formula, each R ¹ independently represents an aliphatic group having 1 to 25 carbon atoms, an aralkyl group, or an aryl group. R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group having 1 to 10 carbon atoms.

The ester compound represented by the general formula (1) is a linear alkyl group in which R ¹¹ , R ^12, and R ¹³ are each independently a C 1-6 alkyl group from the viewpoints of raw material availability, difficult crystallinity, and high viscosity index. More preferably, R ¹¹ , R ¹² and R ¹³ are each independently independently a linear alkyl group having 1 to 4 carbon atoms, and it is more preferable that both R ¹¹ and R ¹² are methyl groups. .

The aliphatic group represented by R ¹ may be an alkyl group or an unsaturated aliphatic group such as an alkenyl group. The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. Is more preferable, and an alkyl group having 5 to 10 carbon atoms is particularly preferable. The alkyl group represented by R ¹ may be either linear or branched, and is preferably branched from the viewpoints of poor crystallinity, high viscosity index, heat resistance, and the like.
The alkyl group represented by R ¹ is preferably a secondary alkyl group, a tertiary alkyl group, or a primary alkyl group containing a branched chain, and a secondary alkyl group or tertiary alkyl group having 1 to 12 carbon atoms. Alternatively, a primary alkyl group containing a branched chain is more preferable, and a secondary alkyl group having 5 to 10 carbon atoms, a tertiary alkyl group, or a primary alkyl group containing a branched chain is more preferable.
The unsaturated aliphatic group represented by R ¹ may be linear or branched. Moreover, it is preferable that carbon number of an unsaturated aliphatic group is 2-25, and it is more preferable that it is 15-23.

The aralkyl group represented by R ¹ is composed of, for example, an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms and an alkyl having 1 to 5 carbon atoms. It is preferably composed of a group.
The aryl group represented by R ¹ is, for example, an aryl group having 6 to 14 carbon atoms, and preferably an aryl group having 6 to 10 carbon atoms.

In a preferred embodiment of the ester compound represented by the general formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms, and R ¹¹ , R ¹² and R ¹³ are each independently a straight chain having 1 to 6 carbon atoms. This is the case with an alkyl group. In a more preferred embodiment of the ester compound, R ¹ is a secondary alkyl group having 1 to 12 carbon atoms, a tertiary alkyl group, or a primary alkyl group containing a branched chain, and R ¹¹ , R ¹² and R ¹³ are each independently In the case of a straight-chain alkyl group having 1 to 4 carbon atoms. In a further preferred embodiment of the ester compound, R ¹ is a secondary alkyl group having 5 to 10 carbon atoms, a tertiary alkyl group, or a primary alkyl group containing a branched chain, wherein R ¹¹ , R ¹² and R ¹³ are independent of each other. In the case of a straight-chain alkyl group having 1 to 4 carbon atoms.

  The ester compound represented by the general formula (1) is, for example, a dehydration condensation reaction between a triol compound represented by the general formula (2) and a carboxylic acid compound (preferably a carboxylic acid compound represented by the general formula (3)). Or a triol compound represented by the general formula (2) and a carboxylic acid ester compound (preferably a carboxylic acid ester compound represented by the general formula (3a)).

In the formula, R ¹ and R ^{11 to} R ¹³ are as described above. Z represents an aliphatic group having 1 to 3 carbon atoms. The aliphatic group represented by Z is preferably an alkyl group having 1 to 3 carbon atoms.

  The diol described in the general formula (2) can be obtained, for example, by hydrogenating and reducing the acetal compound represented by the general formula (4). The reaction conditions for the hydrogenation reduction are not particularly limited, and can be appropriately selected from reaction conditions that are usually used.

In the formula, R ^{11 to} R ¹³ are as described above.

  Further, the acetal compound represented by the general formula (4) can be easily obtained as described in the following reaction formula: 2,2-disubstituted-3-hydroxypropanal and 2-substituted-2-hydroxymethylpropane- It can be obtained by acetalization of 1,3-diol. The reaction conditions for acetalization are not particularly limited, and can be appropriately selected from commonly used reaction conditions.

  Moreover, when synthesizing the ester compound represented by the general formula (1) by a dehydration condensation reaction or a transesterification reaction, the triol compound represented by the general formula (2) may be used alone or in two kinds. You may mix and use the above.

  Examples of carboxylic acid compounds that can be used in the dehydration condensation reaction include aliphatic carboxylic acid compounds, aralkyl carboxylic acid compounds, and aryl carboxylic acid compounds. Among these, the aliphatic carboxylic acid compound may be any of saturated and unsaturated primary carboxylic acid compounds, secondary carboxylic acid compounds, and tertiary carboxylic acid compounds. Further, the aliphatic group portion of the aliphatic carboxylic acid compound may be either linear or branched. Carboxylic acid compounds may be used alone or in combination of two or more.

  Examples of saturated linear primary carboxylic acid compounds include, for example, caproic acid, enanthic acid, caprylic acid, verargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid , Stearic acid, nonadecylic acid, arachidic acid, henicosyl, behenic acid, tricosylic acid, lignoceric acid, and the like, and at least one selected from the group consisting of these is preferable. More preferably, it is at least one selected from the group consisting of caproic acid, enanthic acid, caprylic acid, verargonic acid, capric acid, undecyl acid and lauric acid.

  The branched primary carboxylic acid compound and secondary carboxylic acid compound include structural isomers of these saturated linear primary carboxylic acid compounds. For example, examples of branched primary carboxylic acid compounds include 3,5,5-trimethylhexanoic acid, 3-methylvaleric acid, 4-methylvaleric acid, 5-methylhexanoic acid, 4-methyloctanoic acid, 4-ethyl. Examples include octanoic acid and 4-methylnonanoic acid, and at least one selected from the group consisting of these is preferable. More preferred is 3,5,5-trimethylhexanoic acid.

  Examples of secondary carboxylic acid compounds include 2-methylpentanoic acid, 2-ethylpentanoic acid, 2-propylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 2-ethylheptane. Acid, 2-propylheptanoic acid, 2-methyloctanoic acid, 2-ethyloctanoic acid, 2,4-dimethyloctanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-methylhexadecanoic acid, 2-decyldodecanoic acid, Examples include 2-hexadecyl octadecanoic acid, isomyristic acid and isostearic acid, and at least one selected from the group consisting of these is preferable. More preferably, it is at least one selected from the group consisting of 2-ethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 2-ethylheptanoic acid and 2-propylheptanoic acid. More preferably, it is at least one selected from the group consisting of 2-ethylhexanoic acid, 2-ethylheptanoic acid and 2-propylheptanoic acid.

  Examples of unsaturated primary carboxylic acid compounds include α-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosapentaenoic acid, linoleic acid, γ-linolenic acid, dihomoγ-linolenic acid, arachidonic acid, palmitoleic acid, vaccene Examples include acid, pauric acid, oleic acid, elaidic acid, erucic acid, and nervonic acid, and at least one selected from the group consisting of these is preferable.

  Examples of the tertiary carboxylic acid compound include structural isomers of the above-mentioned saturated linear primary carboxylic acid compound. For example, pivalic acid, 2,2-diisopropylpropionic acid, 2,2-dimethylbutyric acid, 2- Methyl-2-ethylbutyric acid, 2-ethyl-2,3,3-trimethylbutyric acid, 2,2-dimethylpentanoic acid, 2-methyl-2-ethylpentanoic acid, 2,2,3,3-tetramethylpentanoic acid 2,2,3,4-tetramethylpentanoic acid, 2,2,4,4-tetramethylpentanoic acid, 2,2-dimethylhexanoic acid, 2,2-dimethylheptanoic acid, 2,2-dimethyloctane Acid, 2,2-dimethylnonanoic acid, 2,2-dimethyldecanoic acid, 2,2-dimethylundecanoic acid, 2,2-dimethyldodecanoic acid, 2,2-dimethyltridecanoic acid, 2-methyl-2-ethyldo Canic acid, 2,2-dimethylpentadecanoic acid, 2-methyl-2-ethyltetradecanoic acid, 2,2-diethyltridecanoic acid, 2-methyl-2-ethyloctadecanoic acid, 2,2-diethylheptadecanoic acid and 2 , 2-diethylnonadecanoic acid and the like, and at least one selected from the group consisting of these is preferable.

  Moreover, you may add 0.9 equivalent or less dicarboxylic acid compound with respect to a triol compound as a carboxylic acid compound. Examples of the dicarboxylic acid compound include adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and at least one selected from the group consisting of these is preferred.

  The reaction conditions for the dehydration condensation reaction between the triol compound represented by the general formula (2) and the carboxylic acid compound are not particularly limited as long as a desired ester compound is obtained. The dehydration condensation reaction is performed at a reaction temperature of 100 to 250 ° C., for example. What is necessary is just to select reaction time suitably with the scale and temperature of reaction, for example, it is performed for 1 to 50 hours. The pressure is normal pressure or reduced pressure. In the case of reduced pressure, the pressure is usually 0.1 to 80 kPa.

A solvent may be used for the dehydration condensation reaction. When a solvent is used, an azeotropic solvent may be used as the solvent. When an azeotropic solvent is used, a solvent having an appropriate boiling point may be selected. For example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, cumene, and aliphatic carbonization such as heptane, octane, decane, cyclohexane, and decalin. Examples thereof include halogenated hydrocarbon solvents such as hydrogen solvent, chloroform, 1,2-dichloroethane and chlorobenzene, and at least one selected from the group consisting of these is preferable. Moreover, you may use a solvent in mixture of 2 or more types.
When using a solvent, the amount of solvent is 0.5-30 mass times with respect to the triol compound to be used, and 1-10 mass times is preferable.

A catalyst may be used for the dehydration condensation reaction. When using a catalyst, the usage-amount is preferable 0.01-4 mol% with respect to a triol compound. As the catalyst, commonly used organic acids, inorganic acids, Lewis acids and the like can be used. Organic acids include alkane sulfonic acids, aryl sulfonic acids and the like.
Specific examples of the catalyst include alkanesulfonic acid such as methanesulfonic acid and trifluoromethanesulfonic acid, and arylsulfonic acid includes p-toluenesulfonic acid, benzenesulfonic acid, and dodecylbenzenesulfonic acid, and inorganic acid. Examples of the acid include sulfuric acid, hydrochloric acid and phosphoric acid, and examples of the Lewis acid include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, dioctyltin oxide and dibutyltin oxide. At least one selected from the group consisting of Two or more kinds of catalysts can be mixed and used.
As the catalyst, remarkable acceleration of the reaction can be expected particularly when a sulfonic acid-based catalyst having a pKa of 2 or less, such as p-toluenesulfonic acid, methanesulfonic acid and sulfuric acid is used.

  The molar ratio of the triol compound represented by the general formula (2) and the carboxylic acid compound (triol compound: carboxylic acid compound) used in the dehydration condensation reaction is, for example, 1.0: 3.0 to 1.0: 10. 0, preferably 1.0: 3.0 to 1.0: 5.0.

Examples of carboxylic acid ester compounds that can be used in the transesterification reaction include aliphatic carboxylic acid ester compounds, aralkyl carboxylic acid ester compounds, and aryl carboxylic acid ester compounds. Among these, the aliphatic carboxylic acid ester compound may be a saturated or unsaturated primary carboxylic acid ester compound, a secondary carboxylic acid ester compound, or a tertiary carboxylic acid ester compound. Further, the aliphatic group portion of the aliphatic carboxylic acid ester compound may be either linear or branched. The aliphatic carboxylic acid ester compounds may be used alone or in combination of two or more.
As specific examples of the following carboxylic acid ester compounds, only methyl esters are illustrated, but not limited to methyl esters, and may be carboxylic acid ester compounds derived from alcohols having 1 to 3 carbon atoms.

  Examples of saturated primary carboxylic acid ester compounds include methyl caproate, methyl enanthate, methyl caprylate, methyl verargonate, methyl caprate, methyl undecylate, methyl laurate, methyl tridecylate, methyl myristate, pentadecylic acid Examples include methyl, methyl palmitate, methyl margarate, methyl stearate, methyl nonadecylate, methyl arachidate, methyl hehenosyl, methyl behenate, methyl tricosylate, and methyl lignocerate, and are selected from the group consisting of these At least one is preferred. More preferably, it is at least one selected from the group consisting of methyl caproate, methyl enanthate, methyl caprylate, methyl verargonate, methyl caprate, methyl undecylate and methyl laurate. Examples of the saturated secondary and tertiary carboxylic acid ester compounds include structural isomers of the above-described saturated primary carboxylic acid ester compounds.

  Examples of unsaturated primary carboxylic acid ester compounds include methyl α-linolenate, methyl stearidone, methyl eicosapentanoate, methyl docosapentaenoate, methyl linoleate, methyl γ-linolenate, and dihomo γ-linolenic acid. And methyl, arachidonic acid methyl, palmitoleic acid methyl, vaccenate, methyl paurate, methyl oleate, methyl elaidate, methyl erucate and methyl nervate, and at least one selected from the group consisting of these is preferred. .

  The reaction conditions for the transesterification reaction between the triol compound represented by the general formula (2) and the carboxylic acid ester compound are not particularly limited as long as the desired ester compound is obtained. The transesterification reaction is performed, for example, at a reaction temperature of 100 to 250 ° C. while removing alcohol generated from the carboxylic acid ester compound from the reaction system. What is necessary is just to select reaction time suitably with the scale and temperature of reaction, for example, it is performed for 1 to 50 hours. The pressure is normal pressure or reduced pressure. In the case of reduced pressure, the pressure is usually 0.1 to 80 kPa.

A catalyst can be used for the transesterification reaction. The catalysts used are acidic catalysts such as sulfuric acid and p-toluenesulfonic acid, Lewis acid catalysts such as titanate ester, zinc acetate, acetylacetone zinc and dibutyltin oxide, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, water Any selected from basic catalysts such as potassium oxide and sodium methoxide may be used. Two or more kinds of catalysts can be mixed and used.
When using a catalyst, the usage-amount of a catalyst is preferable 0.1-4 mol% corresponding to a triol compound.

  The molar ratio of the triol compound represented by the general formula (2) and the carboxylic acid ester compound (triol compound: carboxylic acid ester compound) used in the transesterification reaction is, for example, 1.0: 3.0 to 1.0: 10.0, preferably 1.0: 3.0 to 1.0: 5.0.

  For the ester compound represented by the general formula (1), commonly used load-resistant additives, oiliness agents, antioxidants, detergent dispersants, antifoaming agents, rust preventives, demulsifiers, pour point depressants, viscosity At least one additive selected from index improvers and the like can be blended as necessary and used as a composition.

  In addition, the ester compound represented by the general formula (1) may include other lubricating base oils such as mineral oil, polyalphaolefin, polybutene, alkylbenzene, animal and vegetable oils, as necessary, as long as the performance is not significantly reduced. It is also possible to mix at least one selected from organic acid esters, polyvinyl ethers, polyphenyl ethers, alkylphenyl ethers, and the like, if necessary, and use them as a composition.

  The use of the ester compound represented by the general formula (1) and the composition containing the ester compound is not particularly limited. For example, an ester compound represented by the general formula (1) is used as a base oil, grease, refrigerating machine oil, insulating oil, hydraulic hydraulic oil, gear operating system lubricating oil, cutting / grinding oil, transmission lubricating oil, wind power generation It can be appropriately used for applications such as a speed increaser oil, an internal combustion engine lubricating oil (engine oil), a power turbine lubricating oil, a compressor lubricating oil, and a bearing lubricating oil.

  In addition, ester compounds represented by the general formula (1) are lipsticks, eye shadows, hair cosmetics, emulsions, water-in-oil hand creams, creamy oil-in-water sunscreen cosmetics, beauty nails, lipsticks as cosmetic raw materials. It can be used by appropriately blending into cream, lip gloss and the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Analysis of the reaction was performed by gas chromatography. For gas chromatography, 6850 manufactured by Agilent Technologies was used. The column used was HP-1 manufactured by J & W. The column temperature was maintained at 100 ° C. for 5 minutes, then heated to 275 ° C. at 10 ° C./minute, and then maintained for 20 minutes. The injection temperature was 270 ° C., the detector was TCD, and the temperature was 290 ° C. Helium was used as the carrier gas.
The product was identified by ¹ H-NMR spectrum. The measured using JEOL Ltd. JNM-ECA500, solvent and CDCl _3, using tetramethylsilane as the internal standard.

Synthesis example 1
Synthesis of 2- (5-ethyl-5-hydroxymethyl- [1,3] dioxan-2-yl) -2-methylpropan-1-ol 2,2-dimethyl-3-hydroxypropionaldehyde (hydroxypivalaldehyde) 45.1 g of Mitsubishi Gas Chemical Co., Inc., purity 99.8%), 59.6 g of 2-ethyl-2-hydroxymethylpropane-1,3-diol (trimethylolpropane, Tokyo Chemical Industry), and benzene 706 g and 5.0 g of granular Nafion (trade name “NR-50”, Sigma-Aldrich Reagent) are placed in a 2 liter round bottom flask and Dean Stark is azeotroped with benzene under normal pressure. -It was extracted out of the system using a trap and allowed to react until the distillation of water stopped. This was filtered and then recrystallized by concentration and cooling to give 2- (5-ethyl-5-hydroxymethyl- [1,3] dioxan-2-yl) -2-methylpropan-1-ol. Crystals were obtained.

  The catalyst used for hydrogenation of acetal was synthesized as follows.

Carrier preparation Zirconium oxide used as a carrier for the metal component was prepared by the following method.
A white precipitate was obtained by dropping 15.5 g of 28 wt% aqueous ammonia with stirring into 505 g of an aqueous zirconium oxynitrate solution having a concentration of 25 wt% in terms of zirconium oxide (ZrO ₂ ). This was filtered, washed with ion-exchanged water, and then dried at 110 ° C. for 10 hours to obtain hydrous zirconium oxide. This is stored in a magnetic crucible, subjected to a baking treatment at 400 ° C. for 3 hours in air using an electric furnace, and then pulverized in an agate mortar to be expressed as powdered zirconium oxide (hereinafter also referred to as “carrier A”). .) The BET specific surface area (measured by the nitrogen adsorption method) of the carrier A was 102.7 m ² / g.

Catalyst preparation A catalyst containing palladium as a specific metal component was prepared by the following method.
0.66 mass% palladium chloride-0.44 mass% sodium chloride aqueous solution was added to 50 g of carrier A, and the metal component was adsorbed on the carrier. A formaldehyde-sodium hydroxide aqueous solution was added thereto to instantaneously reduce the adsorbed metal component. Thereafter, the catalyst was washed with ion-exchanged water and dried to prepare a 1.0 mass% palladium-supported zirconium oxide catalyst (hereinafter also referred to as “catalyst A”).

Synthesis example 2
Synthesis of 2-ethyl-2- (3-hydroxy-2,2-dimethyl-propoxymethyl) -propane-1,3-diol In a 500 mL SUS reactor, 7.5 g of catalyst A, 2- (5 -75 g of ethyl-5-hydroxymethyl- [1,3] dioxan-2-yl) -2-methylpropan-1-ol and 225 g of dioxane were accommodated, and the inside of the reactor was replaced with nitrogen gas. Thereafter, 8.5 MPa of hydrogen gas was charged into the reactor, the temperature was raised to 230 ° C., which is the reaction temperature, and the reaction was performed for 8 hours. Thereafter, the contents of the reactor were recovered by cooling and recrystallized to obtain the desired product.

Example 1
Tris (3,5,5-trimethylhexanoic acid) Synthesis of 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7-diyl 6,6-dimethyl-2-ethyl- To a toluene solution of 2-hydroxymethyl-4-oxaheptane-1,7-diol (20.00 g, 91 mmol) and 3,5,5-trimethylhexanoic acid (51.77 g, 327 mmol, 3.6 eq) at room temperature. p-Toluenesulfonic acid monohydrate (525.2 mg, 2.76 mmol, 3 mol%) was added. Thereafter, the mixture was heated under nitrogen, and water was removed from the system by azeotropy with toluene. Upon heating for 42 hours and cooling, the triester compound was 99 Area% by GC analysis.
After washing with 1M sodium hydroxide, it was washed with water until the washing solution became neutral. 3,5,5-Trimethylhexanoic acid was distilled off under reduced pressure and then treated with activated carbon to obtain 54.7 g of the desired product in a yield of 86%.
FIG. 1 shows an overall view of the ¹ H-NMR spectrum, and FIG. 2 shows an enlarged view of the high magnetic field region.

¹ H-NMR
δ (ppm): 0.86 (t, 3H, J = 7.6 Hz, C H ₃ CH ₂ ), 0.90-0.92 (m, 33H, 2 × (C H ₃ ) ₃ C + (C H ₃ ) ₃ C + 2 × C H ₃ C), 0.97 (d, 6H, J = 6.6 Hz, 2 × C H ₃ CH), 0.98 (d, 3H, J = 6.6 Hz, C H ₃ CH), 1.09-1.15 (m, 3H, 3 × (1H of C H ₂ C (CH ₃ ) ₃ )), 1.21-1.27 (m, 3H, 3 × (C H ₂ C _{(CH 3) 3)} 1H _{of), 1.46 (q, 2H,} J = 7.6Hz, CH 3 C H 2), 1.97-2.08 (m, 3H, 3 × C H CH 3 ), 2.09-2.15 (m, 3H, 3 × (1H of C H ₂ COO)), 2.29-2.35 (1H of m, 3H, 3 × (C H ₂ COO)), 3.13 (s, 2H, OC H ₂ ), 3.28 (s, 2H, OC H ₂ ), 3.84 (d, 1H, J = 10.7 Hz, C H ₂ OCO), 3.87 (d, 1H, J = 10.7 Hz, C H ₂ OCO), 3.96-4.04 (m, 4H, 2 × C H ₂ OCO)

Example 2
Tris (2-ethylhexanoic acid) Synthesis of 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7-diyl 6,6-dimethyl-2-ethyl-2-hydroxymethyl A solution of -4-oxaheptane-1,7-diol (20.07 g, 91 mmol) and 2-ethylhexanoic acid (65.48 g, 454 mmol, 5 eq) was heated to 200 ° C. under a nitrogen stream. After heating for 34 hours, 2-ethylhexanoic acid was distilled off under reduced pressure. The obtained product was treated with activated carbon to obtain the desired product in 52.5 g and a yield of 96%.
FIG. 3 shows an overall view of the ¹ H-NMR spectrum, and FIG. 4 shows an enlarged view of the high magnetic field region.

¹ H-NMR
δ (ppm): 0.84-0.91 (m, 21H, 3 × C H ₃ CH ₂ CH ₂ + 3 × C H ₃ CH ₂ CH + C H ₃ CH ₂ ), 0.92 (s, 6H, 2 × _{C H 3), 1.18-1.36 (m} , 12H, 3 × C H 2 C H 2 CH 3), 1.40-1.69 (m, 14H, 3 × C H 2 CHC H 2 CH ₃ + C H ₂ CH ₃ ), 2.23-2.31 (m, 3H, 3 × C H COO), 3.14 (s, 2H, C H ₂ O), 3.28 (s, 2H, C H ₂ O), 3.86 (s, 2H, C H ₂ OCO), 4.00 (s, 4H, 2 × C H ₂ OCO)

Example 3
Tris (2,2-dimethylbutanoic acid) Synthesis of 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7-diyl 6,6-dimethyl-2-ethyl-2-hydroxy A solution of methyl-4-oxaheptane-1,7-diol (20.00 g, 91 mmol) and 2,2-dimethylbutanoic acid (52.74 g, 454 mmol, 5 eq) was heated to 200 ° C. under a nitrogen stream. After heating for 50 hours, 2,2-dimethylbutanoic acid was distilled off under reduced pressure. The obtained mixture was purified by silica gel column chromatography to obtain the desired product at 37.7 g in a yield of 81%.
FIG. 5 shows an overall view of the ¹ H-NMR spectrum, and FIG. 6 shows an enlarged view of the high magnetic field region.

¹ H-NMR
δ (ppm): 0.82 (t, 6H, J = 7.6 Hz, 2 × C H ₃ CH ₂ ), 0.84 (t, 3H, J = 7.4 Hz, C H ₃ CH ₂ ), 0 .86 (t, 3H, J = 7.6 Hz, C H ₃ CH ₂ ), 0.91 (s, 6H, 2 × C H ₃ C), 1.15 (s, 12H, 4 × C H ₃ C) ), 1.16 (s, 6H, 2 × C H ₃ C), 1.46 (q, 2H, J = 7.6 Hz, C H ₂ CH ₃ ), 1.52-1.59 (m, 6H) , 3 × C H ₂ CH ₃ ), 3.14 (s, 2H, C H ₂ O), 3.28 (s, 2H, C H ₂ O), 3.83 (s, 2H, C H ₂ OCO) ), 3.97 (s, 4H, 2 × C H ₂ OCO)

Example 4
Synthesis of 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7-diyl tribenzoate 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane- 1,7-diol (10.01 g, 45 mmol) and benzoic acid (22.18 g, 182 mmol, 4 eq) were heated to 200 ° C. under a nitrogen stream. In order to suppress sublimation of benzoic acid, m-xylene was added. After heating for 25 hours, benzoic acid was removed by sublimation and then cooled. Ethyl acetate was added to the viscous liquid, washed with saturated sodium bicarbonate, and then washed with water. After the activated carbon treatment, ethyl acetate was distilled off with an evaporator and then dried under reduced pressure to obtain 23.42 g of the desired product in a yield of 97%.
FIG. 7 shows an overall view of the ¹ H-NMR spectrum.

¹ H-NMR
δ (ppm): 0.96 (t, 3H, J = 7.6 Hz, C H ₃ CH ₂ ), 1.00 (s, 6H, 2 × C H ₃ ), 1.67 (q, 2H, J = 7.6 Hz, C H ₂ CH ₃ ), 3.29 (s, 2 H, C H ₂ O), 3.51 (s, 2 H, C H ₂ O), 4.13 (s, 2 H, C H ₂ OCO), 4.38 (d, 2H, J = 7.6 Hz, 2 × (C H ₂ OCO 1H)), 4.41 (d, 2H, J = 7.6 Hz, 2 × (C H ₂ 1H of OCO)) 7.36-7.42 (m, 6H, aromatic ring meta position), 7.50-7.56 (m, 3H, aromatic ring para position), 7.96-8.01 (m , 6H, aromatic ring ortho position)

Comparative Example 1
Tris (3,5,5-trimethylhexanoic acid) Synthesis of 2-ethyl-2-hydroxymethylpropane-1,3-diyl 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4 of Example 1 -In place of oxaheptane-1,7-diol, 2-ethyl-2-hydroxymethylpropane-1,3-diol is used and the reaction is carried out under the same conditions as in Example 1, and water is used as an azeotrope with toluene. Removed from inside. The target product was obtained by performing post-treatment similar to Example 1 after heating.

¹ H-NMR
δ (ppm): 0.89 (t, 3H, J = 7.4 Hz, C H ₃ CH ₂ ), 0.90 (s, 27H, 3 × (C H ₃ ) ₃ C), 0.97 (d , 9H, J = 6.6 Hz, 3 × C H ₃ CH), 1.12 (dd, 3H, J = 14.0, 6.3 Hz, 3 × (C H ₂ C (CH ₃ ) ₃ 1H)) ), 1.22 (dd, 3H, J = 14.0, 4.0 Hz, 3 × (1H of C H ₂ C (CH ₃ ) ₃ )), 1.49 (q, 2H, J = 7.4 Hz) , C H ₂ CH ₃ ), 1.97-2.07 (m, 3H, 3 × C H CH ₃ ), 2.13 (dd, 3H, J = 14.6, 8.3 Hz, 3 × (C H ₂ COO 1H)), 2.32 (dd, 3H, J = 14.6, 5.7 Hz, 3 × (C H ₂ COO 1H)), 3.98-4.05 (m, 6H, 3 × C H ₂ OCO)

Comparative Example 2
Tris (2-ethylhexanoic acid) Synthesis of 2-ethyl-2-hydroxymethylpropane-1,3-diyl 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane of Example 2 The reaction was carried out under the same conditions as in Example 2 except that 2-ethyl-2-hydroxymethylpropane-1,3-diol was used instead of 1,7-diol. After completion of the reaction, the same treatment as in Example 2 was performed to obtain the target product.

¹ H-NMR
δ (ppm): 0.84-0.92 (m, 21H, 3 × C H ₃ CH ₂ CH ₂ + 3 × C H ₃ CH ₂ CH + C H ₃ CH ₂ C), 1.16 to 1.36 (m _{, 12H, 3 × C H 2} C H 2 CH 3), 1.41-1.65 (m, 14H, 3 × OCOCH (C H 2 CH 3) C H 2 CH 2 + C H 2 CH 3), 2 .24-2.32 (m, 3H, 3 x C H COO), 4.02 (s, 6 H , 3 x C H ₂ OCO)

Comparative Example 3
Tris (2,2-dimethylbutanoic acid) Synthesis of 2-ethyl-2-hydroxymethylpropane-1,3-diyl 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane of Example 3 The reaction was carried out under the same conditions as in Example 3 except that 2-ethyl-2-hydroxymethylpropane-1,3-diol was used instead of -1,7-diol. After completion of the reaction, the same treatment as in Example 3 was performed to obtain the target product.

¹ H-NMR
δ (ppm): 0.82 (t, 9H, J = 7.6 Hz, 3 × C H ₃ CH ₂ ), 0.90 (t, 3H, J = 7.6 Hz, C H ₃ CH ₂ ), 1 .15 (s, 18H, 6 × C H ₃ C), 1.50 (q, 2H, J = 7.6 Hz, C H ₂ CH ₃ ), 1.56 (q, 6H, J = 7.6 Hz, 3 × C H ₂ CH ₃ ), 3.99 (s, 6H, 3 × C H ₂ OCO)

Comparative Example 4
Synthesis of 2-ethyl-2-hydroxymethylpropane-1,3-diyl tribenzoate To 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7-diol of Example 4 Instead, 2-ethyl-2-hydroxymethylpropane-1,3-diol was used and the reaction was carried out under the same conditions as in Example 4. After completion of the reaction, the same treatment as in Example 4 was performed to obtain the target product.

¹ H-NMR
δ (ppm): 1.07 (t, 3H, J = 7.6 Hz, C H ₃ CH ₂ ), 1.80 (q, 2H, J = 7.6 Hz, C H ₂ CH ₃ ), 4.51 (S, 6H, 3 × C H ₂ OCO), 7.39-7.44 (m, 6H, aromatic ring meta position), 7.53-7.58 (m, 3H, aromatic ring para position), 7 .99-8.03 (m, 6H, aromatic ring ortho position)

Comparative Example 5
Synthesis of bis (3,5,5-trimethylhexanoic acid) 2,2-dimethylpropane-1,3-diyl 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane of Example 1 The reaction was carried out under the same conditions as in Example 1 using 2,2-dimethylpropane-1,3-diol instead of -1,7-diol, and water was removed from the system by azeotropy with toluene. The target product was obtained by performing post-treatment similar to Example 1 after heating.

¹ H-NMR:
δ (ppm): 0.91, (s, 18H, 2 × C (C H ₃ ) ₃ ), 0.98 (s, 6H, 2 × C H ₃ ), 0.98 (d, 6H, J = 6.6 Hz, 2 × C H ₃ CH ₂ ), 1.13 (dd, 2H, J = 6.3, 14.0 Hz, 2 × C H ₂ C (CH ₃ ) ₃ 1H), 1.24 ( dd, 2H, J = 4.0, 14.0 Hz, 2 × C H ₂ C (CH ₃ ) ₃ 1H), 1.99-2.08 (m, 2H, 2 × C H CH ₃ ), 2 .14 (dd, 2H, J = 8.3, 14.5 Hz, 1H of 2 × OCOC H ₂ ), 2.33 (dd, 2H, J = 5.7, 14.5 Hz, 2 × OCOC H ₂ 1H), 3.861 (d, 1H, J = 10.9 Hz, C H ₂ OCO), 3.866 (d, 1H, J = 10.9 Hz, C H ₂ OCO), 3.899 (d, 1H , J _{10.9Hz, C H 2 OCO),} 3.905 (d, 1H, J = 10.9Hz, C H 2 OCO)

Comparative Example 6
Synthesis of bis (3,5,5-trimethylhexanoic acid) 4-oxa-2,2,6,6-tetramethylheptane-1,7-diyl 6,6-dimethyl-2-ethyl- of Example 1 Using 4-oxa-2,2,6,6-tetramethylheptane-1,7-diol instead of 2-hydroxymethyl-4-oxaheptane-1,7-diol, the reaction was carried out under the same conditions as in Example 1. The water was removed from the system by azeotropy with toluene. The target product was obtained by performing post-treatment similar to Example 1 after heating.

¹ H-NMR:
δ (ppm): 0.91 (s, 18H, 2 × C (C H ₃ ) ₃ ), 0.92 (s, 12H, 4 × C H ₃ ), 0.98 (d, 6H, J = 6) .6 Hz, 2 × C H ₃ CH ₂ ), 1.12 (dd, 2 H, J = 6.2, 14.1 Hz, 1 H of ₂ × C H ₂ C (CH ₃ ) ₃ ), 1.25 (dd , 2H, J = 4.3, 14.1 Hz, 2 × C H ₂ C (CH ₃ ) ₃ 1H), 2.00-2.08 (m, 2H, 2 × C H CH ₃ ), 2. 13 (dd, 2H, J = 8.3, 14.2 Hz, 2 × OCOC H ₂ 1H), 2.32 (dd, 2H, J = 5.7, 14.2 Hz, 2 × OCOC H ₂ 1H ), 3.14 (s, 4H, 2 × OC H ₂ ), 3.85 (d, 2H, J = 10.8 Hz, 1H of 2 × C H ₂ OCO), 3.89 (d, 2H, J = 10.8Hz, 2 × C H ₂ OCO 1H)

Comparative Example 7
Synthesis of bis (2-ethylhexanoic acid) 2,2-dimethylpropane-1,3-diyl 6,6-dimethyl-2-ethyl-2-hydroxymethyl-4-oxaheptane-1,7 of Example 2 The reaction was carried out under the same conditions as in Example 2 except that 2,2-dimethylpropane-1,3-diol was used instead of the diol. After completion of the reaction, the same treatment as in Example 2 was performed to obtain the target product.

¹ H-NMR
δ (ppm): 0.86-0.91 (m, 12H, 2 × C H ₃ CH ₂ + 2 × C H ₃ CH ₂ ), 0.99 (s, 6H, 2 × C H ₃ ), 1. 20-1.35 (m, 8H, 2 × CH 3 C H 2 C H 2), 1.42-1.66 (m, 8H, 2 × COCH (C H 2 CH 3) C H 2 CH 2) , 2.25-2.32 (m, 2H, 2 × OCO CH ), 3.894 (1H of s, 2H, 2 × C H ₂ OCO), 3.896 (s, 2H, 2 × C H ₂ 1H of OCO)

Comparative Example 8
Synthesis of bis (2-ethylhexanoic acid) 4-oxa-2,2,6,6-tetramethylheptane-1,7-diyl 6,6-dimethyl-2-ethyl-2-hydroxymethyl of Example 1 Instead of -4-oxaheptane-1,7-diol, instead of 4-oxa-2,2,6,6-tetramethylheptane-1,7-diol and 3,5,5-trimethylhexanoic acid, 2- Water was removed from the system by azeotropic distillation with a solvent in the same manner as in Example 1 except that ethylhexanoic acid was replaced with toluene and m-xylene was used. The target product was obtained by performing post-treatment similar to Example 1 after heating.

¹ H-NMR
δ (ppm): 0.86-0.91 (m, 12H, 2 × C H ₃ CH ₂ + 2 × C H ₃ CH ₂ ), 0.92 (s, 12H, 4 × C H ₃ ), 20-1.35 (m, 8H, 2 × CH 3 C H 2 C H 2), 1.42-1.66 (m, 8H, 2 × COCH (C H 2 CH 3) C H 2 CH 2) , 2.23-2.31 (m, 2H, 2 × OCOC H ), 3.14 (s, 4H, 2 × OC H ₂ C), 3.87 (s, 4H, 2 × C H ₂ OCO)

<Evaluation>
The following evaluation was performed about the ester compound obtained above.
Melting point: The melting point was determined by differential scanning calorimetry (DSC) measurement. Differential scanning calorimeter (DSC) measurement was performed using DSC7020 manufactured by SII.
Kinematic viscosity: Kinematic viscosity was determined according to JIS K2283 using an Ubbelohde viscometer.
Viscosity index: Viscosity index was determined from kinematic viscosity at 40 ° C. and 100 ° C. according to JIS K2283.
Weight reduction rate: The weight reduction rate of the ester compound was determined by using Thermo Plus TG8120 manufactured by Rigaku Corporation and measuring at a temperature increase rate of 10 ° C./min from room temperature in a nitrogen stream of 150 ml / min.

  The kinematic viscosity was measured for the ester compounds obtained in Examples 1 to 3 and Comparative Examples 1 to 3, and the viscosity index was determined. The results are shown in Table 1.

  As shown in Table 1, in esters with various carboxylic acids such as primary, secondary, and tertiary, the ester compound of the present invention has a corresponding general-purpose 2-ethyl-2-hydroxymethylpropane-1,3- Compared with the ester compound of diol, the viscosity index was large and a great improvement was observed.

  The melting points of the tribenzoic acid esters obtained in Example 4 and Comparative Example 4 were measured. The results are shown in Table 2.

  As shown in Table 2, the benzoate ester of the triol compound according to the present invention had a lower melting point than the general-purpose 2-ethyl-2-hydroxymethylpropane-1,3-diol benzoate ester. The benzoic acid ester of 2-ethyl-2-hydroxymethylpropane-1,3-diol is rapidly crystallized after concentration under reduced pressure, whereas the benzoic acid ester according to the present invention is slow in crystal precipitation. Compared with the benzoic acid ester of ethyl-2-hydroxymethylpropane-1,3-diol, it was hardly crystalline.

  About the ester compound obtained in Examples 1-2, Comparative Examples 1-2, and Comparative Examples 5-8, the weight reduction rate at the time of a heating is calculated | required by TG-GTA measurement, and the weight reduction of 10% and 30% is given. The volatility of the ester was evaluated from the temperature. The results are shown in Table 3.

  As shown in Table 3, the ester compound of the present invention contains 2-ethyl-2-hydroxymethylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol and 4-oxa which are comparative examples. Compared with 3,5,5-trimethylhexanoic acid ester of 2,2,6,6-tetramethylheptane-1,7-diol or 2-ethylhexanoic acid ester, the weight loss during heating is slow and volatilization It was clarified that it has the characteristics of a lubricating oil that can be used up to a high temperature because its properties are small.

  The ester compound according to the present invention synthesized from a triol compound having a specific structure and various carboxylic acid compounds or carboxylic acid ester compounds includes grease, refrigeration oil, insulating oil, hydraulic fluid, lubricant for gear operating system, cutting and grinding. Processing oil, transmission lubricating oil, wind power speed increasing oil, internal combustion engine lubricating oil (engine oil), power turbine lubricating oil, compressor lubricating oil, bearing lubricating oil, and various cosmetics as cosmetic raw materials It can be used for a wide range of applications.

Claims (12)

An ester compound represented by the following general formula (1).

(In the formula, each R ¹ independently represents an aliphatic group having 1 to 25 carbon atoms, an aralkyl group or an aryl group. R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group having 1 to 10 carbon atoms. .) 2. The general formula (1), wherein R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, and R ¹¹ , R ^12, and R ¹³ each independently represents an alkyl group having 1 to 6 carbon atoms. Ester compounds. The ester compound according to claim 1, wherein R ¹¹ and R ^{12 in the} general formula (1) are methyl groups. The ester compound according to any one of claims 1 to 3, wherein R ¹ in the general formula (1) independently represents an alkyl group having 1 to 12 carbon atoms. In the general formula (1), R ¹ each independently secondary alkyl group, tertiary alkyl group or an ester compound according to any one of claims 1 to 4, representing a primary alkyl group containing a branched chain.   The lubricating oil containing the ester compound of any one of Claims 1-5.   Cosmetic raw material containing the ester compound according to any one of claims 1 to 5.   A cosmetic comprising the cosmetic raw material according to claim 7. Production of ester compound represented by general formula (1), comprising dehydrating condensation reaction of triol compound represented by general formula (2) below and at least one carboxylic acid compound represented by general formula (3) Method.

(In the formula, each R ¹ independently represents an aliphatic group having 1 to 25 carbon atoms, an aralkyl group or an aryl group. R ¹¹ , R ¹² and R ¹³ each independently represents an alkyl group having 1 to 10 carbon atoms. .)   Solid acid catalyst in which dehydration condensation reaction is performed in the presence of a catalyst, and the catalyst contains methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, sulfuric acid, sulfonic acid group 10. The ester compound according to claim 9, wherein the ester compound is at least one selected from the group consisting of hydrochloric acid, phosphoric acid, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, dioctyltin oxide and dibutyltin oxide. Manufacturing method. The ester compound represented by the general formula (1) comprising transesterification of a triol compound represented by the following general formula (2) and at least one carboxylic acid ester compound represented by the general formula (3a): Production method.

(In the formula, each R ¹ independently represents an aliphatic group having 1 to 25 carbon atoms, an aralkyl group or an aryl group. Z represents an aliphatic group having 1 to 3 carbon atoms. R ¹¹ , R ¹² and R ^13. Each independently represents an alkyl group having 1 to 10 carbon atoms.)   The transesterification reaction is carried out in the presence of a catalyst, and the catalyst is sulfuric acid, p-toluenesulfonic acid, titanate ester, acetylacetone zinc, dibutyltin oxide, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide. The method for producing an ester compound according to claim 11, which is at least one selected from the group consisting of sodium methoxide and sodium methoxide.