JP5638438B2 - Alkyl diether alkyl monoester compounds of trimethylol alkanes, lubricating base oils, lubricating oils, grease base oils, and greases - Google Patents

Description

  The present invention relates to an alkyldiether alkyl monoester compound of trimethylolalkane, a lubricating base oil, a lubricating oil, a grease base oil, and a grease formed by blending the same.

Lubricating oils are used in a wide range of temperature environments from low to high temperatures. Therefore, for example, a fluid bearing or an impregnated bearing used in a motor such as a hard disk drive is required to have a high viscosity index and good low temperature fluidity. In addition, a grease base oil having a high viscosity index and good low-temperature fluidity is also required for grease used in a wide temperature range from low temperature to high temperature.
In order to answer such needs, various base oils have been proposed. For example, a predetermined diester base oil that has both a high viscosity index and low temperature fluidity has been proposed for lubricating oils or greases (see, for example, Patent Documents 1 to 3).

JP 2003-321691 A JP 2010-275471 A JP 2007-039496 A

  However, even if the base oils described in Patent Documents 1 to 3 are used, it is difficult to provide a lubricating oil or grease that sufficiently satisfies both the high viscosity index and the low temperature fluidity.

  An object of the present invention is to provide a compound having a high viscosity index and excellent low-temperature fluidity, a lubricating base oil containing the compound, a grease base oil, and a lubricating oil and grease using the same. .

In order to solve the above-mentioned problems, the present invention provides the following trimethylolalkane alkyldiether alkyl monoester compounds, lubricating base oils, lubricating oils, grease base oils, and greases.
[1] An alkyl diether alkyl monoester compound of a trimethylolalkane, which is represented by the following general formula (1):

（前記式において、アルキル基Ｒ、Ｒ’の炭素数は、各々独立に５から１８までである。Ｒ”は水素、または炭素数が５以下のアルキル基である。）
〔２〕上述の〔１〕に記載のアルキルジエーテルアルキルモノエステル化合物において、当該化合物の総炭素数が２４から４２までであることを特徴とするアルキルジエーテルアルキルモノエステル化合物。
〔３〕上述の〔１〕または〔２〕に記載のアルキルジエーテルアルキルモノエステル化合物において、前記トリメチロールアルカンがトリメチロールプロパンまたはトリメチロールエタンであることを特徴とするアルキルジエーテルアルキルモノエステル化合物。
〔４〕上述の〔１〕から〔３〕までのいずれか１つに記載のアルキルジエーテルアルキルモノエステル化合物を配合してなることを特徴とする潤滑油基油。
〔５〕上述の〔４〕に記載の潤滑油基油を配合してなることを特徴とする潤滑油。
〔６〕上述の〔５〕に記載の潤滑油が含油軸受用または流体軸受用であることを特徴とする潤滑油。
〔７〕上述の〔１〕から〔３〕までのいずれか１つに記載のアルキルジエーテルアルキルモノエステル化合物を配合してなることを特徴とするグリース基油。
〔８〕上述の〔７〕に記載のグリース基油を配合してなることを特徴とするグリース。

(In the above formula, each of the alkyl groups R and R ′ independently has 5 to 18 carbon atoms. R ″ is hydrogen or an alkyl group having 5 or less carbon atoms.)
[2] The alkyl diether alkyl monoester compound according to [1], wherein the compound has a total carbon number of 24 to 42.
[3] The alkyl diether alkyl monoester compound according to [1] or [2] above, wherein the trimethylolalkane is trimethylolpropane or trimethylolethane. .
[4] A lubricating base oil comprising the alkyl diether alkyl monoester compound according to any one of [1] to [3] above.
[5] A lubricating oil comprising the lubricating base oil described in [4] above.
[6] A lubricating oil according to the above [5], which is for oil-impregnated bearings or fluid bearings.
[7] A grease base oil comprising the alkyl diether alkyl monoester compound according to any one of [1] to [3] above.
[8] A grease comprising the grease base oil described in [7] above.

  The novel alkyl diether alkyl monoester compound of the present invention has a high viscosity index and excellent low temperature fluidity. Therefore, it is useful as a base oil for lubricating oil and can be suitably used as a lubricating oil for oil-impregnated bearings or fluid bearings. Further, it is also useful as a grease base oil and a grease formed by blending it.

¹ H NMR chart of 2,2-bis (nonyloxymethyl) butan-1-ol (intermediate) in Examples. IR chart of 2,2-bis (nonyloxymethyl) butan-1-ol (intermediate) in Examples. ¹ H NMR chart of decanoic acid 2,2-bis (nonyloxymethyl) butyl ester in Examples. IR chart of decanoic acid 2,2-bis (nonyloxymethyl) butyl ester in Examples.

  The present invention provides an alkyl diether alkyl monoester compound of trimethylolalkane represented by the following general formula (1).

In the formula (1), the alkyl groups R and R ′ independently have 5 to 18 carbon atoms. If the carbon number of the alkyl group R is 4 or less, the viscosity index may be lowered.
On the other hand, if the carbon number of the alkyl group R is 19 or more, the kinematic viscosity increases, the fluidity in the low temperature region is deteriorated, and in some cases, it may be solidified. Therefore, the preferred carbon number of the alkyl group R is 8 to 16.
Further, if the carbon number of the alkyl group R ′ is 4 or less, the viscosity index may be lowered. If hydrolysis occurs, a lower fatty acid may be generated and cause corrosion. On the other hand, if the carbon number of the alkyl group R ′ is 19 or more, the kinematic viscosity increases, the fluidity in the low temperature region deteriorates, and in some cases, it may solidify. Therefore, a particularly preferred carbon number of the alkyl group R ′ is 8 to 16.
Here, R ″ is hydrogen or an alkyl group having 5 or less carbon atoms, preferably an alkyl group having 1 or 2 carbon atoms. That is, the trimethylolalkane structure of the formula (1) is trimethylolethane. Alternatively, the structure is preferably trimethylolpropane. If R ″ has 6 or more carbon atoms, the kinematic viscosity may be increased, and it is difficult to obtain raw materials.
Each alkyl group described above is preferably a straight chain from the viewpoint of improving the viscosity index, but may have a branch as long as the effect of the present invention is not impaired.

  The total number of carbon atoms in the compound of formula (1) is preferably from 24 to 42. When this total carbon number is 23 or less, there is a possibility that the viscosity index is lowered and the evaporation property in a high temperature region is increased. On the other hand, if the total number of carbon atoms is 43 or more, the kinematic viscosity increases, the fluidity in the low temperature region is deteriorated, and in some cases, it may be solidified. Therefore, it is particularly preferred that the total carbon number is 26 to 36.

  The compound of the above formula (1) can be easily produced, for example, via an intermediate represented by the following general formula (2).

（前記式において、ＲとＲ”は式（１）と同様である。）

(In the above formula, R and R ″ are the same as in formula (1).)

The intermediate represented by the formula (2) can be produced, for example, by heating and stirring trimethylolalkane and alkyl bromide in a concentrated alkali solution in the presence of a phase transfer catalyst. Preferred reaction conditions and identification methods are as follows.
Temperature: 40-95 ° C (more preferably 60-80 ° C)
Time: 1 to 24 hours (preferably about 8 hours)
Catalyst: Phase transfer catalyst (tetrabutylammonium bromide, tetraisopropylammonium bromide, etc.)
Solvent: Sodium hydroxide aqueous solution with a concentration of 48% by mass or more
(You may replenish solid sodium hydroxide during the reaction.)
Identification: The transition of the reaction can be confirmed by gas chromatography.
(Detailed structure can be identified by mass spectrometry, NMR analysis, IR analysis, etc.)

Then, the diether (intermediate, formula (2)) is separated by distillation from the mixture of monoether, diether and triether obtained by the above-described production method, and used for the production of the compound of formula (1). Specifically, the diether and the alkyl carboxylic acid may be heated and stirred in the presence of an acid catalyst to cause an esterification reaction to remove the generated water.
Also, the compound of formula (1) can be obtained in good yield by reacting the diether (diether monoalcohol) with an alkylcarboxylic acid chloride at room temperature in the presence of a base.
In any reaction, the obtained compound contains impurities, but can be preferably used as a lubricating base oil or a grease base oil by distillation purification.

Two preferred examples of the esterification reaction of diether monoalcohol are given below.
(Reaction of diether monoalcohol (formula (2)) with alkylcarboxylic acid)
Temperature: 100 to 190 ° C. (preferably 120 to 180 ° C.)
Time: 1 to 24 hours (more preferably about 8 hours)
Catalyst: Sulfuric acid, Tetrabutyl titanate, Tetraisopropyl titanate, Tetraethyl titanate Solvent: Toluene, xylene, trimethylbenzene, etc. Reactor: Dehydration using a Dean-Stark apparatus .
(Identified by mass analysis, NMR analysis, IR analysis, etc.

(Reaction of diether monoalcohol (formula (2)) with alkyl carboxylic acid chloride)
Temperature: 10 to 60 ° C. (more preferably 20 to 40 ° C.)
Time: 1 to 24 hours (more preferably about 4 hours)
Base: N, N-dimethylaniline, triethylamine, etc. Solvent: Tetrahydrofuran, dibutyl ether, dimethyl ether, etc. Identification: The transition of the reaction can be confirmed by gas chromatography.
(It can be identified by mass spectrometry, NMR analysis, IR analysis, etc.)

The compound of the above formula (1) has a high viscosity index and excellent low temperature fluidity. Therefore, it is useful as a base oil for lubricating oil and can be suitably used as a lubricating oil for oil-impregnated bearings or fluid bearings. It is also useful as a grease base oil and a grease formed by blending it.
Moreover, when using the compound of this invention as lubricating oil or base oil of grease, the additive for lubricating oil or grease can be mix | blended as needed. For example, antioxidants, rust preventives, solid lubricants, fillers, oiliness agents, metal deactivators, water resistance agents, extreme pressure agents, antiwear agents, viscosity index improvers, colorants, viscosity modifiers, etc. Is mentioned.
Extreme pressure agents include zinc dialkyldithiophosphates, molybdenum dialkyldithiophosphates, ashless dithiocarbamates, zinc dithiocarbamates, molybdenum dithiocarbamates, sulfur compounds (sulfurized oils, sulfurized olefins, polysulfides, sulfide mineral oils, thiophosphorus Acid, thioterpene, dialkylthiodipyropionate, etc.), phosphate ester, phosphite ester (tricresyl phosphate, triphenyl phosphite, etc.) and the like. Examples of the oily agent include alcohols, carboxylic acids, glycerides, esters and the like. The blending amount of these is preferably about 0.1 to 5% by mass (based on the total amount of lubricating oil or grease).

Examples of the antioxidant include amine-based antioxidants such as alkylated diphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, 2,6-di-t-butyl-4-methylphenol, 4,4 Examples thereof include phenol-based antioxidants such as' -methylenebis (2,6-di-t-butylphenol), peroxide-based decomposition agents such as sulfur-based ZnDTP, and the like. Used at a rate of less than%.
Examples of rust preventives include benzotriazole, zinc stearate, succinic acid ester, succinic acid derivative, thiadiazole, benzotriazole, benzotriazole derivative, sodium nitrite, petroleum sulfonate, sorbitan monooleate, fatty acid soap, and amine compound. Can be mentioned.
Examples of the solid lubricant include polyimide, PTFE, graphite, metal oxide, boron nitride, melamine cyanurate (MCA), and molybdenum disulfide.
Further, as a viscosity modifier, a lubricating base oil such as DIOA (diisooctyl adipate) or DIDA (diisodecyl adipate) may be mixed and used in an amount of about 1% by mass to 30% by mass.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not restrict | limited to these description content at all.
In Table 1, the specific example and physical property of a manufacturing intermediate obtained by the method described in the above-mentioned embodiment are shown for reference.

Below, the specific manufacturing method of the intermediate body 2 is described as an example.
(Production of 2,2-bis (nonyloxymethyl) butan-1-ol)
Under a nitrogen stream, 107.3 g (0.8 mol) of trimethylolpropane and 249 g (1.2 mol) of n-nonyl bromide, tetrabutyl were added to a 2 L reactor equipped with a stirrer, a thermometer, a cooling pipe and a gas introduction pipe. 11.4 g of ammonium bromide was added, 360 g of a 50 mass / volume% aqueous sodium hydroxide solution was added, and the mixture was heated and stirred at 70 to 80 ° C. for 4 hours. After completion of the reaction, the mixture was left standing to cool overnight to precipitate white crystals, and the liquid layer was transferred to a separatory funnel by decantation. The lower alkaline layer was separated and removed, and the organic layer was washed with 400 mL of saturated brine and 50 mL of dilute sulfuric acid aqueous solution and washed with distilled water until neutral, and then 190 g of the obtained organic layer was dried over magnesium sulfate.
After passing this organic layer through a column layer of 50 g of silica gel, mass analysis, NMR analysis, and IR analysis were performed on components fractionated by distillation under reduced pressure, and the desired product, 2,2-bis (nonyloxymethyl) butane- 1-ol was confirmed (mass analysis result m / z = 386). The amount obtained was 110 g (0.28 mol) (yield = 47%).
FIG. 1 shows a ¹ H NMR chart and FIG. 2 shows an IR chart of this compound.

  Table 2 shows the physical properties of the compound of the formula (1) and the comparative diester compound obtained by the method described in the above embodiment.

Below, the specific manufacturing method of the compound 2 is described as an example.
(Synthesis of decanoic acid 2,2-bis (nonyloxymethyl) butyl ester)
To a 1 L three-necked flask equipped with a stirrer, thermometer, cooling pipe, and dropping funnel with gas introduction pipe, 73.4 g (0.19 mol) of 2,2-bis (nonyloxymethyl) butan-1-ol, N, N -26.7 g (0.22 mol) of dimethylaniline and 150 mL of tetrahydrofuran were charged, and 38.1 g (0.2 mol) of decyl chloride was added dropwise at room temperature under a nitrogen stream and stirred. After dropping, the mixture was heated to 45 ° C. and stirred for 5 hours. After the reaction, a small amount of distilled water is added to dissolve the produced white solid, transferred to a separatory funnel, and the aqueous layer is separated. Each was washed and washed with distilled water until neutral. The obtained organic layer was dried over magnesium sulfate. After removing the solvent with an evaporator, mass analysis, NMR analysis, and IR analysis were performed on the components fractionated by distillation under reduced pressure from 100 g of the mixture to confirm that it was the target ester (mass analysis result m / z = 540). ). The amount obtained was 61.8 g (0.114 mol) (yield = 60%).
The ¹ H NMR chart of this compound is shown in FIG. 3, and the IR chart is shown in FIG.

  From Table 2, it can be seen that when the compound of the present invention is compared with a comparative compound not having the predetermined structure of the present invention, the compound of the present invention has a higher viscosity index and excellent low-temperature fluidity. Therefore, it can also be understood that the compound of the present invention is useful as a base oil for lubricating oils and greases.

Claims (8)

An alkyl diether alkyl monoester compound of trimethylolalkane,
An alkyl diether alkyl monoester compound represented by the following general formula (1):

(In the above formula, each of the alkyl groups R and R ′ independently has 5 to 18 carbon atoms. R ″ is hydrogen or an alkyl group having 5 or less carbon atoms.) The alkyl diether alkyl monoester compound according to claim 1,
An alkyl diether alkyl monoester compound, wherein the compound has a total carbon number of 24 to 42. In the alkyl diether alkyl monoester compound according to claim 1 or 2,
The alkyl diether alkyl monoester compound, wherein the trimethylol alkane is trimethylolpropane or trimethylolethane. A lubricating base oil comprising the alkyl diether alkyl monoester compound according to any one of claims 1 to 3. A lubricating oil comprising the lubricating base oil according to claim 4. The lubricating oil according to claim 5 is for oil-impregnated bearings or fluid bearings. A grease base oil comprising the alkyl diether alkyl monoester compound according to any one of claims 1 to 3. A grease comprising the grease base oil according to claim 7.

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