JP4871606B2 - Polyether compound and lubricating oil base oil and lubricating oil composition containing the same - Google Patents

Description

  The present invention relates to a tetraether compound, a diether compound, and a lubricating oil base oil and lubricating oil composition containing them. More specifically, the present invention relates to a novel tetraether compound having physical properties such as low viscosity, high viscosity index, low temperature fluidity, and low evaporation property, which can be suitably used for base oils for lubricating oils, lubricating oil compositions, etc. And a diether compound, and a base oil for lubricating oil and a lubricating oil composition containing these compounds.

In the lubricating oil field, in recent years, reducing friction is an important function of the lubricating oil composition in order to achieve energy saving and fuel saving, but if a high viscosity lubricating oil composition is used, the lubricating oil composition There is a disadvantage that a load is applied to the pump used to supply the product and that the stirring loss of the lubricating oil composition is increased. In order to solve these problems, the viscosity of the lubricating oil composition is usually reduced, but the lubricating oil composition that has been reduced in viscosity by a conventional method is used particularly in a high-temperature atmosphere. In this case, there is a problem that evaporation loss of the lubricating oil composition occurs. In addition, there is a problem in that the friction coefficient of the lubrication portion increases as the viscosity of the lubricating oil composition decreases.
On the other hand, the engine for internal combustion engines has progressed to a fuel-saving type, and the viscosity of engine oil has been further lowered to meet the demand. Since low-viscosity oil tends to evaporate due to the high temperature in the engine, it is discharged together with exhaust gas as it is used, and as a result, the viscosity gradually increases, resulting in deterioration of fuel efficiency. In order to solve such problems of conventional oils, a Noack test (Noack test) is newly introduced as an evaporative index, and as a result, the use of low-viscosity base oils that satisfy the requirements for low evaporability is increased. I came.

  Further, when a mineral base oil is used to obtain a low viscosity lubricating oil composition, there is a problem that the amount of evaporation of the lubricating oil composition increases significantly. Thus, attempts have been made to use various synthetic base oils. Ester base oils are known as lubricating base oils with low viscosity and low evaporation (see, for example, Patent Documents 1, 2, and 3). It is hydrolyzed by moisture to produce an acid, which causes corrosion of the metal and has a problem of high polarity and adverse effect (swelling) on the organic material. For example, when used for engine oil, there is a problem that rubber used for a sealing material swells, and when used for fluid bearing oil, there is a problem that a plastic material is adversely affected.

Furthermore, in motors mounted on hard disk drives, ball bearings and roller bearings were used as bearings. However, fluid bearings have been developed and used in recent years due to demands for motor miniaturization, low vibration and low noise. It has become.
On the other hand, there have been remarkable progresses in reducing the size and weight of video / audio equipment and personal computers, increasing the capacity, and increasing the speed of information processing. These electronic devices use various rotating devices, for example, rotating devices that drive magnetic disks and optical disks such as FD, MO, mini disk, compact disk, DVD, and hard disk. The increase in capacity and speed is largely due to improvements in bearings that are indispensable for rotating devices.
Fluid bearings consisting of a sleeve and a rotating shaft that face each other via lubricating oil do not have ball bearings, so they are suitable for miniaturization and weight reduction, as well as excellent quietness and economy. Demand is increasing for audio equipment, visual equipment, and car navigation systems.
Lubricating oils used in such hydrodynamic bearings have low viscosity even in the low temperature range, good low temperature fluidity, low viscosity reduction even in the high temperature range, and low evaporation properties. Is required.
As described above, in the lubricating oil field, a lubricating oil base having physical properties such as low viscosity, high viscosity index, low temperature fluidity and low evaporation, metal corrosion due to hydrolysis, and less adverse effects on organic materials. There is an increasing demand for oil and lubricating oil compositions.

JP 2005-154726 A JP 2005-232434 A JP 2005-291332 A

  Under such circumstances, the present invention is a lubricating oil that has physical properties such as low viscosity, high viscosity index, low temperature fluidity, and low evaporation, and that suppresses metal corrosion due to hydrolysis and has little adverse effect on organic materials. It is an object of the present invention to provide a base oil and a compound that gives a lubricating oil composition, and a lubricating base oil and lubricating oil composition containing this compound.

In order to achieve the above-mentioned object, the present inventors have conducted extensive research focusing on the polyether compound, and as a result, the object can be achieved by a tetraether compound and a diether compound having a novel specific structure. I found. The present invention has been completed based on such findings.
That is, the present invention
(1) General formula (I)
R ¹ —O—CHR ² —CHR ³ —O—CHR ⁴ —CHR ⁵ —O—CHR ⁶ —CHR ⁷ —O—R ⁸
... (I)
(In the formula, R ¹ and R ⁸ each independently represent an alkyl group having 6 to 14 carbon atoms, and any one of R ² and R ³ , R ⁴ and R ^5, and R ⁶ and R ^{7 is} a combination thereof. Is a methyl group and the other is a hydrogen atom.)
A tetraether compound having a structure represented by:
(2) The tetraether compound according to (1) above, wherein the kinematic viscosity at a temperature of −20 ° C. is 210 mm ² / s or less,
(3) The tetraether compound according to (1) or (2), wherein the pour point is −40 ° C. or lower,
(4) The tetraether compound according to any one of (1) to (3) above, wherein the evaporation loss after heat treatment at 120 ° C. for 24 hours is 3% by mass or less,
(5) General formula (II)
_{^{R 9 -O-CH 2 -CH (}} C 2 H 5) -CH 2 -CH (C 2 H 5) -CH 2 -O-R 10
... (II)
(In the formula, R ⁹ and R ¹⁰ each independently represents an alkyl group having 6 to 14 carbon atoms.)
A diether compound having a structure represented by:

(6) The diether compound according to item (5), wherein the kinematic viscosity at a temperature of −20 ° C. is 210 mm ² / s or less,
(7) The diether compound according to (5) or (6), wherein the pour point is −40 ° C. or lower,
(8) The diether compound according to any one of (5) to (7) above, wherein the evaporation loss after heat treatment at 120 ° C. for 24 hours is 2% by mass or less,
(9) A base oil for lubricating oil comprising the tetraether compound according to any one of (1) to (4) above (hereinafter sometimes referred to as base oil I for lubricating oil),
(10) A base oil for lubricating oil comprising the diether compound according to any one of (5) to (8) above (hereinafter sometimes referred to as base oil II for lubricating oil),
(11) A lubricating oil composition (hereinafter sometimes referred to as lubricating oil composition I), comprising the tetraether compound according to any one of (1) to (4) above,
(12) A lubricating oil composition (hereinafter sometimes referred to as lubricating oil composition II) comprising the diether compound according to any one of (5) to (8) above, and (13) ) The lubricating oil composition according to (11) or (12) above, which is used for fluid bearings,
Is to provide.

  According to the present invention, a base oil or lubricant for lubricating oil that has physical properties such as low viscosity, high viscosity index, low-temperature fluidity, and low evaporation, suppresses metal corrosion due to hydrolysis, and has little adverse effect on organic materials. It is possible to provide a novel compound that gives an oil composition, and a base oil for lubricating oil and a lubricating oil composition containing the compound.

The tetraether compound of the present invention has the general formula (I)
R ¹ —O—CHR ² —CHR ³ —O—CHR ⁴ —CHR ⁵ —O—CHR ⁶ —CHR ⁷ —O—R ⁸ (I)
(In the formula, R ¹ and R ⁸ each independently represent an alkyl group having 6 to 14 carbon atoms, and any one of R ² and R ³ , R ⁴ and R ^5, and R ⁶ and R ^{7 is} a combination thereof. Is a methyl group and the other is a hydrogen atom.)
It is a novel compound which has a structure represented by these.
In the general formula (I), the alkyl group having 6 to 14 carbon atoms represented by R ¹ and R ⁸ may be linear, branched or cyclic, for example, a hexyl group, an isohexyl group, a heptyl group, Octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, 3,5,5-trimethylhexyl group, isononyl group, decyl group, 3,7-dimethyloctyl group, 2-propylheptyl group, undecyl group, dodecyl group, 2-butyloctyl group, tridecyl group, tetradecyl group, 2-pentylnonyl group, cyclohexyl group, cyclohexylmethyl group and the like. R ¹ and R ⁸ may be the same or different from each other, but are preferably the same from the viewpoint of ease of production of the tetraether compound.
Examples of the tetraether compound represented by the general formula (I) include tri (propylene glycol) dioctyl ether, tri (propylene glycol) dinonyl ether, tri (propylene glycol) didecyl ether, and tri (propylene glycol) nonylun. Examples include decyl ether, tri (propylene glycol) dodecyl octyl ether, tri (propylene glycol) diundecyl ether, and tri (propylene glycol) bis (3,7-dimethyloctyl) ether.

Next, the manufacturing method of the said tetraether compound is demonstrated.
(A) In the tetraether compound represented by the general formula (I), when R ¹ and R ⁸ are the same group R ^1a , for example, in an aqueous medium, in the presence of an alkali and a phase transfer catalyst used as desired. General formula (III)
HO—CHR ² —CHR ³ —O—CHR ⁴ —CHR ⁵ —O—CHR ⁶ —CHR ⁷ —OH
... (III)
(Wherein R ^{2 to} R ⁷ are the same as described above.)
Is reacted with a tri (alkylene ether glycol) represented by the formula ( ^Ia ): R ^1a -X (X is a halogen atom).
R ^1a —O—CHR ² —CHR ³ —O—CHR ⁴ —CHR ⁵ —O—CHR ⁶ —CHR ⁷ —O—R ^1a
... (Ia)
(R ^1a and R ^{2 to} R ⁷ are the same as described above.)
The tetraether compound represented by these can be manufactured.

(B) In the tetraether compound represented by the general formula (I), when R ¹ and R ⁸ are different groups R ^1b and R ^8b , for example, in an aqueous medium, alkali and phase transfer used as desired In the presence of a catalyst, tri (alkylene ether glycol) represented by the above general formula (III) and R ^1b -X (X is a halogen atom) are first reacted to form a terminal monoether body. Then, R ^8b —X (X is a halogen atom) is subjected to a secondary reaction in the same manner as described above to give a general formula (1-b)
R ^1b —O—CHR ² —CHR ³ —O—CHR ⁴ —CHR ⁵ —O—CHR ⁶ —CHR ⁷ —O—R ^8b (Ib)
(In the formula, R ^1b , R ^8b and R ^{2 to} R ⁷ are the same as described above.)
The tetraether compound represented by these can be manufactured. The tetraether compound can also be produced by a one-step reaction in which R ^1b —X and R ^8b —X are reacted simultaneously.
Examples of the alkali used in the reaction include sodium hydroxide and potassium hydroxide, and examples of the phase transfer catalyst include a tetraalkylammonium halide such as tetrabutylammonium bromide. Examples of X in R ^1a -X, R ^1b -X, and R ^8b -X include a chlorine atom and a bromine atom.

In the reaction (a) and the primary reaction and secondary reaction (b), the reaction temperature is usually about 40 to 95 ° C., preferably 50 to 80 ° C. The reaction time varies depending on the reaction temperature, Although it cannot be generally determined, about 1 to 24 hours is sufficient.
In the reaction (a), after completion of the reaction, the organic layer is separated, sufficiently washed with water, and subjected to distillation under reduced pressure to obtain a target tetraether compound fraction. On the other hand, in the reaction (b), after completion of the primary reaction, the same operation as described above is performed to obtain a terminal monoether. In addition, after the secondary reaction is completed, the same operation as described above is performed to obtain the target tetraether compound fraction.
The objective tetraether compound fraction can be identified by mass spectrometry, NMR analysis, IR analysis and the like.

In the tetraether compound of the present invention represented by the general formula (I), the kinematic viscosity at a temperature of −20 ° C. is usually 210 mm ² / s or less, and the lower limit is about 65 mm ² / s. The pour point is usually −40 ° C. or lower, and the viscosity index is usually 120 or higher. The kinematic viscosity and the viscosity index are values measured according to JIS K 2283, and the pour point is a value measured according to JIS K 2265.
Further, the evaporation loss after the heat treatment at 120 ° C. for 24 hours is usually 3% by mass or less, preferably 2% by mass or less. The evaporation loss is a value measured in accordance with the thermal stability test of JIS C 201.
Thus, since the tetraether compound of the present invention has physical properties such as low viscosity, high viscosity index, low temperature fluidity and low evaporation, and is an ether compound, metal corrosion due to hydrolysis like an ester compound is not caused. Since it is suppressed and has little adverse effect on the organic material, it can be suitably used for a base oil for lubricating oil or a lubricating oil composition.

The diether compound of the present invention has the general formula (II)
_{^{R 9 -O-CH 2 -CH (}} C 2 H 5) -CH 2 -CH (C 2 H 5) -CH 2 -O-R 10
... (II)
(In the formula, R ⁹ and R ¹⁰ each independently represents an alkyl group having 6 to 14 carbon atoms.)
It is a novel compound which has a structure represented by these.
In general formula (I), the alkyl group having 6 to 14 carbon atoms represented by R ⁹ and R ¹⁰ may be linear, branched or cyclic. Examples of R ⁹ and R ¹⁰ include the same groups as those exemplified in the description of R ¹ and R ⁸ in the general formula (I).
R ⁹ and R ¹⁰ may be the same or different from each other, but are preferably the same from the viewpoint of ease of production of the diether compound.
Examples of the diether compound represented by the general formula (II) include 1.5-dioctyloxy-2,4-diethylpentane, 1-octyloxy-5-nonyloxy-2,4-diethylpentane, 1,5- Dinonyloxy-2,4-diethylpentane, 1,5-didecyloxy-2,4-diethylpentane, 1-dodecyloxy-5-octyloxy-2,4-diethylpentane, 1,5-diundecyloxy-2,4-diethyl Examples include pentane and 1,5-bis (3,7-dimethyloctyloxy) -2,4-diethylpentane.

Next, the manufacturing method of the said diether compound is demonstrated.
(A) In the diether compound represented by the general formula (II), when R ⁹ and R ¹⁰ are the same R ^9a , for example, in the same manner as the above-mentioned tetraether compound, in the aqueous medium, the alkali and optionally used phase In the presence of a transfer catalyst, the formula (IV)
_{HO-CH 2 -CH (C 2} H 5) -CH 2 -CH (C 2 H 5) -CH 2 -OH ··· (IV)
Is reacted with R ^9a -X (wherein X is a halogen atom) to give a compound of the general formula (II-a)
_{^{R 9a -O-CH 2 -CH (}} C 2 H 5) -CH 2 -CH (C 2 H 5) -CH 2 -O-R 9a
... (II-a)
[Wherein, R ^9a is the same as defined above. ]
The diether compound represented by these can be manufactured.
(B) In the diether compound represented by the general formula (II), when R ⁹ and R ¹⁰ are different groups R ^9b and R ^10b , for example, in an aqueous medium, an alkali and a phase transfer catalyst used as desired In the presence of 2,4-diethyl ... 1,5-pentanediol represented by the above general formula (IV) and R ^9b -X (X is a halogen atom) is first subjected to a primary reaction to produce a terminal monoether. Then, R ^10b -X (X is a halogen atom) is subjected to a secondary reaction in the same manner as described above to give a general formula (II-b)
_{^{R 9b -O-CH 2 -CH (}} C 2 H 5) -CH 2 -CH (C 2 H 5) -CH 2 -O-R 10b
... (II-b)
[Wherein, R ^9b and R ^10b are the same as defined above. ]
The diether compound represented by these can be manufactured. The diether compound can also be produced by a one-step reaction in which R ^9b -X and R ^10b -X are reacted simultaneously.

The alkali and phase transfer catalyst used in this reaction, as well as the reaction conditions and post-treatment, are the same as in the case of producing the above-mentioned tetraether compound.
The finally obtained diether compound fraction can be identified by mass spectrometry, NMR analysis, IR analysis and the like.
In the diether compound of the present invention represented by the general formula (II), the kinematic viscosity at a temperature of −20 ° C. is usually 210 mm ² / s or less, and the lower limit is about 90 mm ² / s. The pour point is usually −40 ° C. or lower, and the viscosity index is usually 120 or higher. The method for measuring the viscosity index is as described above.
Further, the evaporation loss after the heat treatment at 120 ° C. for 24 hours is usually 2% by mass or less. The method for measuring the evaporation loss is also as described above.
As described above, the diether compound of the present invention has physical properties such as low viscosity, high viscosity index, low temperature fluidity and low evaporation property as well as the above-described tetraether compound, and is an ether compound. Since the metal corrosion due to such hydrolysis is suppressed and the adverse effect on the organic material is small, it can be suitably used for a base oil for lubricating oil or a lubricating oil composition.

Next, the base oil I for lubricating oil of the present invention comprises the tetraether compound of the present invention represented by the aforementioned general formula (I), and the base oil II for lubricating oil of the present invention is the above-mentioned It contains the diether compound of this invention represented by general formula II of these.
The base oil I for lubricating oil of the present invention contains at least one selected from the tetraether compounds of the present invention in an amount of 50 to 100% by mass, preferably 70 to 100% by mass, more preferably 80 to 100% by mass, More preferably, it can be contained at a ratio of 90 to 100% by mass.
Further, the base oil II for lubricating oil of the present invention contains at least one selected from the diether compounds of the present invention in an amount of 50 to 100% by mass, preferably 70 to 100% by mass, more preferably 80 to 100% by mass. More preferably, it can be contained in a proportion of 90 to 100% by mass.
Further, a mixture of at least one selected from the tetraether compounds of the present invention and at least one selected from the diether compounds of the present invention is 50 to 100% by mass, preferably 70 to 100% by mass, More preferably, it can be contained in a proportion of 80 to 100% by mass, and more preferably 90 to 100% by mass.

In the base oils I and II for lubricating oils of the present invention, together with the tetraether compound and diether compound, the other base oil is 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably. It can be contained at a ratio of 10% by mass or less.
Examples of other base oils include mineral oils, polyalphaolefin oils, and ester oils such as diesters and polyol esters.
Such lubricating base oils I and II of the present invention are suitably used for the preparation of various lubricating oil compositions that require low viscosity, high viscosity index, low temperature fluidity, low evaporation and the like.

Next, the lubricating oil composition I of the present invention comprises the tetraether compound of the present invention represented by the aforementioned general formula (I), and the lubricating oil composition II of the present invention comprises the aforementioned The diether compound of the present invention represented by the general formula (II) is included.
In addition, the lubricating oil composition I of the present invention can contain the diether compound of the present invention together with the tetraether compound of the present invention, while the lubricating oil composition II of the present invention includes the diether compound of the present invention, The tetraether compound of the present invention can be included.
The said tetraether compound may be contained individually by 1 type, and may be contained 2 or more types. These compounds are usually contained in the lubricating oil composition of the present invention as a base oil.
In the lubricating oil composition of the present invention, various additives such as antioxidants, lubricity improvers, detergent dispersants, conductive additives, rust preventives, metal deactivators, antifoaming agents, viscosity index improvements Agents, pour point depressants, etc. can be included as desired.

Examples of the antioxidant include amine-based antioxidants such as alkylated diphenylamine, phenyl-α-naphthylamine, and alkylated-naphthylamine, 2,6-di-t-butylphenol, 4,4′-methylenebis (2,6 -Di-t-butylphenol) and the like, and these are usually from 0.01 to 3% by mass, preferably from 0.1 to 1% by mass, based on the total amount of the composition Used in.
Examples of the lubricity improver include oil-based agents, antiwear agents / extreme pressure agents such as phosphate ester compounds, sulfur compounds and organometallic compounds.

Examples of the oily agent include aliphatic saturated and unsaturated monocarboxylic acids such as stearic acid and oleic acid, polymerized fatty acids such as dimer acid and hydrogenated dimer acid, hydroxy fatty acids such as ricinoleic acid and 12-hydroxystearic acid, Aliphatic saturated and unsaturated monoalcohols such as lauryl alcohol and oleyl alcohol, aliphatic saturated and unsaturated monoamines such as stearylamine and oleylamine, aliphatic saturated and unsaturated monocarboxylic amides such as lauric acid amide and oleic acid amide Can be mentioned.
The preferable compounding quantity of these oiliness agents is the range of 0.01-10 mass% on the basis of the composition whole quantity, and the range of 0.1-5 mass% is especially preferable.
Examples of phosphoric acid ester compounds include phosphoric acid esters, acidic phosphoric acid esters, acidic phosphoric acid ester amine salts, phosphorous acid esters, acidic phosphorous acid esters, and acidic phosphorous acid ester amine salts.

  Examples of the phosphate ester include triaryl phosphate, trialkyl phosphate, trialkylaryl phosphate, triarylalkyl phosphate, trialkenyl phosphate, and the like, for example, triphenyl phosphate, tricresyl phosphate, benzyldiphenyl phosphate, ethyl diphenyl phosphate. , Tributyl phosphate, ethyl dibutyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethyl phenyl diphenyl phosphate, di (ethylphenyl) phenyl phosphate, propylphenyl diphenyl phosphate, di (propylphenyl) phenyl phosphate, triethylphenyl phosphate, tripropyl Phenyl phosphate, butyl phenol Rudiphenyl phosphate, di (butylphenyl) phenyl phosphate, tributylphenyl phosphate, trihexyl phosphate, tri (2-ethylhexyl) phosphate, tridecyl phosphate, trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate, tristearyl phosphate, trio Examples include rail phosphate.

  Examples of the acidic phosphate ester include di-2-ethylhexyl acid phosphate, didecyl acid phosphate, didodecyl acid phosphate (dilauryl acid phosphate), tridecyl acid phosphate, dioctadecyl acid phosphate (distearyl acid phosphate), di- 9-octadecenyl acid phosphate (dioleoyl acid phosphate) and the like. Examples of the phosphite ester include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri (nonyl). Phenyl) phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, triisooctyl phosphite, diphe Louis-Soviet decyl phosphite, tristearyl phosphite, and the like can be given trio rail phosphite.

Examples of acidic phosphites include di-2-ethylhexyl hydrogen phosphite, didecyl hydrogen phosphite, didodecyl hydrogen phosphite (dilauryl hydrogen phosphite), and dioctadecyl hydrogen phosphite (distearyl). Hydrogen phosphite), di-9-octadecenyl hydrogen phosphite (dioleyl hydrogen phosphite), diphenyl hydrogen phosphite and the like.
Examples of the acid phosphate amine salt and the acid phosphite amine salt include salts of the aforementioned acid phosphate ester and acid phosphite ester with the following amines. As the amines, mono-substituted amines, di-substituted amines or tri-substituted amines are used.

  Examples of mono-substituted amines include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, benzylamine, etc. Examples of disubstituted amines include dibutylamine, Dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl propanolamine, benzyl monoethanolamine, Phenyl monoethanolamine, tolyl monopropanolamine and the like. Examples of trisubstituted amines include tributylamine, tripentylamine. , Trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl monopropanolamine, dioctyl monoethanolamine, dihexyl monopropanol Amine, dibutyl propanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine, triyl Examples include ethanolamine and tripropanolamine.

Acid phosphate ester amine salts such as monomethyl hydrogen phosphate, monoethyl hydrogen phosphate, monopropyl hydrogen phosphate, monobutyl hydrogen phosphate, mono-2-ethylhexyl hydrogen phosphate, etc. Salts with amines can also be used.
In this invention, this phosphate ester type compound may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount is usually about 0.05 to 3% by mass based on the total amount of the composition.

Examples of sulfur compounds include sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiadiazole compounds, thiophosphate esters (thiophosphites, thiophosphates), alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds, A dialkyl thiodipropionate compound etc. can be mentioned. These are usually used in a proportion of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total amount of the composition.
Examples of the organometallic compound include zinc dithiophosphate (ZnDTP), zinc dithiocarbamate (ZnDTC), sulfurized oxymolybdenum organophosphorodithioate (MoDTP), and sulfurized oxymolybdenum dithiocarbamate (MoDTC). These compounding quantities are 0.05-5 mass% normally on the basis of the composition whole quantity, Preferably it is 0.1-3 mass%.

Examples of the detergent / dispersant include succinimides, boron-containing succinimides, benzylamines, boron-containing benzylamines, succinic acid esters, monovalent or divalent carboxylic acid amides represented by fatty acids or succinic acid. Ashless dispersants, neutral metal sulfonates, neutral metal phenates, neutral metal salicylates, neutral metal phosphonates, basic sulfonates, basic phenates, basic salicylates, overbased sulfonates, overbased salicylates And metal detergents such as overbased phosphonates. These compounding quantities are 0.1-20 mass% normally on the basis of the composition whole quantity, Preferably it is 0.5-10 mass%.
As the conductive additive, amine derivatives, succinic acid derivatives, poly (oxyalkylene) glycols or partial esters of polyhydric alcohols which are nonmetallic antistatic agents are preferable.

  Examples of rust inhibitors include alkenyl succinic acid and partial esters thereof, and examples of metal corrosion inhibitors include benzotriazole, benzimidazole, benzothiazole, thiadiazole, and the like as metal deactivators. For example, benzotriazole, benzotriazole derivative, benzothiazole, benzothiazole derivative, triazole, triazole derivative, dithiocarbamate, dithiocarbamate derivative, imidazole, imidazole derivative and the like are used. Examples of the antifoaming agent include dimethylpolysiloxane and polyacrylate, and examples of the surfactant include polyoxyethylene alkylphenyl ether.

As the viscosity index improver, for example, polymethacrylate, dispersed polymethacrylate, olefin copolymer (for example, nitrylene-propylene copolymer, etc.), dispersed olefin copolymer, styrene copolymer (for example, Examples of the pour point depressant include polymethacrylate and the like.
Since the lubricating oil composition of the present invention contains a base oil containing a tetraether compound represented by the general formula (I) and / or a diether compound represented by the general formula (II), it has a low viscosity, In addition to having a high viscosity index, low-temperature fluidity, and low evaporation properties, it has favorable properties such that corrosion of metals due to hydrolysis is suppressed and there is little adverse effect on organic materials. Therefore, it can be used for various applications where the properties are required. In particular, it is suitably used for a fluid bearing used in a rotating device for driving a magnetic disk or optical disk such as FD, MO, mini disk, compact disk, DVD, and hard disk.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the physical property of the compound obtained in each case was calculated | required according to the following method.
(1) Kinematic viscosity (-20 ° C, 40 ° C, 100 ° C)
The measurement was performed according to JIS K 2283.
(2) Viscosity index (VI)
The measurement was performed according to JIS K 2283.
(3) Pour point Measured according to JIS K 2269.
(4) Evaporation loss It measured based on the thermal stability test of JISC201.

Production Example 1 (Compound of Example 3)
In a 2-liter glass flask, 96.2 g (0.5 mol) of tri (propylene glycol), 244 g (1.1 mol) of 1-bromodecane, 14.3 g of tetrabutylammonium bromide, and 442 g of a 52 mass% aqueous sodium hydroxide solution were added. The mixture was stirred and reacted at 70 ° C. for 8 hours.
After completion of the reaction, the reaction mixture was transferred to a separatory funnel, the aqueous layer was removed, and the remaining organic layer was washed 5 times with 200 ml of water. Water was removed with a vacuum evaporator until the liquid became transparent, and then poured into a column filled with 40 g of silica gel and filtered to obtain an organic substance.
Mass analysis, NMR analysis, and IR analysis of components fractionated from this organic substance by distillation under reduced pressure were conducted to confirm that it was the target tri (propylene glycol) didecyl ether (N10-TPG-N10) component (mass spectrometry). Result: m / z = 472). The yield was 72 g (yield 30.5%).
The physical properties of this compound are shown in Table 1, a ¹ H-NMR chart is shown in FIG. 1, and an IR chart is shown in FIG.

Production Example 2 (Compound of Example 1)
The same treatment was carried out except that 213 g of 1-bromooctane was used instead of 1-bromodecane in Production Example 1 to obtain a tri (propylene glycol) dioctyl ether (N8-TPG-N8) component. The amount obtained was 60 g (yield 29%).
The physical properties of this compound are shown in Table 1.
Production Example 3 (Compound of Example 2)
The same treatment was carried out except that 228 g of 1-bromononane was used instead of 1-bromodecane in Production Example 1 to obtain a tri (propylene glycol) dinonyl ether (N9-TPG-N9) component. The yield was 68 g (yield 30.5%).
The physical properties of this compound are shown in Table 1.

Production Example 4 (Compound of Example 4)
A 2 liter glass flask was charged with 96.2 g of tri (propylene glycol), 114 g of 1-bromononane, 130 g of 1-bromoundecane, 14.3 g of tetrabutylammonium bromide, and 442 g of a 52 mass% aqueous sodium hydroxide solution. The reaction was stirred for an hour.
After completion of the reaction, the reaction mixture was transferred to a separatory funnel, the aqueous layer was removed, and the remaining organic layer was washed 5 times with 200 ml of water. Water was removed with a vacuum evaporator until the liquid became transparent, and then poured into a column filled with 40 g of silica gel and filtered to obtain an organic substance.
The component fractionated from this organic material by distillation under reduced pressure was confirmed to be the target tri (propylene glycol) nonyl undecyl ether (N9-TPG-N11) component by analysis. The yield was 31.7 g (yield 13.5%).
The physical properties of this compound are shown in Table 1.

Production Example 5 (Compound of Example 5)
In a 2 liter glass flask, 192.3 g (1 mol) of tri (propylene glycol), 212.4 g (1.1 mol) of 1-bromooctane, 14.3 g of tetrabutylammonium bromide, 442 g of a 52 mass% aqueous sodium hydroxide solution The mixture was stirred and reacted at 60 ° C. for 10 hours.
After completion of the reaction, the reaction mixture was transferred to a separatory funnel, the aqueous layer was removed, and the remaining organic layer was washed 5 times with 200 ml of water. Water was removed with a vacuum evaporator until the liquid became transparent, and then poured into a column filled with 40 g of silica gel and filtered to obtain an organic substance.
From this organic material, 199.1 g of a tri (propylene glycol) monooctyl ether component was separated by distillation under reduced pressure.
Into 152 g (0.5 mol) of this compound, 138 g (0.55 mol) of 1-bromododecane, 7.2 g of tetrabutylammonium bromide, and 230 g of a 52 mass% sodium hydroxide aqueous solution were added and stirred at 70 ° C. for 8 hours to be reacted. It was.
After completion of the reaction, the reaction mixture was transferred to a separatory funnel, the aqueous layer was removed, and the remaining organic layer was washed 5 times with 100 ml of water. Water was removed with a vacuum evaporator until the liquid became transparent, and then poured into a column filled with 40 g of silica gel and filtered to obtain an organic substance.
Tri (propylene glycol) dodecyl octyl ether (N8-TPG-N12) component was obtained from this organic substance by distillation under reduced pressure. The yield was 78 g (33% yield).
The physical properties of this compound are shown in Table 1.

Production Example 6 (Compound of Example 6)
The same treatment was carried out except that 260 g of 1-bromoundecane was used instead of 1-bromodecane in Production Example 1 to obtain a tri (propylene glycol) diundecyl ether (N11-TPG-N11) component. The yield was 84 g (yield 33.5%).
The physical properties of this compound are shown in Table 1.
Production Example 7 (Compound of Example 7)
The same treatment was carried out except that 244 g of 1-bromo-3,7-dimethyloctane was used instead of 1-bromodecane in Production Example 1, and tri (propylene glycol) -bis (3,7-dimethyloctyl) ether ( DMC8-TPG-DMC8) component was obtained. The yield was 71 g (yield 30%).
The physical properties of this compound are shown in Table 1.

Production Example 8 (Compound of Example 10)
In a 1-liter glass flask, 80 g (0.5 mol) of 2,4-diethyl-1,5-pentanediol, 230 g (0.11 mol) of 1-bromononane, 14.3 g of tetrabutylammonium bromide, 52% by mass water 442 g of an aqueous sodium oxide solution was added, and the reaction was stirred at 70 ° C. for 12 hours.
After completion of the reaction, the reaction mixture was transferred to a separatory funnel, the aqueous layer was removed, and the remaining organic layer was washed 5 times with 200 ml of water. Water was removed with a vacuum evaporator until the liquid became transparent.
Next, the solution was poured into a column packed with 40 g of silica gel and filtered to obtain a light brown liquid.
The organic substance is fractionated by distillation under reduced pressure, and mass analysis, NMR analysis and IR analysis of its components are carried out, and the target 1,5-dinonyloxy-2,4-diethylpentane (N9-O-DEC5-O-N9) is obtained. (Mass analysis result: m / z = 412). The yield was 48 g (23% yield).
The physical properties of this compound are shown in Table 1, a ¹ H-NMR chart is shown in FIG. 3, and an IR chart is shown in FIG.

Production Example 9 (Compound of Example 8)
The same treatment was carried out except that 212 g of 1-bromooctane was used instead of 1-bromononane in Production Example 8, and 1,5-dioctyloxy-2,4-diethylpentane (N8-O-DEC5-O-N8) Ingredients were obtained. The amount obtained was 54.5 g (yield 28%).
The physical properties of this compound are shown in Table 1.
Production Example 10 (Compound of Example 11)
The same treatment was carried out except that 243 g of 1-bromodecane was used instead of 1-bromononane in Production Example 8, and a 1,5-didecyloxy-2,4-diethylpentane (N10-O-DEC5-O-N10) component was added. Obtained. The yield was 56 g (yield 25.5%).
The physical properties of this compound are shown in Table 1.

Production Example 11 (Compound of Example 9)
In a 3-liter glass flask, 320.5 g (2 mol) of 2,4-diethyl-1,5-pentanediol, 386 g (2 mol) of 1-bromooctane, 28.6 g of tetrabutylammonium bromide, 52% by mass hydroxylation 900 g of an aqueous sodium solution was added, and the mixture was stirred at 70 ° C. for 10 hours for reaction.
After completion of the reaction, the reaction mixture was transferred to a separatory funnel, the aqueous layer was removed, and the remaining organic layer was washed 5 times with 500 ml of water. Water was removed with a vacuum evaporator until the liquid became transparent, and then the solution was poured into a column packed with 60 g of silica gel and filtered to obtain an organic substance. By distillation under reduced pressure from this organic substance, 124 g of 1-octyloxy-2,4-diethylpentan-5-ol was obtained (yield 45.5%).
122.5 g (0.45 mol) of this compound was placed in a 1-liter glass flask, 102 g of 1-bromononane, 7.0 g of tetrabutylammonium bromide, and 200 g of a 52 mass% aqueous sodium hydroxide solution were added, and the mixture was heated at 70 ° C. for 8 hours. Stir to react.
After completion of the reaction, the reaction mixture was transferred to a separatory funnel, the aqueous layer was removed, and the remaining organic layer was washed 5 times with 100 ml of water. Water was removed with a vacuum evaporator until the liquid became transparent, and then poured into a column filled with 40 g of silica gel and filtered to obtain an organic substance.
Mass analysis, NMR analysis and IR analysis of components fractionated from this organic substance by distillation under reduced pressure were carried out, and the target 1-octyloxy-5-nonyloxy-2,4-diethylpentane (N8-O-DEC5-O-N9) was obtained. ) 67 g (mass analysis result: m / z = 398). (Yield 37.5%)
The physical properties of this compound are shown in Table 1, a ¹ H-NMR chart is shown in FIG. 5, and an IR chart is shown in FIG.

Production Example 12 (Compound of Example 12)
274 g of 1-bromododecane was used instead of 1-bromononane in 110 g (0.4 mol) of the intermediate 1-octyloxy-2,4-diethylpentan-5-ol obtained in the same manner as in Production Example 11. Except for the above, the same treatment as in Production Example 11 was performed to obtain a 1-dodecyloxy-5-octyloxy-2,4-diethylpentane (N8-O-DEC5-O-N12) component. The yield was 73 g (yield 41%).
The physical properties of this compound are shown in Table 1.
Production Example 13 (Compound of Comparative Example 2)
The same treatment was carried out except that 53 g of neopentyl glycol was used instead of 2,4-diethyl-1,5-pentanediol in Production Example 8 and 212 g of 1-bromooctane was used instead of 1-bromodecane. Dioctyloxyneopentane (N8-NPG-N8) component was obtained. The yield was 49 g.
The physical properties of this compound are shown in Table 1.
Production Example 14 (Compound of Comparative Example 3)
The same treatment was performed except that 166 g of 1-bromopentane was used instead of 1-bromodecane in Production Example 1 to obtain a tri (propylene glycol) dipentyl ether (N5-TPG-N5) component. The yield was 52.5 g.
The physical properties of this compound are shown in Table 1.

Production Example 16 (Compound of Comparative Example 4)
A 1-liter glass flask was charged with 250 g of tri (propylene glycol) monobutyl ether (Aldrich), 170 g of 1-bromohexadecane, 14.3 g of tetrabutylammonium bromide, and 442 g of a 52 mass% aqueous sodium hydroxide solution. The reaction was stirred for an hour.
After completion of the reaction, the reaction mixture was transferred to a separatory funnel, the aqueous layer was removed, and the remaining organic layer was washed 5 times with 200 ml of water. Water was removed with a vacuum evaporator until the liquid became transparent, and then poured into a column filled with 40 g of silica gel and filtered to obtain an organic substance.
Tri (propylene glycol) butyl hexadecyl ether component (N4-TPG-N16) was obtained from this organic substance by distillation under reduced pressure. The yield was 61 g.
The physical properties of this compound are shown in Table 1.

  The tetraether compound and diether compound of the present invention have physical properties such as low viscosity, high viscosity index, low temperature fluidity, and low evaporation property, metal corrosion due to hydrolysis is suppressed, and there are few adverse effects on organic materials. It is suitably used for lubricating oil base oils, lubricating oil compositions, and the like.

2 is a ¹ H-NMR chart of tri (propylene glycol) didecyl ether which is the compound of Example 3. FIG. 4 is an IR chart of tri (propylene glycol) didecyl ether which is the compound of Example 3. FIG. 2 is a ¹ H-NMR chart of 1,5-dinonyloxy-2,4-diethylpentane, which is the compound of Example 10. 4 is an IR chart of 1,5-dinonyloxy-2,4-diethylpentane, which is the compound of Example 10. 2 is a ¹ H-NMR chart of ¹ -octyloxy-5-nonyloxy-2,4-diethylpentane, which is the compound of Example 9. FIG. 4 is an IR chart of 1-octyloxy-5-nonyloxy-2,4-diethylpentane, which is the compound of Example 9.

Claims (13)

Formula (I)
R ¹ —O—CHR ² —CHR ³ —O—CHR ⁴ —CHR ⁵ —O—CHR ⁶ —CHR ⁷ —O—R ⁸
... (I)
[Wherein, R ¹ and R ⁸ each independently represents an alkyl group having 6 to 14 carbon atoms, and in the combination of R ² and R ³ , R ⁴ and R ⁵ and R ⁶ and R ⁷ , either one of It is a methyl group, and the other is a hydrogen atom. ]
The tetraether compound which has a structure represented by these. The tetraether compound according to claim 1, wherein the kinematic viscosity at a temperature of −20 ° C. is 210 mm ² / s or less.   The tetraether compound according to claim 1 or 2, which has a pour point of -40 ° C or lower.   The tetraether compound according to any one of claims 1 to 3, wherein an evaporation loss after heat treatment at 120 ° C for 24 hours is 3% by mass or less. General formula (II)
_{^{R 9 -O-CH 2 -CH (}} C 2 H 5) -CH 2 -CH (C 2 H 5) -CH 2 -O-R 10
... (II)
[Wherein R ⁹ and R ¹⁰ each independently represents an alkyl group having 6 to 14 carbon atoms. ]
The diether compound which has a structure represented by these. The diether compound according to claim 5, wherein the kinematic viscosity at a temperature of −20 ° C. is 210 mm ² / s or less.   The diether compound according to claim 5 or 6, which has a pour point of -40 ° C or lower.   The diether compound according to any one of claims 5 to 7, wherein the evaporation loss after heat treatment at 120 ° C for 24 hours is 2 mass% or less.   A base oil for lubricating oil comprising the tetraether compound according to claim 1.   A base oil for lubricating oil comprising the diether compound according to claim 5.   A lubricating oil composition comprising the tetraether compound according to claim 1.   A lubricating oil composition comprising the diether compound according to claim 5.   The lubricating oil composition according to claim 11 or 12, which is used for a hydrodynamic bearing.

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