JP2019014854A - Lubricant composition - Google Patents

Abstract

To provide a lubricant composition having improved lubricity.SOLUTION: The lubricant composition contains component A in an amount of 0.1-10.0 mass%, an extreme pressure agent B containing one or more element selected from phosphorus and sulfur in an amount of 0.1-10.0 mass%, and a lubrication base oil C in an amount of 80.0-99.8 mass%. The component A is an alkyloxirane derivative represented by formula 1, and satisfies a relationship of formula 2. RO-(AO)-H (1) (Ris a C1-22 hydrocarbon group; AO is a C3 oxyalkylene group; and n is an integer of 25 or more). 0.35≤M/M≤0.75 (2) (Mand Mare obtained from a chromatogram obtained by a gel permeation chromatography measurement).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a lubricating oil composition having excellent lubricity.

  Lubricating oils are used by adding additives to animal oils and fats, mineral oils, synthetic oils, and mixtures thereof as base oils. In addition, metal working oil used for metal working such as cutting, grinding, drawing, and pressing, engine oil, drive system oil, and the like have severe friction conditions, and extreme pressure agents are used. In particular, chlorine-based extreme pressure agents are used in processing oils such as difficult processing, heavy processing, and difficult processing material processing.

  Chlorine extreme pressure agents are worried about toxicity, especially carcinogenicity, and the development of metalworking oils that do not use chlorinated additives is being promoted from recent environmental considerations. For example, Patent Document 1 discloses a lubricating oil composition having improved lubricity by using a specific ester base oil and a zinc dithiophosphate compound in combination.

  However, with the increase in size and precision of processing machinery, the increase in hardness of metal materials, and the increase in metal processing conditions at high speed and high pressure, the required performance required for lubricating oil is further increased. Under such a background, techniques for improving lubricity by various methods have been developed. For example, Patent Document 2 discloses a combination of a mixed base oil composed of a specific mineral oil and a specific oil and a phosphorus additive. Thus, a metal working oil with improved lubricity is shown.

JP-A-10-88170 JP-A-2005-272818

  In recent years, the general technical level has been advanced, and the use conditions of the lubricating oil have become increasingly severe. As a result, since the conventional lubricating oil may have insufficient lubricity, there is a need for a lubricating oil with improved lubricity.

  This invention is made | formed in view of such a situation, The objective is to provide the lubricating oil composition which improved lubricity.

  As a result of intensive studies to achieve the above object, the present inventors have found that an ester mixture containing a specific alkyl oxirane derivative, an extreme pressure agent, and a lubricating base oil in a specific quantity ratio has an extreme pressure agent. It has been found that it has excellent lubricity even under severe lubrication conditions as required, and has completed the present invention.

That is, the present invention comprises 0.1 to 10.0% by mass of the following component (A), 0.1 to 10.0% of an extreme pressure agent (B) containing one or more elements selected from the group consisting of phosphorus and sulfur. The present invention relates to a lubricating oil composition characterized by containing 10.0% by mass and 80.0 to 99.8% by mass of the lubricating base oil (C).

(Component (A)):
An alkyloxirane derivative represented by the following formula (1) and satisfying the relationship of the following formula (2)

R ¹ O— (AO) _n —H (1)

(In the formula (1),
R ¹ represents a hydrocarbon group having 1 to 22 carbon atoms,
AO represents an oxyalkylene group having 3 carbon atoms,
n represents a number of 25 or more. )

_{0.35 ≦ M L / M H ≦} 0.75 ···· (2)

(On the chromatogram where the length of the perpendicular from the maximum point K at which the refractive index intensity on the chromatogram obtained by gel permeation chromatography measurement is maximum to the base line B is L and the refractive index intensity is L / 2) Of the two points, the earlier elution time is designated as point O, the later elution time is designated as point Q, and the intersection of the straight line G connecting point O and point Q and the perpendicular drawn from the maximum point K to the base line when is P, a distance between the point O and the intersection P and M _H, the distance between the point Q and the point of intersection P and M _L.)

  Since the lubricating oil composition of the present invention has excellent lubricity even under severe lubrication conditions that require an extreme pressure agent, it is a metal that is particularly required to have load resistance such as wear resistance and extreme pressure. It can be suitably used as a lubricating oil such as processing oil or gear oil.

It is a model figure of the chromatogram obtained by the gel permeation chromatography of an alkyl oxirane derivative. It is a model figure of the chromatogram for demonstrating the calculation method of As.

Hereinafter, the lubricating oil composition of the present invention will be described in more detail.
In addition, the numerical value range prescribed | regulated using the symbol "~" in this specification shall contain the numerical value of the both ends (upper limit and lower limit) of "~". For example, “2 to 10” represents 2 or more and 10 or less.

  The lubricating oil composition of the present invention (hereinafter, also simply referred to as “the lubricating oil composition of the present invention”) comprises an alkyloxirane derivative of component (A), an extreme pressure agent of component (B), and a lubrication of component (C). Oil base oil composition.

[Component (A)]
Component (A) used in the present invention is an alkyloxirane derivative, which is a compound represented by the formula (1).

R ¹ O— (AO) n—H (1)

In the formula (1), R ¹ is a hydrocarbon group having 1 to 22 carbon atoms, and AO is an oxyalkylene group having 3 carbon atoms. n is an average addition mole number of the oxyalkylene group AO and is 25 or more.

In the formula (1), the hydrocarbon group having 1 to 22 carbon atoms represented by R ¹ is a functional group composed of carbon and hydrogen, and is selected from an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group. An alkyl group or an alkenyl group, more preferably an alkyl group or alkenyl group having 1 to 14 carbon atoms, still more preferably an alkyl group or alkenyl group having 1 to 6 carbon atoms, and 1 to carbon atoms. Most preferred is an alkyl group of 6. The alkyl group having 1 to 6 carbon atoms may be linear or branched, but is more preferably linear. Examples of the linear alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. The hydrocarbon group having 1 to 22 carbon atoms represented by R ¹ may be only one type or two or more types.

AO is an oxyalkylene group having 3 carbon atoms.
N is an average added mole number of the oxyalkylene group AO and is 25 or more. If n is less than 25, the viscosity is low and the load bearing performance may be insufficient.

  Also, the viscosity increases as n increases. From the viewpoint of ease of blending with the lubricating base oil, n is preferably 150 or less, and more preferably 120 or less.

The alkyloxirane derivative (A) is defined by a chromatogram obtained by using a differential refractometer in gel permeation chromatography (GPC). This chromatogram is a graph showing the relationship between refractive index intensity and elution time. In the alkyloxirane derivative of the present invention, the chromatogram is asymmetrical and satisfies the relationship of formula (2). In addition, the shape of a chromatogram becomes left-right symmetric, so that M _L / _MH becomes a value close to 1.

_{0.35 ≦ M L / M H ≦} 0.75 ···· (2)

  Here, FIG. 1 is a model diagram of a chromatogram obtained by gel permeation chromatography of an alkyloxirane derivative. The horizontal axis represents the elution time, and the vertical axis represents the refractive index strength obtained using a differential refractometer. Show.

  When a sample solution is injected into a gel permeation chromatograph and developed, elution starts from the molecule with the highest molecular weight, and the elution curve increases as the refractive index intensity increases. Thereafter, when the maximum point K at which the refractive index intensity is maximum is passed, the elution curve is lowered.

  Further, in the gel permeation chromatography of the alkyl oxirane derivative (A), when there are a plurality of refractive index intensity maximum points in the chromatogram, the point having the highest refractive index intensity is set as the maximum point K. Further, when there are a plurality of local maximum points having the same refractive index intensity, the longer elution time is set as the local maximum point K of the refractive index intensity. At this time, the peak due to the developing solvent used in the gel permeation chromatography and the pseudo peak due to the fluctuation of the baseline due to the column or apparatus used are excluded.

M _L / M _H is calculated from the chromatogram as follows.
(1) A perpendicular line is drawn from the maximum point K of the refractive index intensity on the chromatogram to the base line B, and the length of the perpendicular line is L.
(2) Of the two points on the chromatogram having a refractive index intensity of L / 2, the point with the earlier elution time is designated as point O, and the point with the later elution time is designated as point Q.
(3) Let P be the intersection of a straight line G connecting point O and point Q and a perpendicular drawn from the local maximum point K of the refractive index intensity to the base line B.
(4) point O and the intersection point P distance _{M H} of the distance of an intersection P and the point Q and _{M L.}

In the alkyloxirane derivative (A), M _L / M _H satisfies 0.35 ≦ M _L / M _H ≦ 0.75. When M L _/ M _H is greater than 0.75, it may not show sufficient load bearing performance in the formulated lubricating oil composition. From this viewpoint, M _L / _{MH is set} to 0.75 or less, and more preferably set to 0.62 or less.

Further, as M _L / M _H becomes smaller, the bias on the high molecular weight side in the molecular weight distribution becomes larger, and an increase in viscosity derived therefrom is observed. When M _L / _{M H} is less than 0.35, too high viscosity, difficult to dissolve into the lubricating oil base oil. From this point of view, M _L / _MH is 0.35 or more, and more preferably 0.36 or more.

In a preferred embodiment, in gel permeation chromatography, the chromatogram represented by the refractive index intensity and the elution time obtained using a differential refractometer is asymmetrical, and the chromatogram obtained as shown below is used. The asymmetry value As of the gram peak satisfies the following expressions (3) and (4).

As = W _1/2 / W _5% (3)
0.30 ≦ As ≦ 0.70 (4)

  The method for calculating As will be further described with reference to the model diagram of the chromatogram in FIG. The horizontal axis represents the elution time, and the vertical axis represents the refractive index intensity obtained using a differential refractometer.

  When a sample solution is injected into a gel permeation chromatograph and developed, elution starts from the molecule with the highest molecular weight, and the elution curve increases as the refractive index intensity increases. After that, the maximum point where the refractive index intensity is maximum is passed, and the elution curve is lowered.

(1) A perpendicular line is drawn from the maximum point K of the refractive index intensity on the chromatogram to the base line B, and its length is set to L.
(2) Of the two points on the chromatogram where the refractive index intensity is L / 20, point with the earlier elution time as point R and point with the later elution time as point S.
(3) Let T be the intersection of a straight line H connecting point R and point S and a perpendicular drawn from the maximum point K of the refractive index intensity to the base line B.
(4) The distance between the point R and the intersection T is W _1/2 , and the distance between the point R and the point S is W _5% .

  In a preferred embodiment, As satisfies 0.30 ≦ As ≦ 0.70. By setting As to 0.70 or less, excellent load bearing performance tends to be obtained. From this viewpoint, it is more preferable that As is 0.65 or less.

  Moreover, as As becomes smaller, the deviation of both sides of the polymer in the molecular weight distribution becomes larger, and an increase in viscosity derived therefrom is observed. By setting As to 0.30 or more, it is possible to suppress the viscosity from becoming too high, and to easily blend in the lubricating base oil. In this respect, As is more preferably 0.57 or more.

In the present invention, gel permeation chromatography (GPC) for determining M _L , _MH and As is SHODEX® as a system.
GPC101GPC dedicated system, equipped with three consecutive SODEX RI-71s as a differential refractometer, SHODEX KF-G as a guard column, three HODEX KF804L as columns, and a column temperature of 40 ° C. and tetrahydrofuran as a developing solvent at a flow rate of 1 ml / min. Then, 0.1 ml of a 0.1 wt% tetrahydrofuran solution of the obtained reaction product is injected, and a chromatogram represented by refractive index intensity and elution time is obtained using a BORWIN GPC calculation program.

When producing the alkyloxirane derivative (A) of the present invention, a double metal cyanide catalyst (hereinafter abbreviated as DMC catalyst) is preferably used as an initiator.
Ring-opening addition of an alkylene oxide having 3 carbon atoms, that is, methyloxirane. In the reaction vessel, an initiator having at least one hydroxyl group in the molecule and a DMC catalyst are added, and methyl oxirane is added continuously or intermittently under stirring in an inert gas atmosphere to perform addition polymerization. Methyloxirane may be added under pressure, or may be added under atmospheric pressure.

At this time, there is no limitation on the average supply rate of methyloxirane, but it is desirable to change it depending on the amount of methyloxirane charged. Speed between Specifically supplies 20 to 50 wt% speed (supply amount per unit time) of V _1, the total supply amount of methyl oxirane between supplying 5 to 20 wt% of the total feed amount of methyl oxirane the _{V 2,} when the speed between the supplying 50～100Wt% of the total feed amount of methyl oxirane was _{V 3, V 1 / V 2} = 1.1~2.0, V 2 / V 3 = 1. It is preferable to control the average supply rate of methyloxirane so as to be 1 to 1.5.

  Moreover, 50 to 150 degreeC is preferable and, as for reaction temperature, 70 to 110 degreeC is more preferable. If the reaction temperature is higher than 150 ° C, the catalyst may be deactivated. When reaction temperature is lower than 50 degreeC, reaction rate is slow and it is inferior to productivity.

As the initiator of the present invention, in formula (1), it may be used a monohydric alcohol having a hydrocarbon group having 1 to 22 carbon atoms represented by R ^1.

  The amount of water contained in the initiator and methyloxirane is not particularly limited, but the amount of water contained in the initiator is preferably 0.5 wt% or less, and methyloxirane is preferably 0.01 wt% or less. .

  Although the usage-amount of a DMC catalyst is not restrict | limited in particular, 0.0001-0.1 wt% is preferable with respect to the alkyl oxirane derivative to produce | generate, 0.001-0.05 wt% is more preferable. The DMC catalyst may be introduced into the reaction system all at once, or may be introduced in divided portions. After completion of the polymerization reaction, the composite metal complex catalyst is removed. The catalyst can be removed by a known method such as filtration, centrifugation, or treatment with a synthetic adsorbent.

As the DMC catalyst used in the present invention, a known one can be used. For example, it can be represented by the formula (5).

Ma [M′x (CN) y] b (H ₂ O) c · (R) d (5)

In formula (5), M and M ′ are metals, R is an organic ligand, a, b, x and y are positive integers that vary depending on the valence and coordination number of the metal, and c and d are metals It is a positive integer that varies depending on the coordination number.

  As the metal M, Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Al (III), Sr (II), Mn (II), Cr (III), Examples thereof include Cu (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), W (VI), etc. Among them, Zn (II) is preferably used.

  As the metal M ′, Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ni (II) , V (IV), V (V), etc., among which Fe (II), Fe (III), Co (II), and Co (III) are preferably used.

As the organic ligand R, alcohol, ether, ketone, ester and the like can be used, and alcohol is more preferable. Preferred organic ligands are water-soluble, and specific examples include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N, N-dimethylacetamide, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether ( Diglyme). Particularly preferred is Zn ₃ [Co (CN) ₆ ] ₂ coordinated with tert-butyl alcohol.

[Component (B)]
The component (B) used in the present invention is an extreme pressure agent containing one or more elements selected from the group consisting of phosphorus and sulfur.

The extreme pressure agent used in the present invention is not particularly limited as long as it does not impair the characteristics of the lubricating oil composition, but is preferably sulfurized fatty acid, sulfurized olefin, sulfurized ester, zinc dithiophosphate, zinc dithiocarbamate, molybdenum dithiophosphate. Examples thereof include a compound, a phosphate ester compound, and a thiophosphate ester compound.
In the above extreme pressure agent, zinc dithiophosphate compounds and phosphate ester compounds are more preferable from the viewpoint of solubility in base oil and lubricating performance.

[Component (C)]
The component (C) used in the present composition is not particularly limited as long as it is a lubricating base oil, but various base oils conventionally used can be used. Representative examples include mineral oils, animal and vegetable oils and fats, and synthetic oils.

  Mineral oils are, for example, distillate obtained by subjecting paraffinic crude oil, intermediate-based crude oil, or naphthenic-based crude oil to atmospheric distillation or distillation of atmospheric residue oil under reduced pressure, or by refining them. Solvent refined oil, hydrogenated refined oil, dewaxed oil, etc. can be mentioned.

  Examples of animal and plant oils include rapeseed oil, soybean oil, safflower oil, sunflower oil, palm oil, palm olein oil, palm kernel oil, coconut oil, jatropha oil, beef tallow, and pork fat.

  Synthetic oils include esters, poly-α-olefins, olefin copolymers alkylbenzenes, alkylnaphthalenes, polyoxyalkylene glycols, and the like. Among these, examples of the ester include methyl oleate, 2-ethylhexyl oleate, di-2-ethylhexyl adipate, neopentyl glycol diolate, trimethylolpropane trioleate, pentaerythritol tetraoleate and the like.

  Of these lubricating base oils, mineral oil, animal and vegetable oils and esters are preferred from the viewpoint of supplyability and cost. Further, esters are preferable from the viewpoint of volatility resistance and lubricity, and neopentyl polyol esters are most preferable from the viewpoint of thermal stability.

[Lubricating oil composition]
The lubricating composition of the present invention comprises the above-described component (A), component (B), and component (C). Content of each component of this invention is component (A) 0.1-10.0 mass%, component (B) 0.1-10.0 mass%, component (C) 80.0-99.8 mass%. It is. However, the total content of components (A), (B) and (C) is 100% by mass.

  When the content of the component (A) is less than 0.1% by mass, sufficient load bearing performance may not be obtained, so it is 0.1% by mass or more, preferably 0.3% by mass or more, 0.5 mass% or more is still more preferable. Further, when the content of the component (A) exceeds 10.0% by mass, it may be difficult to dissolve in the base oil, so that it is 10.0% by mass or less, but 9.0% by mass or less. Preferably, 8.0 mass% or less is more preferable.

  When the content of the component (B) is less than 0.1% by mass, sufficient load bearing performance may not be obtained. The content is preferably 03% by mass or more, and more preferably 0.5% by mass or more. In addition, when the content of the component (B) exceeds 10.0% by mass, the performance reaches a peak and the load bearing performance commensurate with the addition amount may not be obtained. 9.0 mass% or less is preferable, and 8.0 mass% or less is still more preferable.

  Content of a component (C) is the remainder remove | excluding the content of the component (A) and content of the component (B) from 100 mass%, and is 80.0-99.8 mass%.

  Although the method of mixing each component is not particularly limited, for example, a method of measuring an arbitrary amount of component (A), component (B), and component (C) in a beaker and stirring and mixing them using a stirring blade can be mentioned. .

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, the scope of the present invention is not restrict | limited by the following actual example.

Component A: Synthesis Example of Alkyloxirane Derivative (Reference Synthesis Example: Synthesis of Double Metal Cyanide Complex Catalyst)
15 ml of an aqueous solution containing 0.84 g of potassium hexacyanocobaltate K ₃ Co (CN) ₆ was dropped into 2.0 ml of an aqueous solution containing 2.1 g of zinc chloride over 15 minutes while stirring at 40 ° C. After completion of dropping, 16 ml of water and 16 g of tert-butyl alcohol were added, the temperature was raised to 70 ° C., and the mixture was stirred for 1 hour. After cooling to room temperature, a filtration operation (first filtration) was performed to obtain a solid. To this solid, 14 ml of water and 8.0 g of tert-butyl alcohol were added and stirred for 30 minutes, followed by filtration (second filtration) to obtain a solid.

  Further, 18.6 g of tert-butyl alcohol and 1.2 g of methanol were added to this solid again, and the mixture was stirred for 30 minutes and then filtered (third filtration). The obtained solid was dried at 40 ° C. under reduced pressure for 3 hours. As a result, 0.7 g of a double metal cyanide complex catalyst was obtained.

(Synthesis Example 1)
Reference synthesis with 200g of n-butanol in a 5L stainless steel pressure tank equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blowing pipe, stirrer, vacuum exhaust pipe, cooling coil and steam jacket The composite metal cyanide complex catalyst 0.2g of an example was prepared. After nitrogen substitution, the temperature was raised to 110 ° C., and 243 g of methyloxirane (manufactured by Sumitomo Chemical Co., Ltd., LOT.151212D) was charged over 16 hours from a nitrogen gas blowing tube under a condition of 0.3 MPa or less. At this time, changes in pressure and temperature in the reaction tank over time were measured.

  After 16 hours, the pressure in the reaction vessel suddenly decreased. Thereafter, while maintaining the inside of the reaction vessel at 110 ° C., methyloxirane was gradually introduced from the nitrogen gas blowing tube under the condition of 0.6 MPa or less, and 3,270 g of methyloxirane in total was continuously added with stirring. Pressure was applied. At this time, the time required for introducing 987 g of methyloxirane was 60 minutes, the time required for introducing 2,470 g was 180 minutes, and the time required for introducing 3,270 g was 270 minutes.

  After completion of the addition, the mixture was reacted at 110 ° C. for 1 hour. 2220 g was withdrawn from the reaction tank, the residue in the reaction tank was heated to 110 ° C., and 1,110 g of methyloxirane was added from a nitrogen gas blowing tube over 2 hours under the condition of 0.6 MPa or less. After completion of the addition, the mixture was reacted at 110 ° C. for 1 hour. Again, 1.044 g was extracted from the reaction vessel, the temperature in the reaction vessel was raised to 110 ° C., and 312 g of methyloxirane was added from the nitrogen gas blowing tube over 40 minutes under the condition of 0.6 MPa or less. After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and filtration was performed after reducing the pressure at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas. The obtained reaction product (Synthesis Example 1) was measured by gel permeation chromatography.

For gel permeation chromatography, a system exclusively for SHODEX GPC101GPC is used as a system, SHODEX RI-71S as a differential refractometer, SHODEX KF-GS as a guard column, three HODEX KF804L as columns, and column temperature 40 ° C., developing solvent Then, 0.1 ml of a 0.1 wt% tetrahydrofuran solution of the obtained reaction product was poured at a flow rate of 1 ml / min, and a chromatograph represented by refractive index intensity and elution time was calculated using a BORWIN GPC calculation program. Got gram.
When _ML / _MH was calculated | required from this chromatogram, it was 0.52 and As was 0.58.

(Synthesis Examples 2 to 6)
200 g of butylpropylene glycol and a reference pressure reactor of 5 liters (internal volume 4,890 ml) made of stainless steel equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blowing pipe, stirrer, vacuum exhaust pipe, cooling coil and steam jacket The composite metal cyanide complex catalyst 0.2g of the synthesis example was prepared. After nitrogen substitution, the temperature was raised to 110 ° C., and 210 g of methyloxirane was charged from a nitrogen gas blowing tube over 4 hours under the condition of 0.3 MPa or less. At this time, changes in pressure and temperature in the reaction tank over time were measured.

  After 4 hours, the pressure in the reaction vessel suddenly decreased. Thereafter, while maintaining the inside of the reaction vessel at 110 ° C., methyl oxirane was gradually added from a nitrogen gas blowing tube under the condition of 0.6 MPa or less, and 3,287 g of methyl oxirane was continuously added under stirring. did. At this time, the time until 840 g of methyloxirane was added was 60 minutes, the time until 2,100 g was added was 108 minutes, and the time until 3,287 g was added was 132 minutes.

  After completion of the addition, the mixture was reacted at 110 ° C. for 1 hour, and 1,680 g was extracted from the reaction vessel. The residue in the reaction vessel was heated to 110 ° C., and 696 g of methyloxirane was added from a nitrogen gas blowing tube over 77 minutes under the condition of 0.6 MPa or less. After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and then 1,188 g was again extracted from the reaction vessel, and filtered under reduced pressure at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas.

The obtained reaction product (Synthesis Example 2) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.62, As was 0.65.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 291 g of methyl oxirane was added from a nitrogen gas blowing tube over 35 minutes under the condition of 0.6 MPa or less while maintaining the inside of the reaction vessel at 110 ° C. After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and then 752 g was extracted from the reaction vessel again, and filtered under reduced pressure at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas. The obtained reaction product (Synthesis Example 3) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.58, As was 0.63.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 174 g of methyloxirane was added from a nitrogen gas blowing tube over 20 minutes under the condition of 0.6 MPa or less while maintaining the inside of the reaction vessel at 110 ° C. . After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and then 619 g was extracted from the reaction vessel again, and filtered under reduced pressure at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas. The obtained reaction product (Synthesis Example 4) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.52, As was 0.61.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 121 g of methyloxirane was added from a nitrogen gas blowing tube over 30 minutes under the condition of 0.6 MPa or less while keeping the inside of the reaction vessel at 110 ° C. After completion of the addition, the mixture was reacted at 110 ° C. for 1 hour, and then 370 g was extracted from the reaction vessel again, and filtered under reduced pressure at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas. The obtained reaction product (Synthesis Example 5) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.42, As was 0.59.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 122 g of methyloxirane was added from a nitrogen gas blowing tube over 30 minutes under the condition of 0.6 MPa or less while keeping the inside of the reaction vessel at 110 ° C. After making it react at 110 degreeC for 1 hour, it filtered after 75-85 degreeC and pressure reduction processing at 50-100 Torr for 1 hour, blowing in nitrogen gas. The obtained reaction product (Synthesis Example 6) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.36, As was 0.57.

(Comparative Synthesis Example 1)
Reaction with methyl oxirane in a 5 liter stainless steel pressure-resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blowing pipe, stirrer, vacuum exhaust pipe, cooling coil and steam jacket 250 g of polyoxypropylene butyl ether having a molecular weight of 1,290 thus obtained and 5.4 g of potassium hydroxide were charged. At 100 ° C., 2322 g of methyl oxirane was reacted, the remaining methyl oxirane was removed under reduced pressure at 0 ° C. for 30 minutes, the reaction product was transferred to a 5 L eggplant flask, quickly neutralized with 1N hydrochloric acid, After dehydration, filtration was performed.

  The obtained reactant (Comparative Synthesis Example 1) was measured by gel permeation chromatography.

Table 1 shows the values of _ML / _MH and As obtained from the chromatograms of Synthesis Examples 1 to 6 and Comparative Synthesis Example 1, and the characteristics of the compounds.
In addition, since the maximum point of the refractive index of the chromatogram of Comparative Synthesis Example 1 is not one and is not a single peak, the values of M _L / _MH and As at the peak having the maximum point of the maximum refractive index intensity are Show.

  In Table 1, the hydroxyl value is measured according to JIS K-1557-1, the kinematic viscosity is measured according to JIS K-2283, the degree of unsaturation is measured according to JIS K-1557, and the molecular weight is calculated from the hydroxyl value. It is.

Lubricating oil composition formulation examples Using the components (A), (B) and (C) listed in Table 2, lubricating oil composition formulation examples 1 to 9 (Examples 1 to 9) and blending Examples 10-14 (Comparative Examples 1-5) were prepared. Tables 3 and 4 show the blending ratio of each component.

Lubricity test (SRV test)
The lubricating oil composition was evaluated for lubricity with an SRV tester. The SRV test was performed with a ball / disk, and test pieces made of SUJ-2 were used. The test conditions were a test temperature of 40 ° C., a load of 100 N, an amplitude of 1 mm, and a vibration frequency of 50 Hz, and the wear scar diameter after a test time of 25 minutes was measured. The results of the lubricity test are shown in Tables 3 and 4.

  As is clear from the results shown in Table 3, the lubricating oil composition of the present invention containing component (A), component (B), and component (C) is excellent in lubricity.

The compositions of Comparative Examples 1, 2, and 4 use alkyloxirane derivatives in which M _L / M _H and As are outside the scope of the present invention, but have a large wear scar diameter under high load.
The compositions of Comparative Examples 3 and 5 do not contain the alkyloxirane derivative represented by the formula (1), but still have a large wear scar diameter under high load.

The lubricating oil composition of the present invention can be used as metalworking oil, engine oil, and gear oil used under severe lubricating conditions that require extreme pressure agents.

Claims (1)

0.1 to 10.0% by mass of the following component (A), 0.1 to 10.0% by mass of an extreme pressure agent (B) containing one or more elements selected from the group consisting of phosphorus and sulfur, And a lubricating base oil (C) in an amount of 80.0 to 99.8% by mass.

(Component (A)):
An alkyloxirane derivative represented by the following formula (1) and satisfying the relationship of the following formula (2)

R ¹ O— (AO) _n —H (1)

(In the formula (1),
R ¹ represents a hydrocarbon group having 1 to 22 carbon atoms,
AO represents an oxyalkylene group having 3 carbon atoms,
n represents a number of 25 or more. )

_{0.35 ≦ M L / M H ≦} 0.75 ···· (2)

(On the chromatogram where the length of the perpendicular from the maximum point K at which the refractive index intensity on the chromatogram obtained by gel permeation chromatography measurement is maximum to the base line B is L and the refractive index intensity is L / 2) Of the two points, the earlier elution time is designated as point O, the later elution time is designated as point Q, and the intersection of the straight line G connecting point O and point Q and the perpendicular drawn from the maximum point K to the base line when is P, a distance between the point O and the intersection P and M _H, the distance between the point Q and the point of intersection P and M _L.)

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