JP2019070060A - Alkyl oxirane derivative and lubricant - Google Patents

Abstract

To provide a novel alkyl oxirane derivative as a lubricant excellent in lubricity.SOLUTION: There is provided an alkyl oxirane derivative having Mand Mcalculated from a chromatogram obtained by a gel permeation chromatography satisfying a relationship of formula 1. 0.35≤M/M≤0.75 (1), wherein a length of perpendicular from a maximum point K at which refractive index intensity on the chromatogram becomes maximum to a base line B is L, a point with earlier elution time of two points with refractive index intensity of L/2 on the chromatogram is point O, a point with later elution time is point Q, an intersection point between a linear G binding the point O and the point Q and the perpendicular from the refractive index intensity maximum point K to the base line is P, a distance between the point and the intersection point P is Mand a distance between the point Q and the intersection point P is M.SELECTED DRAWING: Figure 1

Description

  The present invention relates to novel alkyl oxirane derivatives that can be effectively used as lubricants and the like.

  In general, alkyl oxirane derivatives are synthesized by anionic polymerization using an alkali metal hydroxide such as potassium hydroxide and ring-opening addition of alkyl oxiranes such as oxirane, methyl oxirane or ethyl oxirane to an initiator having active hydrogen such as alcohol. Be done. In particular, when ethyl oxirane derivative is synthesized using ethyl oxirane in this anionic polymerization, ethyl oxirane is less reactive than oxirane or methyl oxirane, so it takes a long time to polymerize the ethyl oxirane derivative, Industrial productivity is very bad. In addition, as the molecular weight distribution becomes less reactive, and the molecular weight distribution has a problem that the proportion of low molecular weight products due to side reactions increases, the ethyloxirane derivative having a molecular weight of 10,000 or more is industrially It was difficult to synthesize.

  This problem also occurs when synthesizing a methyl oxirane derivative, but in the case of a methyl oxirane derivative, a compound having a P = N bond such as a phosphazene compound, a complex metal cyanide complex catalyst to solve this problem Etc. are used. By using these catalysts, high molecular weight methyl oxirane derivatives can be synthesized. Among these catalysts, composite metal cyanide complex catalysts have higher catalytic activity than the former catalysts, and are useful polymerization catalysts for producing methyl oxirane derivatives (Non-patent Document 1).

  Moreover, it is also reported that the high molecular weight methyl oxirane derivative synthesize | combined using this composite metal cyanide complex catalyst has narrow molecular weight distribution. As the methyl oxirane derivative having a narrow molecular weight distribution has a low viscosity and is easy to handle, it is considered to be very useful as a raw material of polyurethane, and a method for producing a methyl oxirane derivative having a narrow molecular weight distribution has been reported (Patent Document 1, 2, 3).

  On the other hand, no specific synthesis example has been reported for high molecular weight ethyl oxirane derivatives.

  Lubricants are used in a wide variety of applications such as metal cutting oil, rolling oil, brake oil and gear oil. In addition, it is also used as an extrusion aid for improving extrusion processability of assembly oil and plastics and ceramics used at the time of rubber material insertion into metal parts. In order to further improve the quality, performance and production efficiency, a lubricant capable of imparting higher lubricity is desired, and the lubricant is also imparted by the additive. On the other hand, the lubricity of a lubricant generally depends largely on the performance of a base oil.

  Alkyl oxirane derivatives are used in these lubricants. Among them, ethyl oxirane derivatives are used in a wide range of applications because they are soluble in mineral oil and liquid paraffin generally used as base oils for lubricants and can be used by blending with such oils. For example, in Patent Document 4, an ethyl oxirane derivative is used as a base oil of a lubricating oil composition for processing an aluminum tube.

ACS Symposium Series, Vol. 6, pp 20-37 (1975)

JP 10-007787 Patent document 1: JP-A-2004-269776 WO2011 / 034030 Japanese Patent Application Laid-Open No. 2010-065231

  An object of the present invention is to provide a novel alkyloxirane derivative having excellent lubricity, which can not be obtained by the conventional alkyloxirane derivative.

  As a result of intensive investigations in view of the above-mentioned matters, the present inventors obtain an alkyl oxirane derivative in which the molecular weight pattern determined by gel permeation chromatography measurement is asymmetrical and the molecular weight distribution is biased to the high molecular weight side. It has been found that when the oxirane derivative is used, for example, as a lubricant, the above problem is solved.

That is, the present invention is as follows.
[1] An alkyl oxirane represented by the formula (1) and characterized in that M _H and M _L calculated from a chromatogram determined by gel permeation chromatography satisfy the relation of the formula (2) Derivative.

R ¹ O- (BO) n-H (1)

(In the formula (1),
R ¹ represents a hydrocarbon group having 1 to 22 carbon atoms,
BO represents an oxybutylene group formed upon ring-opening addition of ethyl oxirane having 4 carbon atoms,
n represents a number of 25 or more. )

_{0.35 ≦ M L / M H ≦} 0.75 ···· (2)

(The length of the perpendicular from the maximum point K where the refractive index intensity on the chromatogram is maximum to the baseline B is L, and the elution time is at two points on the chromatogram where the refractive index intensity is L / 2 Assuming that the earlier one is point O and the later elution time is point Q, let P be the point of intersection of a straight line G connecting point O and point Q and a perpendicular drawn from the refractive index intensity maximum point K to the baseline. Then, let the distance between the point O and the point of intersection P be M _H and the distance between the point Q and the point of intersection P be M _L.

[2] The alkyl oxirane derivative of [1], wherein As calculated from the chromatogram satisfies the relationship of Formula (3) and Formula (4).

As = W _1/2 / W _5% (3)
0.30 ≦ As ≦ 0.80 (4)

(A straight line H connecting the point R and the point S is a straight line connecting the point R and the point S with the earlier one of the two elution points on the chromatogram having a refractive index intensity of L / 20 and the later one being the later elution time. Let T be the point of intersection between the refractive index maximum point K and the perpendicular drawn to the base line B, let T _{1/2 be} the distance between point R and point of intersection T, and W _{5% be} the distance between point R and point S.

[3] The alkyloxirane derivative of [1] or [2], wherein the peak top molecular weight indicated by the refractive index intensity maximum point K on the chromatogram calculated from the chromatogram is 1,500 to 10,000.

[4] The alkyloxirane derivative according to any one of [1] to [3], which has one refractive index intensity maximum point in the chromatogram.

[5] A lubricant comprising the alkyl oxirane derivative according to any one of [1] to [4].

  The alkyl oxirane derivatives exhibiting a specific molecular weight distribution according to the invention have significantly improved lubricity and are suitable, for example, for lubricating oils.

FIG. 1 is a model chromatogram diagram for explaining M _L and M _H defined in the present invention. FIG. 2 is a model chromatogram diagram for explaining W _1/2 and W _5% defined in the present invention. FIG. 3 is a chromatogram of Synthesis Example 1. FIG. 4 is a chromatogram of Comparative Synthesis Example 1.

The alkyl oxirane derivative of the present invention is a compound represented by formula (1).

R ¹ O- (BO) n-H (1)

In the formula (1), R ¹ is a hydrocarbon group having 1 to 22 carbon atoms, and BO is an oxybutylene group formed upon ring-opening addition of ethyl oxirane having 4 carbon atoms, ie, 1,2-oxy butylene _{(-O-CH (CH 2 CH} 3) -CH 2 -) a. n is an average added mole number of 1,2-oxybutylene group and is 25 or more. n can be calculated from the hydroxyl value of the alkyl oxirane derivative.

In Formula (1), examples of the hydrocarbon group having 1 to 22 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an allyl group, a butyl group, an isobutyl group and a sec-butyl group. Tert-Butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, Aliphatic hydrocarbon groups such as isooctadecyl group, octyldodecyl group and docosyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, cresyl group, butylphenyl group and naphthyl group, etc. are mentioned, and these are only one kind. But two or more may be used. It is preferably a hydrocarbon group having 1 to 4 carbon atoms such as methyl group, ethyl group, allyl group and butyl group, more preferably methyl group and butyl group.

  BO is an oxybutylene group formed upon ring-opening addition of ethyl oxirane having 4 carbons.

  Further, n is an average addition mole number of the oxybutylene group BO formed along with the ring opening addition of ethyl oxirane having 4 carbon atoms, and is 25 or more. When n is less than 25, the formation of a high molecular weight polymer having a molecular weight of more than 10,000 is small, and there is a possibility that the lubricity improvement upon blending with other lubricating oils such as mineral oil and liquid paraffin is insufficient. There is. From such a viewpoint, n is set to 25 or more, preferably 30 or more.

  Also, as n increases, the viscosity tends to increase. Viscosity control is very important for the lubricating oil, and n is preferably 400 or less, more preferably 300 or less, from the viewpoint of ease of production and handling of the lubricating oil.

The alkyl oxirane derivatives according to the invention are defined in gel permeation chromatography (GPC) by means of a chromatogram obtained using a differential refractometer. The chromatogram is a graph showing the relationship between the refractive index intensity and the elution time. In the alkyl oxirane derivative of the present invention, the chromatogram is left-right asymmetric, satisfying the relationship of formula (2). The closer the value of M _L / M _H to 1, the more symmetrical the shape of the chromatogram.
_{0.35 ≦ M L / M H ≦} 0.75 ···· (2)

  Here, FIG. 1 is a model of a chromatogram obtained by gel permeation chromatography of an alkyl oxirane derivative, the abscissa represents the elution time, and the ordinate represents the refractive index intensity 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 rises as the refractive index intensity increases. After that, when the refractive index intensity maximum point K is reached, the elution curve descends.

  Further, in the gel permeation chromatography of the alkyl oxirane derivative of the present invention, when there are a plurality of refractive index maximum points in the chromatogram, the point having the largest refractive index intensity is taken as the refractive index intensity maximum point K. Furthermore, when there are a plurality of maximum points of the same refractive index intensity, the later one of the elution times is taken as the refractive index maximum point K. Under the present circumstances, the peak resulting from the developing solvent etc. which were used for gel permeation chromatography, and the pseudo peak by the fluctuation of the baseline resulting from the used column and apparatus are remove | excluded.

M _L / M _H is calculated from the chromatogram as follows, respectively.
(1) Draw a perpendicular from the refractive index intensity maximum point K on the chromatogram to the baseline B, and let L be the length of the perpendicular.
(2) Of the two points on the chromatogram where the refractive index intensity is L / 2, the one with the earlier elution time is taken as point O and the one with the later elution time is taken as point Q.
(3) Let P be the point of intersection of a straight line G connecting point O and point Q, and a perpendicular drawn from the refractive index intensity maximum point K to the baseline B.
(4) The distance between the point O and the intersection point P is M _H , and the distance between the intersection point P and the point Q is M _L.

The alkyl oxirane derivative of the present invention is one in which M _L / M _H satisfies 0.35 ≦ M _L / M _H ≦ 0.75. When M _L / M _H becomes larger than 0.75, the lubricity of the alkyl oxirane derivative decreases, and when this is blended with other lubricating oils such as mineral oil and liquid paraffin, sufficient lubricity improvement effect is not exhibited .

In addition, as M _L / M _H decreases, the bias on the high molecular weight side in the molecular weight distribution increases, and an increase in viscosity derived therefrom and the like can be seen. When M _L / M _H is smaller than 0.35, the viscosity becomes too high, and when considering blending into other lubricating oils such as mineral oil and liquid paraffin, the influence on the base oil viscosity becomes large, It becomes difficult to mix since handling is significantly deteriorated. From this viewpoint, although M _L / M _H is 0.35 or more, it is more preferably 0.40 or more, and particularly preferably 0.50 or more.

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

As = W _1/2 / W _5% (3)
0.30 ≦ As ≦ 0.80 (4)

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

  When a sample solution is injected into a gel chromatograph and developed, elution starts from the molecule with the highest molecular weight, and the elution curve rises as the refractive index intensity increases. Thereafter, the elution curve descends past the refractive index intensity maximum point where the refractive index intensity becomes maximum.

(1) Draw a perpendicular line from the refractive index intensity maximum point K on the chromatogram to the baseline B, and let its length be L.
(2) Of the two points on the chromatogram where the refractive index intensity is L / 20, the one with the earlier elution time is taken as point R, and the one with the later elution time is taken as point S.
(3) Let T be an intersection of a straight line H connecting the point R and the point S and a perpendicular drawn from the refractive index intensity maximum point K to the base line B.
(4) The distance between the point R and the intersection point 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 ≦ 0.80. By setting As to 0.80 or less, the lubricity is improved, and when the alkyl oxirane derivative is blended in, for example, a lubricant, the lubricity tends to be significantly improved. From this viewpoint, it is more preferable to set As to 0.75 or less.

  In addition, as As decreases, the bias on both sides of the polymer in the molecular weight distribution increases, and the increase in viscosity derived from it can be seen. By setting As to 0.30 or more, it is possible to suppress that the viscosity is increased and the handling is significantly deteriorated, and it can be easily blended in other lubricating oils such as mineral oil and liquid paraffin. From this viewpoint, As is more preferably 0.60 or more.

  By setting the peak top molecular weight indicated by the refractive index intensity maximum point K on the chromatogram calculated from the chromatogram to 1,500 to 10,000, the lubricity can be improved without causing the deterioration of the handling property due to the viscosity increase. It can be improved. From this viewpoint, it is preferable to set the peak top molecular weight indicated by the refractive index intensity maximum point K to 1,800 to 5,000. Furthermore, 0.5% to 50% of the peak area of the compound as a whole in the chromatogram, a high molecular weight product having a molecular weight of at least 5 times the peak top molecular weight indicated by the refractive index intensity maximum point K on the chromatogram calculated from the chromatogram. By containing 0%, the lubricity can be improved without causing the deterioration of the handling property due to the viscosity increase. The improvement of lubricity can not be expected if the content of the polymer having a molecular weight of not less than 5 times the peak top molecular weight indicated by the refractive index maximum intensity point K is 0.5% or less of the peak area of the whole compound in the chromatogram. If the content is 50.0% or more, the viscosity is increased and the handling is significantly deteriorated. From this point of view, it is preferable to contain 0.5% to 35.0% of the peak area of the whole compound in the chromatogram at least 5 times as high as the peak top molecular weight indicated by the refractive index intensity maximum point K.

In the present invention, gel permeation chromatography (GPC) for determining M _L , M _H and As is a system exclusively for SHODEX® GPC 101 GPC as a system, SHODEX RI-71s as a differential refractometer, and SHODEX KF as a guard column. -G, three columns of SHODEX KF 804L are continuously attached as a column, tetrahydrofuran is flowed at a flow rate of 1 ml / min as a developing solvent at a column temperature of 40 ° C, and 0.1 ml of a 0.1 wt% tetrahydrofuran solution of the obtained reaction product is injected. The BORWIN GPC calculation program is used to obtain a chromatogram represented by refractive index intensity and elution time.

  When producing the alkyl oxirane derivative of the present invention, preferably, the ring opening addition of ethyl oxirane having 4 carbon atoms is carried out in the presence of a double metal cyanide catalyst (hereinafter abbreviated as DMC catalyst) as an initiator. . In the reaction vessel, an initiator having at least one hydroxyl group in the molecule and a DMC catalyst are added, and after the reaction vessel is in an inert gas atmosphere, the alkyl oxirane is continuously or under pressure or under atmospheric pressure. Addition polymerization is carried out by intermittent addition and stirring.

At this time, although the average feed rate of the alkyl oxirane does not matter, in order to stably produce, it is desirable to change it by the total charged molar equivalent of the alkyl oxirane to the initiator. Specifically, the average feed rate V ₁ of alkyl oxirane when the total molar equivalent of alkyl oxirane is less than 60 with respect to the initiator V ₁ = 2 to 50 molar equivalent / hour, the total molar equivalent of alkyl oxirane is 60 or more, Average feed rate V ₂ of alkyl oxirane in the case of less than 100 V ₂ = 4 to 40 molar equivalents / hour, average feed rate of alkyl oxirane V _{3 in the range of} 100 or more and less than 250 It is preferable to control the average feed rate of alkyl oxirane so that the average feed rate of alkyl oxirane V ₄ = 7 to 30 mole equivalent / hour when the molar equivalent / hour, the total feed mole equivalent of alkyl oxirane is 250 or more .

  Moreover, 50 degreeC-150 degreeC are preferable, and 70 degreeC-110 degreeC of reaction temperature are more preferable. When the reaction temperature is higher than 150 ° C., the catalyst may be inactivated. When the reaction temperature is lower than 50 ° C., the reaction rate is slow and the productivity is poor.

Specific examples of the initiator in the present invention include, but are not limited to, the following.
Methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, allyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, pentyl alcohol, isopentyl alcohol, neopentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol Nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, icosyl alcohol, hen icosyl alcohol, Docosyl alcohol, tricosyl alcohol, butyl propylene glycol Such as call. Also, ethyl oxirane adducts of these initiators can be used as initiators as well. The amount of water contained in the initiator is not particularly limited, but the amount of water contained in the initiator is preferably 0.5 wt% or less.

  The amount of the DMC catalyst used is not particularly limited, but preferably 0.0001 to 0.1 wt%, more preferably 0.001 to 0.05 wt%, based on the alkyl oxirane derivative to be produced. The introduction of the DMC catalyst into the reaction system may be initially introduced all at once, or may be introduced successively in portions. After completion of the polymerization reaction, the composite metal complex catalyst is removed. The removal of the catalyst can be carried out by filtration, adsorbent treatment or the like.

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

_{Ma [M'x (CN) y]} b (H 2 O) c · (R) d ··· (5)

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

  As the metal M, Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Al (III), Sr (II), Mn (II), Cr (III), Cu (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), W (VI) etc. may be mentioned, and 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) And 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 ( Jig grime). Particularly preferred is Zn ₃ [Co (CN) ₆ ] ₂ in which tert-butyl alcohol is coordinated.

The alkyl oxirane derivative of the present invention can be incorporated into lubricating oils as base oils for lubricating oils and additives.
By blending the alkyl oxirane derivative of the present invention into a lubricating oil, it is useful in that it exhibits the effect of improving the lubricity which has not been found in conventional alkyl oxirane derivatives.

  The alkyl oxirane derivative of the present invention is used as a lubricant base oil or additive, and its concentration is preferably 0.01 to 100 wt%. By setting the concentration of the alkyl oxirane derivative to 0.01 wt% or more, the effect can be sufficiently exhibited.

  Further, the lubricant of the present invention can be used by blending various additives. Specifically, as the antioxidant, zinc dithiophosphate, organic sulfur compounds, hindered phenols, aromatic amines and the like can be mentioned. As oiliness improvers, long-chain fatty acids, fatty acid esters, higher alcohols, alkylamines and the like can be mentioned. As an antiwear agent, phosphate ester etc. are mentioned. As an extreme pressure agent, organic sulfur, a phosphorus compound, and an organic halogen compound are mentioned. Examples of metal deactivators include benzotriazole, N, N'-disalicylidene-1,2-diaminopropane and the like. Examples of the antifoaming agent include polymethylsiloxane, organic fluorine compounds, metal soaps, fatty acid esters, phosphoric acid esters, higher alcohols, and polyalkylene glycol compounds.

Hereinafter, the present invention will be described in detail by way of examples.
(Reference synthesis example: synthesis of complex metal cyanide complex catalyst)
Into 2.0 ml of an aqueous solution containing 2.1 g of zinc chloride, 15 ml of an aqueous solution containing 0.84 g of potassium hexacyanocobaltate K ₃ Co (CN) ₆ was added dropwise over 15 minutes while stirring at 40 ° C. After completion of the dropwise addition, 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, 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 after stirring for 30 minutes, filtration operation (second filtration) was performed to obtain a solid.

  Furthermore, 18.6 g of tert-butyl alcohol and 1.2 g of methanol are added to this solid again, and after stirring for 30 minutes, filtration operation (third filtration) is performed, and the obtained solid is dried at 40 ° C. under reduced pressure for 3 hours. Thus, 0.7 g of a composite metal cyanide complex catalyst was obtained.

Synthesis Example 1
Stainless steel 5 liter (4,890 ml inner volume) pressure-resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas injection tube, stirrer, vacuum exhaust tube, cooling coil, steam jacket, 74 g (1 n-butanol) Mol) and 0.2 g of the composite metal cyanide complex catalyst of the reference synthesis example. After the nitrogen substitution, the temperature was raised to 110 ° C. and 216 g (3 moles) of ethyl oxirane was charged over 1 hour from a nitrogen gas blowing pipe while stirring under the condition of 0.6 MPa or less. At this time, temporal changes in pressure and temperature in the reaction vessel were measured.

  After 3 hours, the pressure in the reaction vessel decreased sharply. Thereafter, while maintaining the inside of the reaction vessel at 110 ° C., under pressure of 0.6 MPa or less, ethyl oxirane is gradually added by pressure from a nitrogen gas blowing pipe, and 3,750 g (52 moles) of ethyl oxirane is stirred in total. The pressure was continuously added below. At this time, it took 360 minutes to charge the whole amount of ethyl oxirane.

  After completion of the addition, the reaction was allowed to proceed at 110 ° C. for 1 hour, and while filtering with nitrogen gas at 75 to 85 ° C. and 50 to 100 Torr for 1 hour, filtration was performed. The obtained reaction product (Synthesis example 1) was measured by gel permeation chromatography.

For gel permeation chromatography, a system dedicated to SHODEX GPC101GPC as a system, SHODEX RI-71S as a differential refractometer, SHODEX KF-GS as a guard column, and three HODEX KF804L as a column, column temperature 40 ° C, developing solvent Tetrahydrofuran is flowed at a flow rate of 1 ml / min, 0.1 ml of a 0.1 wt% tetrahydrofuran solution of the obtained reaction product is injected, and a chromatograph represented by refractive index strength and elution time using a BORWIN GPC calculation program I got a gram. FIG. 3 is the obtained chromatogram. From this chromatogram, M _L / M _H was determined to be 0.72, and As was 0.75.

(Composition example 2)
A reaction product was obtained by conducting the reaction in the same manner as in Synthesis Example 1 except that 215 g of tetradecyl alcohol was used instead of n-butanol as the initiator. The obtained reaction product was measured by gel permeation chromatography. As a result, M _L / M _H was 0.74, and As was 0.76.

(Composition example 3)
A reaction product was obtained by conducting the reaction in the same manner as in Synthesis Example 1 except that a total amount of 5048 g (70 moles) of ethyl oxirane was added. The obtained reaction product was measured by gel permeation chromatography. As a result, M _L / M _H was 0.61 and As was 0.70.

(Comparative Example 1)
50 g of n-butanol in a stainless steel 5-liter (internal volume: 4,890 ml) pressure-resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blowing pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket. 0.7 mol) and 7.7 g (0.1 mol) of sodium methoxide were charged. At 120 ° C., 3,750 g (52 moles) of ethyl oxirane were reacted for 80 hours. The remaining ethyl oxirane was removed under reduced pressure at 75 to 85 ° C. for 30 minutes, the reaction product was transferred to a 5 L eggplant flask, neutralized immediately with 1 N hydrochloric acid, dehydrated under a nitrogen gas atmosphere, and filtered.

The obtained reaction product (Comparative Synthesis Example 1) was measured by gel permeation chromatography. When M _L / M _H was determined from the chromatogram in the same manner as in Synthesis Example 1, it was 1.45 and As was 1.47.

In Table 1, the hydroxyl value is measured in accordance with JIS K-1557-1 and the kinematic viscosity in accordance with JIS K-2283, and the BO addition mole number (n) is calculated from the molecular weight converted from the hydroxyl value. Moreover, dynamic viscosity in Table 1 is measured based on JIS K-2283.
Further, Table 2 also shows the content ratio of the high-molecular weight compound 5 times or more the peak top molecular weight indicated by the refractive index intensity maximum point K.

(Examples 1 to 4, Comparative Examples 1 and 2)
In order to evaluate the lubricity of the lubricating oil of the formulation shown in Table 2, the dynamic friction coefficient was measured.

(Dynamic coefficient of friction measurement)
The dynamic friction coefficient was measured using a static friction measurement machine (TL201 Tt, Trinity Lab., Ltd.). In addition, as measurement conditions, it measured as an indenter; urethane rubber, load: 50 gf, scanning speed: 30 mm / s, and movement distance; 40 mm. The measurement was performed using a steel plate (standard test plate, JIS G 3141, Nippon Test Panel Co., Ltd.) and an aluminum plate (standard test plate, A1050P, Nippon Test Panel Co., Ltd.) as the metal plate.

  Lubricants using the alkyl oxirane derivative having a specific molecular weight distribution of the present invention shown in Examples 1 and 4 have hitherto been generally used as lubricant components shown in Comparative Examples 1 and 2 Compared with alkyl oxirane derivatives having a molecular weight distribution that spreads to the low molecular weight side and having the same degree of kinematic viscosity, the coefficient of dynamic friction between various metals and urethane rubber is clearly lower, showing excellent lubricity.

In addition, also in the lubricant using the alkyl oxirane derivative having a specific molecular weight distribution of the present invention shown in Examples 2 and 3, the dynamic friction coefficient between various metals and urethane rubber is low, and the lubricant exhibits excellent lubricity. I understand.

Claims (5)

An alkyl oxirane derivative, which is represented by the formula (1) and calculated from a chromatogram determined by gel permeation chromatography, and M _H and M _L satisfy the relationship of the formula (2).

R ¹ O- (BO) n-H (1)

(In the formula (1),
R ¹ represents a hydrocarbon group having 1 to 22 carbon atoms,
BO represents an oxybutylene group formed upon ring-opening addition of ethyl oxirane having 4 carbon atoms,
n represents a number of 25 or more. )


_{0.35 ≦ M L / M H ≦} 0.75 ···· (2)

(The length of the perpendicular from the maximum point K where the refractive index intensity on the chromatogram is maximum to the baseline B is L, and the elution time is at two points on the chromatogram where the refractive index intensity is L / 2 Let the earlier one be point O, the later one with elution time be point Q, and let P be the point of intersection of the straight line G connecting point O and point Q and the perpendicular drawn from the refractive index intensity maximum point K to the baseline. , And the distance between the point O and the intersection point P is M _H, and the distance between the point Q and the intersection point P is M _L.
The alkyl oxirane derivative according to claim 1, wherein As calculated from the chromatogram satisfies the relationship of Formula (3) and Formula (4).

As = W _1/2 / W _5% (3)
0.30 ≦ As ≦ 0.80 (4)

(On the chromatogram, one of the two points at which the refractive index intensity is L / 20 is the earlier elution time, and the later one is the straight line H connecting the point R and the point S. Let T be the point of intersection of the refractive index intensity maximum point K with the perpendicular drawn to the base line B, let T _{1/2 be} the distance between point R and point of intersection T, and W _{5% be} the distance between point R and point S. )
The alkyl oxirane according to claim 1 or 2, wherein the peak top molecular weight indicated by the refractive index intensity maximum point K on the chromatogram calculated from the chromatogram is 1,500 to 10,000. Derivative.
The alkyloxirane derivative according to any one of claims 1 to 3, wherein the chromatogram has one of the refractive index intensity maximum points.
A lubricant comprising the alkyl oxirane derivative according to any one of claims 1 to 4.

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