JP2003105365A - Viscosity regulator for lubricant and lubricant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a viscosity regulator for a lubricant, providing a lubricant composition having excellent balance of low-temperature characteristics, lubrication at high temperature, and activities for improving a viscosity index, and hardly causing phase separation, and further to provide the lubricant containing the viscosity regulator and having the excellent low-temperature characteristics. SOLUTION: This viscosity regulator for the lubricant comprises [A] an ethylene-α-olefin copolymer of a copolymer of ethylene and a 3-20C α-olefin, having 65-79 wt.% ethylene content (E), and [B] an ethylene-α-olefin copolymer of the copolymer of the ethylene and the 3-20C α-olefin, and having 40-55 wt.% ethylene content. The lubricant composition contains [I] the viscosity regulator for the lubricant and [II] a lubricant base regulated so that the content of the viscosity regulator for the lubricant is 1-20 wt.%. In another aspect, the lubricant composition contains [I] the viscosity regulator for the lubricant, [II] the lubricant base and [III] an agent for reducing the fluid point, regulated so that the proportion of the viscosity regulator [I] for the lubricant is 0.1-5 wt.%, and the proportion of the agent [III] for reducing the fluid point is 0.05-5 wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a viscosity modifier for lubricating oil and a lubricating oil composition, and more particularly to a lubricating oil composition for obtaining a lubricating oil composition having excellent low temperature characteristics and lubricity at high temperatures. The present invention relates to a viscosity modifier and a lubricating oil composition containing the viscosity modifier.

[0002]

BACKGROUND OF THE INVENTION Petroleum products generally have a large change in viscosity when the temperature changes, but it is preferable that the lubricating oil for automobiles, for example, has a small temperature dependence of the viscosity.
Therefore, in recent years, an ethylene / α-olefin copolymer has been widely used as a viscosity modifier having a viscosity index improving effect for the purpose of reducing the temperature dependence of the lubricating oil.

[0003] In addition, when the temperature of the lubricating oil becomes low, the wax component in the lubricating oil crystallizes and loses its fluidity. Therefore, the lubricating oil also contains a pour point depressant in order to lower the solidification temperature. The pour point depressant lowers the pour point of the lubricating oil by inhibiting the formation of a three-dimensional network due to the crystallization of the wax component in the lubricating oil. By the way, among the low temperature characteristics of a lubricating oil containing a viscosity modifier having a viscosity index improving effect and a pour point depressant, the viscosity at a high shear rate depends on the compatibility between the lubricating oil base material and the viscosity modifier. However, the viscosity under low shear rate is strongly influenced by the pour point depressant.
Further, it is known that when ethylene / α-olefin copolymerization having a specific composition is used as a viscosity modifier, the effect of the pour point depressant is significantly reduced by the interaction with the pour point depressant (US 3,697, 429, US 3,551,33
No. 6 specification).

For this reason, a viscosity adjusting agent to be added to a lubricating oil, particularly a lubricating oil which is required to have excellent low temperature characteristics, is required to have an excellent effect of improving the viscosity index and not inhibit the action of the pour point depressant. To be Examples of viscosity modifiers that satisfy such requirements include Japanese Patent Publication No. 6-96624.
Japanese Patent Laid-Open Publication No. 2003-242242 discloses an ethylene / α-olefin copolymer having an inhomogeneous distribution of ethylene units and α-olefin units, having an ethylene content of 30 to 80% by weight and a weight average molecular weight of A copolymer having a Mw / Mn of less than 2 is disclosed, which is 20,000 to 750,000.

By the way, since 2000, the specifications of automobile lubricating oils have been revised in North America, and the low temperature characteristics of the lubricating oils have become more important. For this reason, the advent of a viscosity modifier capable of providing a lubricating oil composition that satisfies the requirements for the new standard has been desired. The inventors of the present invention have investigated a viscosity modifier for such a new standard, and found that a high ethylene content
When an ethylene / propylene copolymer (for example, 70 to 78% by weight) is used as a viscosity modifier, the viscosity modifier is dramatically improved, but the viscosity modifier is phase-separated from the mineral oil under low temperature-high shear rate. However, it was found that there are points to be improved such as clogging of the mesh.

As a result of studies to solve the above-mentioned problems, the inventors of the present invention found that a high ethylene content and high molecular weight ethylene / α-olefin copolymer was added to a lubricating oil as a viscosity modifier. With excellent low temperature characteristics,
It was considered that a lubricating oil composition having excellent lubricating properties at high temperatures and a good balance of the effect of improving the viscosity index could be obtained. However, high ethylene content and high molecular weight ethylene / α
It has been discovered that when an olefin copolymer is blended with a lubricating oil as a viscosity modifier, phase separation easily occurs.

As a result of further investigation, as a viscosity modifier, an ethylene / α-olefin copolymer having an ethylene content (E) of 65 to 79% by weight and an ethylene content (E) were used.
When a composition comprising 40 to 55% by weight of an ethylene / α-olefin copolymer is used as a viscosity modifier, all of the above problems are solved, and low temperature characteristics, lubricity at high temperature, and viscosity index improving effect are obtained. The inventors have found that a lubricating oil composition having an excellent balance of the above and a phase separation that is difficult to obtain can be obtained, and thus completed the present invention.

[0008]

An object of the present invention is to provide a lubricating oil composition comprising a specific ethylene / α-olefin copolymer, which has an excellent balance of low-temperature characteristics, lubricity at high temperatures, and an effect of improving the viscosity index, and which is difficult to undergo phase separation. It is an object of the present invention to provide such a viscosity adjusting agent for lubricating oil and a lubricating oil composition containing the viscosity adjusting agent and having excellent low temperature properties.

[0009]

SUMMARY OF THE INVENTION The viscosity modifier for lubricating oil according to the present invention is
[A] A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein the ethylene content (E) is 65 to 79% by weight.
Which is an ethylene / α-olefin copolymer of [B] ethylene and an α-olefin having 3 to 20 carbon atoms and has an ethylene content (E) of 40 to 55% by weight.
It is characterized by being composed of an α-olefin copolymer.

Such a viscosity modifier for lubricating oil is a ¹³ C-NM of ethylene / α-olefin copolymer [A].
The intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα determined by R spectrum is 0.5 or less, and ¹³ C-NMR of the ethylene / α-olefin copolymer [B] is obtained.
¹³ C-NM of ethylene / α-olefin copolymer [A] having an intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα determined by a spectrum of more than 0.5
The intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα determined by R spectrum is larger than 0.5, and ¹³ C-NMR of the ethylene / α-olefin copolymer [B] is obtained.
The intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα determined by the spectrum is 0.5 or less, or ¹³ C-NM of ethylene / α-olefin copolymer [A]
The intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα determined by the R spectrum is 0.5 or less, and the intensity of Sαβ relative to Sαα determined by the ¹³ C-NMR spectrum of the ethylene / α-olefin copolymer [B]. The ratio D (Sαβ / Sαα) is preferably 0.5 or less.

The ethylene / α-olefin copolymer
The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of [A] is 70,000.
It is preferably in the range of 0 to 400,000. Mw / Mn of the ethylene / α-olefin copolymer [A]
(Mw: weight average molecular weight, Mn: number average molecular weight)
It is preferably 2.4 or less.

The ethylene / α-olefin copolymer
The melting point (Tm) of [A] is preferably in the range of 15 to 60 ° C. The ethylene / α-olefin copolymer
The ethylene content (E) and melting point (Tm) of [A] are calculated by the following formula
It is preferable to satisfy the relational expression represented by (1). 3.31 × E-186 ≧ Tm (1) The polystyrene-equivalent weight average molecular weight of the ethylene / α-olefin copolymer [B] measured by gel permeation chromatography is 70,000-40.
It is preferably in the range of 0000.

The ethylene / α-olefin copolymer
The Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) of [B] is preferably 2.4 or less. The ethylene / α-olefin copolymer [B] has a melting point (T
It is preferred that m) is not higher than -15 ° C or does not contain a crystalline part. It is preferable that the ethylene content (E) and the melting point (Tm) of the ethylene / α-olefin copolymer [B] satisfy the relational expression represented by the following formula (1).

3.31 × E-186 ≧ Tm (1) In the viscosity adjusting agent for lubricating oil according to the present invention, [A] ethylene
The weight ratio ([A] / [B]) of the α-olefin copolymer and the [B] ethylene / α-olefin copolymer is 99/1 to 1/99.
It is preferably in the range of. The lubricating oil composition according to the present invention comprises [I] the above-mentioned lubricating oil viscosity modifier and [II] a lubricating oil base material, and the lubricating oil viscosity modifier [I] is in an amount of 1 to 20% by weight. It is characterized by being included in.

The lubricating oil composition according to the present invention is [I]
The viscosity modifier for lubricating oil, [II] a lubricating oil base material, and [III]
A pour point depressant, and the viscosity modifier for lubricating oil [I] is contained in a proportion of 0.1 to 5% by weight.
I] is contained in an amount of 0.05 to 5% by weight.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The viscosity modifier for lubricating oil and the lubricating oil composition according to the present invention will be specifically described below. [Viscosity modifier for lubricating oil] The viscosity modifier for lubricating oil according to the present invention is a copolymer of [A] ethylene and an α-olefin having 3 to 20 carbon atoms and an ethylene content (E) of 65. ~ 79
% Ethylene-α-olefin copolymer, [B] ethylene-C3-20 α-olefin copolymer, ethylene content (E) is 40-55 wt% ethylene It is characterized by being composed of an α-olefin copolymer. Thus, the viscosity adjusting agent for lubricating oils, which is composed of two kinds of ethylene / α-olefin copolymers having a specific amount of ethylene, has an excellent balance of low-temperature characteristics, lubricity at high temperatures, and the effect of improving the viscosity index.

Ethylene / α-olefin copolymer [A] The ethylene / α-olefin copolymer [A] comprises a repeating unit derived from ethylene and a repeating unit derived from an α-olefin having 3 to 20 carbon atoms. Yes, 3 to 2 carbon atoms
Examples of the α-olefin of 0 include propylene, butene-1,
Pentene-1,3-methylbutene-1, hexene-1,4-
Methylpentene-1, octene-1, decene-1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1 and the like can be mentioned. Of these, propylene is particularly preferable. The α-olefin has 4 to 2 carbon atoms.
In the case of an α-olefin of 0, especially low temperature characteristics, for example, low temperature fluidity are improved.

The ethylene content of the ethylene / α-olefin copolymer [A] is, for example, 65 to 79% by weight, preferably 70 to 79% by weight, more preferably 71 to 78% by weight, further preferably 72 to 78% by weight. It is in the range of%.
Others are repeating units derived from an α-olefin having 3 to 20 carbon atoms. The ethylene content in the ethylene / α-olefin copolymer is determined by ¹³ C-NMR according to the method described in the above-mentioned "Polymer Analysis Handbook" (edited by the Society for Analytical Chemistry, Japan, published by Kinokuniya Bookstore).
Measured at.

The ethylene / α-olefin copolymer [A] is at least one monomer selected from cyclic olefins and polyenes (hereinafter sometimes referred to as "other monomer") within a range not impairing the object of the present invention. The repeating unit derived from (1) may be contained in a proportion of, for example, 5% by weight or less, preferably 1% by weight or less. In addition, in this invention, it is one preferable aspect that it does not contain a polyene. In this case, it is particularly excellent in heat resistance. Furthermore, it is also a preferred embodiment that the polymer consists essentially of ethylene and α-olefin. (1) Weight average molecular weight Such an ethylene / α-olefin copolymer [A] is
The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) was 70,
000 to 400,000, preferably 70,000 to 32
0000, more preferably 70,000 to 200,0
The range of 00 is desirable.

A lubricating oil composition containing an ethylene / α-olefin copolymer having a weight average molecular weight (Mw) within the above range has a particularly excellent balance between low-temperature characteristics and viscosity index improving performance. When the weight average molecular weight (Mw) is within the above range, the concentrated solution containing the ethylene / α-olefin copolymer is separated from the lubricating oil base material under low temperature / high shear rate to prevent clogging of the mesh. Less likely to cause problems. If the weight average molecular weight is within the above lower limit,
Sufficient viscosity index improving performance can be obtained. (2) Molecular weight distribution Further, such ethylene / α-olefin copolymer
[A] is Mw / Mn (M which is an index showing the molecular weight distribution.
w: weight average molecular weight, Mn: number average molecular weight) is 2.4
Below, it is desirable to be in the range of preferably 1.5 to 2.3.

When the molecular weight distribution is 2.4 or less, the shear stability of the lubricating oil viscosity becomes good when the ethylene / α-olefin copolymer [A] is blended in the lubricating oil base material. (3) Melting point The melting point of the ethylene / α-olefin copolymer [A] (T
m) is in the range of 15 to 60 ° C, preferably 25 to 50 ° C, more preferably 25 to 45 ° C.

Such an ethylene / α-olefin copolymer [A] further has the above-mentioned ethylene content (E:% by weight).
And the melting point (Tm: ° C) preferably satisfy the relationship represented by the following formula (1). 3.31 × E-186 ≧ Tm (1) Preferably 3.31 × E-192 ≧ Tm (1-1) More preferably 3.31 × E-193 ≧ Tm (1-2) The ethylene / α-olefin copolymer [A] satisfying the condition (1) is particularly excellent in cold resistance and no turbidity when blended in a lubricating oil.

Ethylene / α-olefin copolymer [B] The ethylene / α-olefin copolymer [B] comprises a repeating unit derived from ethylene and a repeating unit derived from an α-olefin having 3 to 20 carbon atoms. Yes, 3 to 2 carbon atoms
Examples of the α-olefin of 0 include the same as those exemplified in the above ethylene / α-olefin copolymer [A].

The ethylene content of the ethylene / α-olefin copolymer [B] is, for example, 40 to 55% by weight, preferably 43 to 53% by weight, more preferably 45 to 51% by weight.
Is in the range. Others are repeating units derived from an α-olefin having 3 to 20 carbon atoms. Also ethylene / α
The olefin copolymer [B] has a repeating unit derived from at least one monomer selected from cyclic olefins and polyenes (hereinafter sometimes referred to as “other monomer”) within a range not impairing the object of the present invention. , For example 5
It may be contained in an amount of not more than 1% by weight, preferably not more than 1% by weight. In the present invention, the fact that polyene is not included is 1
This is one preferred embodiment. In this case, it is particularly excellent in heat resistance. Furthermore, it is also a preferred embodiment that the polymer consists essentially of ethylene and α-olefin. (1) Weight average molecular weight Such an ethylene / α-olefin copolymer [B] is
The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) was 70,
000 to 400,000, preferably 70,000 to 32
0000, more preferably 70,000 to 200,0
The range of 00 is desirable.

A lubricating oil composition containing an ethylene / α-olefin copolymer having a weight average molecular weight (Mw) within the above range has a particularly excellent balance between low-temperature characteristics and viscosity index improving performance. When the weight average molecular weight (Mw) is within the above range, the concentrated solution containing the ethylene / α-olefin copolymer is separated from the lubricating oil base material under low temperature / high shear rate to prevent clogging of the mesh. Less likely to cause problems. If the weight average molecular weight is within the above lower limit,
Sufficient viscosity index improving performance can be obtained. (2) Molecular weight distribution Further, such ethylene / α-olefin copolymer
[B] is Mw / Mn (M
w: weight average molecular weight, Mn: number average molecular weight) is 2.4
Below, it is desirable to be in the range of preferably 1.5 to 2.3.

When the molecular weight distribution is 2.4 or less, the shear stability of the lubricating oil viscosity becomes good when the ethylene / α-olefin copolymer [B] is blended in the lubricating oil base material. (3) Melting point The ethylene / α-olefin copolymer [B] preferably has a melting point (Tm) of -15 ° C or does not contain a crystalline part.

The melting point is preferably -20 ° C or lower, more preferably -30 ° C or lower.
Regarding the melting point, an endothermic curve of a differential scanning calorimeter (DSC) was obtained, and the temperature at the maximum peak position was taken as the melting point. For the measurement, the sample was packed in an aluminum pan, heated up to 200 ° C. at 10 ° C./min, held at 200 ° C. for 5 minutes, and then at −20 ° C./min −15.
It was determined from the endothermic curve when the temperature was lowered to 0 ° C. and then at 10 ° C./min, that is, the 2nd run.

Those having no crystalline part are judged to have no endothermic peak by measuring DSC. Such ethylene / α-olefin copolymer
[B] is preferably such that the ethylene content (E: wt%) and the melting point (Tm: ° C) satisfy the relationship represented by the following formula (1).

3.31 × E-186 ≧ Tm (1) Preferably 3.31 × E-192 ≧ Tm (1-1) More preferably 3.31 × E-193 ≧ Tm (1-2) The ethylene / α-olefin copolymer [B] satisfying the above formula (1) is particularly excellent in cold resistance and turbidity-free. (4) Strength ratio D (Sαβ / Sαα) In the viscosity adjusting agent for lubricating oil according to the present invention, the ethylene / α-olefin copolymers [A] and [B] are ethylene / α-olefin copolymers. S determined by the ¹³ C-NMR spectrum of at least one of the combined [A] and [B]
The intensity ratio D (Sαβ / Sαα) of Sαβ to αα is
It is preferably 0.5 or less.

The intensity ratio D (Sαβ / Sαα) is 0.
When the ethylene / α-olefin copolymer having a ratio of 5 or less is contained, it is possible to obtain a lubricating oil composition having a better balance between low temperature characteristics and lubricating oil characteristics at high temperatures. Examples of such a combination of the ethylene / α-olefin copolymers [A] and [B] include the following. ¹³ C-NM of ethylene / α-olefin copolymer [A]
The intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα determined by R spectrum is 0.5 or less, and ¹³ C-NMR of the ethylene / α-olefin copolymer [B] is obtained.
The intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα obtained by the spectrum is larger than 0.5. ¹³ C-NM of ethylene / α-olefin copolymer [A]
The intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα determined by R spectrum is larger than 0.5, and ¹³ C-NMR of the ethylene / α-olefin copolymer [B] is obtained.
An intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα obtained by the spectrum is 0.5 or less. ¹³ C-NM of ethylene / α-olefin copolymer [A]
The intensity ratio D (Sαβ / Sαα) of Sαβ to Sαα determined by the R spectrum is 0.5 or less, and the intensity of Sαβ relative to Sαα determined by the ¹³ C-NMR spectrum of the ethylene / α-olefin copolymer [B]. The ratio D (Sαβ / Sαα) is 0.5 or less.

Ethylene / α-with a strength ratio D value of 0.5 or less
The D value of the olefin copolymer is more preferably 0.4 or less, and further preferably 0.3 or less.
When the strength ratio D (Sαβ / Sαα) of the ethylene / α-olefin copolymers [A] and [B] is such a combination as described above, the fluidity of the lubricating oil at low temperatures can be improved and Further, it is possible to improve the lubrication characteristics at high temperatures, and further, it is particularly excellent in the balance of both (low temperature fluidity and high temperature lubrication characteristics).

Sαβ and Sαα obtained by ¹³ C-NMR spectrum are CH _{2 in} a structural unit derived from ethylene or an α-olefin having 3 or more carbon atoms, respectively.
Peak intensity of two types of CH at the positions shown below
Means _two .

[0033]

[Chemical 1]

The spectrum measured by ¹³ C-NMR was measured by JC Randall (Review Macromolecular Chemistry).
Physics, C29, 201 (1989)) and analyzed to determine Sαβ and Sαα. The intensity ratio D is calculated by the integrated value (area) ratio of each peak portion. The intensity ratio D thus obtained is generally the ratio of the 1,1 addition reaction of the α-olefin followed by the 2,1 addition reaction, or the 1,2 addition reaction of the α-olefin followed by the 1,2 addition reaction. It is considered to be a measure of the rate at which an addition reaction occurs. Therefore, the larger the strength ratio D value, the more irregular the bonding direction of the (b) α-olefin. Conversely, the smaller the D value, the more regular the bonding direction of the (b) α-olefin.

The ethylene / α-olefin copolymers [A] and [B] have the above-mentioned ethylene content,
It can be produced by copolymerizing ethylene, an α-olefin and, if necessary, another monomer in the presence of a known olefin polymerization catalyst. As a known olefin polymerization catalyst, a metallocene catalyst, a solid titanium catalyst, a vanadium catalyst, or the like is used.

When producing the α-olefin copolymer [A] and / or [B] having a strength ratio D (Sαβ / Sαα) of more than 0.5, a vanadium catalyst is preferably used. Further, an ethylene / α-olefin copolymer [A] and / or [B] having a strength ratio D (Sαβ / Sαα) of 0.5 or less.
When producing, a metallocene catalyst or a solid titanium catalyst is used, and a metallocene catalyst is particularly preferable,
Among them, a metallocene catalyst comprising a metallocene compound of a transition metal selected from Group 4 of the periodic table and an ionized ionic compound capable of reacting with an organoaluminum oxy compound and / or a transition metal metallocene compound to form ions Particularly preferably used. Particularly preferably, a combination of a metallocene compound of a transition metal and an ionized ionic compound capable of reacting with the transition metal metallocene compound to form an ion is preferable from the viewpoint of composition distribution.

(1) Metallocene-based catalyst The metallocene compound of the transition metal selected from Group 4 of the periodic table forming the metallocene-based catalyst is specifically represented by the following general formula (i). expressed. MLx (i) In the formula (i), M is a transition metal selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, and x is the valence of the transition metal.

L is a ligand that coordinates to a transition metal, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton and has this cyclopentadienyl skeleton. The ligand may have a substituent. Examples of the ligand having a cyclopentadienyl skeleton include, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-
Or i-propylcyclopentadienyl group, n-, i-, se
c-, t-, butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, penta Methylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, ethylbutylcyclo Alkyl- or cycloalkyl-substituted cyclopentadienyl groups such as pentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl And the like.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. Of these, alkyl-substituted cyclopentadienyl groups are particularly preferred. When the compound represented by the general formula (i) has two or more groups having a cyclopentadienyl skeleton as the ligand L, the groups having two cyclopentadienyl skeletons are ethylene and propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group, or a methylphenylsilylene group.

Examples of L other than the ligand having a cyclopentadienyl skeleton include a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (-SO ₃ ^Ra ), halogen. And an atom or a hydrogen atom (wherein R ^a is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group) and the like.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, a methyl group,
Alkyl group such as ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group , A cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, and an aralkyl group such as a benzyl group and a neofil group.

As the alkoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group,
Examples thereof include n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group and octoxy group. Examples of the aryloxy group include a phenoxy group and the like, and a sulfonic acid-containing group (—SO ₃ ^Ra )
Examples thereof include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, and a p-chlorobenzenesulfonato group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the metallocene compound in which M is zirconium and at least two ligands having a cyclopentadienyl skeleton are shown below. Bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl)
Zirconium dichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, etc.

Further, compounds in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be mentioned. Further, in the present invention, a compound represented by the following general formula (ii) can be used as the metallocene compound. _{^{L 1 M 1 X z ... (}} ii) ( wherein M is a metal of Group 4 of the periodic table or lanthanum series, L ¹ is a derivative of a delocalized π bond group, a metal M ¹ active site The constraint geometry is given to
Are each independently hydrogen, halogen or a hydrocarbon group containing 20 or less carbon, silicon or germanium,
It is a silyl group or a germyl group. ) Among such compounds represented by the general formula (ii),
The compound represented by the following general formula (iii) is preferable.

[0045]

[Chemical 2]

In the formula, M ¹ is titanium, zirconium or hafnium, and X is the same as above. Cp is M
A substituted cyclopentadienyl group having a π bond to ¹ and having a substituent Z. Z is oxygen, sulfur, boron or an element of Group 14 of the periodic table (for example, silicon, germanium or tin), Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y are condensed rings. May be formed.

Specific examples of the compound represented by the general formula (iii) include [dimethyl (t-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silane]
Titanium dichloride, [(t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dichloride, [dibenzyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) Silane] titanium dichloride, [dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane] dibenzyl titanium, [dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane ] Dimethyl titanium, [(t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl] dibenzyl titanium, [(methylamido) (tetramethyl-η ⁵ -cyclopentadienyl)- 1,2-ethanediyl] dineopentyl titanium, [(phenylphosphide) (tetramethyl-η ^5-
Cyclopentadienyl) methylene] diphenyl titanium,
[Dibenzyl (t-butylamide) (tetramethyl-η ^5-
Cyclopentadienyl) silane] dibenzyl titanium,
[Dimethyl (benzylamido) (η ⁵ -cyclopentadienyl) silane] di (trimethylsilyl) titanium, [dimethyl (phenylphosphide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] dibenzyltitanium,
[(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl] dibenzyl titanium, [2-η ^5- (Tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2
-)] Dibenzyl titanium, [2-η ^5- (tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)] dimethyl titanium, [2-((4a, 4b, 8a, 9,9a -η) -9H-fluorene
-9-yl) cyclohexanolate (2-)] dimethyl titanium, [2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)] Examples thereof include dibenzyl dititanium.

In addition, compounds in which titanium metal is replaced with zirconium metal or hafnium metal in the above compounds can also be mentioned. These metallocene compounds may be used alone or in combination of two or more. In the present invention, as the metallocene compound represented by the general formula (i), a zirconocene compound having a central metal atom of zirconium and having a ligand containing at least two cyclopentadienyl skeletons is preferably used. . Further, the above general formula (ii) or (iii)
In the metallocene compound represented by, the central metal atom is preferably titanium. Among the above metallocene compounds, compounds represented by the general formula (iii), in which the central metal atom is titanium, are particularly preferable.

The organoaluminum oxy compound forming the metallocene catalyst may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound. The conventionally known aluminoxane is specifically represented by the following general formula.

[0050]

[Chemical 3]

(In the above general formulas (iv) and (v), R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group and an ethyl group, and particularly preferably a methyl group. in and, m is 2 or more, preferably 5 to 40 integer.) here, the aluminoxane formulas (OAl (R ¹⁾⁾ alkyloxy aluminum units and formula represented by (OAl (R ² )) Alkyloxyaluminum unit [wherein R ¹ and R ² can be the same hydrocarbon groups as R, and R ¹ and R ² represent different groups]. It may be formed from oxyaluminum units.

Examples of the ionized ionic compound which forms the metallocene catalyst include Lewis acids and ionic compounds. As the Lewis acid, BR ₃ (R
Is a phenyl group which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group, or fluorine. ), For example, trifluoroboron, triphenylboron, tris (4-
Fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl)
Boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron,
Examples include tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts and triarylphosphonium salts. Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl). ) Boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o,
p-Dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, etc. To be

As the N, N-dialkylanilinium salt,
For example, N, N-dimethylanilinium tetra (phenyl) boron,
N, N-diethylanilinium tetra (phenyl) boron,
Examples thereof include N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron.

Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate. In particular, ionized ionic compounds are preferably used because they control the composition distribution of the ethylene / α-olefin copolymer.

When forming the metallocene catalyst, an organoaluminum compound may be used together with the organoaluminum oxy compound and / or the ionized ionic compound. Examples of the organoaluminum compound include compounds represented by the following general formula (vi).

R ¹ _n AlX _3-n (vi) In the formula, R ¹ has ¹ to 15 carbon atoms, preferably 1 to 4 carbon atoms.
X is a halogen atom or a hydrogen atom, and n is 1 to 3. The number of such carbon atoms is 1
Examples of the hydrocarbon group of to 15 include an alkyl group, a cycloalkyl group or an aryl group, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group and a hexyl group. , Octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum,
Trialkylaluminums such as trioctylaluminum and tri2-ethylhexylaluminum; general formula (i-
. C ₄ H ₉₎ in _{x Al y (C 5 H 10} ) z ( wherein, x, y, z are each a positive number, and z ≧ 2x) alkenyl aluminum such as isoprenyl aluminum represented by; Trialkenyl aluminum such as triisopropenyl aluminum; Dialkyl aluminum halide such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide; methyl aluminum sesquichloride, ethylaluminium sesquichloride, isopropyl aluminum sesquichloride. Alkyl aluminum sesquihalides such as butyl aluminum sesquichloride, ethyl aluminum sesquibromide, methyl aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; Dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; Alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride.

In the presence of the metallocene catalyst as described above, ethylene and an α-olefin having 3 to 20 carbon atoms and, if necessary, another monomer are usually copolymerized in a liquid phase. At this time, a hydrocarbon solvent is generally used as a polymerization solvent, but an α-olefin such as propylene may be used. (2) Solid Titanium Catalyst As the solid titanium catalyst, (a) a titanium compound and (b) a formula MgOR ^a OR ^b [R ^a and R ^b are an alkyl group or an aryl group, and R ^a and R ^b May be the same or different. ] With a magnesium compound represented by
(c) A solid titanium catalyst component formed by contacting an electron donor is used. (a) Titanium compound As the titanium compound, a tetravalent titanium compound is particularly preferably used. Examples of such a tetravalent titanium compound include compounds represented by the following formula.

In the formula Ti (OR) _g X _4-g , R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4. Specific examples of such compounds include TiCl ₄ and TiB.
Tetrahalogenated titanium such as r ₄ and TiI ₄ , Ti (OCH)
₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , T
Trihalogenated alkoxytitanium such as i (OC ₂ H ₅ ) Br ₃ and Ti (O-iso-C ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ Cl ₂ and Ti
(OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H
₅ ) Dihalogenated dialkoxy titanium such as ₂ Br ₂ , Ti
_{(OCH 3) 3 Cl, Ti} (OC 2 H 5) 3 Cl, Ti (On-C 4 H 9)
Mono-halogenated trialkoxy titanium such as ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br, Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti
Examples thereof include tetraalkoxytitanium such as (On-C ₄ H ₉ ) ₄ , Ti (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. You may use these titanium compounds in combination of 2 or more types. The titanium compound may be diluted with a hydrocarbon or a halogenated hydrocarbon before use. (b) Magnesium Compound The magnesium compound is represented by the formula MgOR ^a OR ^b . In the formula, R ^a and R ^b are an alkyl group or an aryl group, preferably an alkyl group or an aryl group having 1 to 8 carbon atoms. R ^a and R ^b may be the same or different.

As such a magnesium compound,
Specifically, dimethoxy magnesium, diethoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, di n-octoxy magnesium, di2-ethylhexoxy magnesium, ethoxypropoxy magnesium, ethoxybutoxy magnesium and other alkoxy magnesium, diphenoxy Examples thereof include magnesium and allyloxy magnesium such as dimethylphenoxy magnesium.

These may be used in combination of two or more kinds. Among these, diethoxy magnesium is preferable. Incidentally, the magnesium compound as described above
(b) can also be used after being contacted with a titanium compound and / or a hydrocarbon solvent in advance. As the titanium compound, the titanium compound (a) as described above can be used, and titanium tetrachloride is preferably used. Examples of the hydrocarbon solvent include propane, butane,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, kerosene, cyclopentane,
Examples thereof include alicyclic hydrocarbons such as cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as ethylene chloride and chlorobenzene. These may be used in combination. Among these hydrocarbon solvents, halogenated hydrocarbons and aromatic hydrocarbons are preferable, and aromatic hydrocarbons are particularly preferable.

The magnesium compound (b) is preferably used as a suspension of the magnesium compound by contacting it with an aromatic hydrocarbon. The contact between the magnesium compound (b) and the titanium compound as described above can also be carried out in the presence of a hydrocarbon solvent. Specific examples of the (c) electron donor used in the preparation of the solid titanium catalyst include the following compounds. Amines such as methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, tributylamine and tribenzylamine; pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole; pyrroline; pyrrolidine; indole; pyridine , Pyridines such as methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, and pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines; tetrahydrofuran, 1,4-Cineol, 1,8-Cineol, Pinolfuran, Methylfuran, Dimethylfuran, Diphenylfuran, Benzofuran, Coumaran, Futara Cyclic oxygenates such as tetrahydropyran, pyran and ditedropyran; methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol Alcohols having 1 to 18 carbon atoms such as isopropyl alcohol and isopropylbenzyl alcohol; carbon which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol Phenols having 6 to 20 atoms; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetone Ketones having 3 to 15 carbon atoms such as ruacetone and benzoquinone; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate , Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexanecarboxylate, methyl benzoate, benzoate Ethyl acid, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-cyclohexenecarboxylic acid
Hexyl, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, etc. C2 to C30 organic acid ester; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether,
Ethers having 2 to 20 carbon atoms such as amyl ether, anisole, diphenyl ether epoxy-p-menthane; 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-isobutyl-1,3-dimethoxypropane , 2,2
-Isopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2-isopropyl-1,3-dimethoxypropane,
2,2-isopentyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane,
2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 1,2-bis-methoxymethyl-bicyclo- [2,2,1] -heptane, Diphenyldimethoxysilane, isopropyl-t-
Diethers such as butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopentyl-2-isopropyl-1,3-dimethoxycyclohexane; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide Nitriles such as acetonitrile, benzonitrile and tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride are used.

As the electron donor, a silicon compound represented by the general formula (vii) described below can be used. The solid titanium catalyst component can be prepared by contacting the above titanium compound, magnesium compound and electron donor by a known method. When the titanium compound, the magnesium compound and the electron donor are brought into contact with each other, the following carrier compound can be used to prepare the carrier-supported solid titanium catalyst component (a).

When preparing the solid titanium catalyst component,
In addition to these compounds, organic and inorganic compounds containing silicon, phosphorus, aluminum and the like, which are used as carrier compounds and reaction aids, may be used. Such carrier compounds include Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ ,
MgO, CaO, TiO ₂ , ZnO, SnO ₂ , BaO, Th
Resins such as O and styrene-divinylbenzene copolymer can be used. Among these, Al ₂ O ₃ and SiO ₂
A styrene-divinylbenzene copolymer is preferably used.

In the solid titanium catalyst, an organometallic compound catalyst component and an electron donor are used together with the solid titanium catalyst component as described above. Organometallic compound catalyst component The organometallic compound catalyst component preferably contains a metal selected from Group I to Group III of the periodic table, and specifically,
Examples thereof include organic aluminum compounds, complex alkyl compounds of group I metal and aluminum, and organic metal compounds of group II metal.

As such an organoaluminum compound, for example, an organoaluminum compound represented by the following formula can be exemplified. R ^a _n AlX _3-n (wherein R ^a
Is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1 to 3. ) ^Ra is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group. Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum, and alkenyl such as isoprenylaluminum. Dialkyl aluminum halides such as aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, and dimethyl aluminum bromide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesqui Bu Alkylaluminum sesquihalide such as bromide, methyl aluminum dichloride, ethyl aluminum dichloride,
Examples thereof include alkyl aluminum dihalides such as isopropyl aluminum dichloride and ethyl aluminum dibromide, and alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound, a compound represented by the following formula can also be used. R ^a _n AlY _{3-n In the} above formula, R ^a is the same as above, and Y is -OR.
^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group,
A —SiR ^f ₃ group or a —N (R ^g ) AlR ^h ₂ group, and n is 1
To R 2, R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, and the like, and ^Re is hydrogen, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ^f and R ^g are methyl group, ethyl group and the like.

As such an organoaluminum compound, the following compounds are specifically used. (i) R ^a _n Al (OR ^b ) _3-n : dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc., (ii) R ^a _n Al (OSi)
_{^{R c) 3-n: Et}} 2 Al (OSiMe 3), (iso-Bu) 2 Al (O
(SiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc., (iii)
R ^a _n Al (OAl R ^d ₂ ) _3-n : Et ₂ AlOAlEt ₂ , (iso-B
u) ₂ AlOAl (iso-Bu) _{2 and the} like, (iv) R ^a _n Al (N
_{^{R e 2) 3-n:}} Me 2 AlNEt 2, Et 2 AlNHM e, Me 2 Al
NHET, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN
(Me ₃ Si) ₂ etc., (v) R ^a _n Al (SiR ^f ₃ ) _3-n : (iso-B
u) ₂ AlSiMe _{3 and the} like, (vi) R ^a _n Al [N (R ^g ) -Al
R ^h _{2] 3-n: Et 2 AlN (} Me) -AlEt 2 (iso-Bu) 2 AlN
(Et) Al (iso-Bu) ₂ etc.

Further, a compound similar to this, for example, an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can be mentioned. More _{specifically, (C 2 H 5) 2} AlOAl (C 2 H 5) 2, (C 4 H 9) 2
_{AlOAl (C 4 H 9) 2} , (C 2 H 5) 2 AlN (C 2 H 5) Al
(C ₂ H ₅ ) ₂ and the like, as well as aluminoxanes such as methylaluminoxane.

Among the above organoaluminum compounds,
R^a ₃Al, R^a _nAl (OR^b)_3-n , R ^a _nAl (OAlR^d ₂)
_3-n And a preferred example of an organoaluminum compound represented by
Can be listed. Group I metal and aluminum
The complex alkylated compound of is a compound represented by the following general formula:
The thing can be illustrated.

M ¹ AlR ^j ₄ (M ¹ is Li, Na, K, and R ^j has 1 to 15 carbon atoms.
Specifically, LiAl (C ₂ H ₅ ) ₄ ,
LiAl (C ₇ H ₁₅ ) _{4 and the} like can be mentioned. Examples of the organometallic compound of the Group II metal include compounds represented by the following general formula.

R ^k R ^l M ² (R ^k and R ^l are hydrocarbon groups having 1 to 15 carbon atoms or halogen, and they may be the same or different from each other.
Except when both are halogen. M ² is Mg, Z
Specific examples include diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, and the like.

Two or more of these compounds can be used in combination. Electron Donor As the electron donor, for example, an organosilicon compound represented by the following general formula (vii) can be used. R _n Si (OR ′) _4-n (vii) (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysisilane, diisopropyldimethoxysilane,
t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane , Screw p-
Tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethylsilane Dimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane,
Methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane Silane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, Dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane Orchid, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, etc.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane, etc. It is preferably used.

Further, in the present invention, as the electron donor,
2,6-Substituted piperidines, 2,5-Substituted piperidines, N, N,
Substituted methylenediamines such as N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethylmethylenediamine, 1,3-dibenzylimidazolidine, 1,3-dibenzyl-2
-Nitrogen-containing electron donors such as substituted methylenediamines such as phenylimidazolidine, triethylphosphite,
Phosphorus-containing electron donors such as trin-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, and diethyl phenyl phosphite , 6-substituted tetrahydropyrans, 2,
Oxygen-containing electron donors such as 5-substituted tetrahydropyrans can also be used.

Two or more of these electron donors can be used in combination. The olefin polymerization catalyst according to the present invention may contain other components useful for the polymerization of olefins, in addition to the above-mentioned components. The olefin polymerization catalyst may be prepolymerized. The prepolymerization catalyst preliminarily (co) polymerizes olefins and polyene compounds used in the main polymerization described below in the presence of a solid titanium catalyst component, an organometallic compound catalyst component and, if necessary, an electron donor. It is obtained by (3) Vanadium-based catalyst The vanadium catalyst comprises (a) a soluble vanadium compound and (b)
It consists of an organic aluminum compound.

Solubility to form vanadium-based catalyst (a)
The vanadium compound (v-1) is specifically represented by the following general formula:
expressed. VO (OR)_aX_b   Or V (OR)_cX_d In the formula, R is an alkyl group, a cycloalkyl group, an aryl group
Represents a hydrocarbon group, X represents a halogen atom,
a, b, c, d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 respectively
≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦
4 is satisfied. (It is preferable that the a satisfies 1 <a ≦ 3.
It is preferable that c satisfies 1 <c ≦ 3.
Further, it is preferable that the d satisfies 0 ≦ d <4. ) As a soluble vanadium compound represented by the above general formula
Is, specifically, VOCl₃, VO (OCH₃) Cl₂, VO
(OC₂H_Five) Cl₂, VO (OC₂H_Five)_1.5Cl_{1 .Five}, VO (O
C₂H_Five)₂Cl, VO (O n-C₃H₇) Cl₂, VO (O iso-
C₃H₇) Cl ₂, VO (O n-C_FourH₉) Cl₂, VO (O iso-
C_FourH₉) Cl₂, VO (O sec-C_FourH₉) Cl₂, VO (O t-
C_FourH₉) Cl₂, VO (OC₂H_Five)₃, VOBr₂, VCl_Four,
VOCl₂, VO (O n-C_FourH₉)₃, VOCl₃・ 2OC₈
H₁₇OH etc. are mentioned.

As the organoaluminum compound forming the vanadium-based catalyst, the organoaluminum compounds exemplified for the metallocene catalyst are used. Ethylene above
-The olefin copolymer (A) is preferably a liquid in which ethylene and an α-olefin having 3 to 20 carbon atoms and, if necessary, other monomers are usually added in the presence of the metallocene catalyst or the vanadium catalyst as described above. Manufactured by copolymerization in phase. At this time, a hydrocarbon solvent is generally used as a polymerization solvent, but liquid α-olefin such as propylene may be used.

The hydrocarbon solvent used for polymerizing the ethylene / α-olefin copolymer is pentane,
Hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons and their halogen derivatives; cyclohexane, methylcyclopentane, methylcyclohexane and other alicyclic hydrocarbons and their halogen derivatives; benzene, toluene, xylene and other fragrances Group hydrocarbons and halogen derivatives such as chlorobenzene are used. These solvents may be used alone or in combination of two or more.

Ethylene, an α-olefin having 3 to 20 carbon atoms, and optionally other monomers can be copolymerized by either a batch method or a continuous method, but the continuous method can be used. It is preferable to carry out the copolymerization by a continuous method using a stirred layer reactor. When the copolymerization is carried out by the continuous method, the metallocene catalyst is used at the following concentrations, for example.

The concentration of the metallocene compound in the polymerization system is usually 0.00005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.05 mmol / liter.
It is a liter. The organoaluminum oxy compound has a molar ratio of aluminum atom to transition metal in the metallocene compound in the polymerization system (Al / transition metal) of 1 to
It is supplied in an amount of 10,000, preferably 10-5000.

The ionized ionic compound is a molar ratio of the ionized ionic compound to the metallocene compound in the polymerization system (ionized ionic compound / metallocene compound).
It is supplied in an amount of 0.5 to 30, preferably 1 to 25.
When an organoaluminum compound is used, it is generally used in an amount of about 0 to 5 mmol / liter (polymerization volume), preferably about 0 to 2 mmol / liter.

In the presence of the above metallocene catalyst, ethylene and an α-olefin having 3 to 20 carbon atoms,
When other monomers are copolymerized as necessary, the copolymerization reaction is usually carried out at a temperature of -20 ° C to 150 ° C, preferably 0 ° C to 120 ° C, more preferably 0 ° C to 100 ° C.
The pressure is more than 0 and 80 kg / cm ² or less, preferably more than 0 and 50 kg / cm ² or less. The above-mentioned polymerization conditions are preferably constant in the continuous polymerization method.

When a solid titanium catalyst is used as a catalyst, the amount is usually about 0.001 to 100 mmol, preferably about 0.005 to 20 mmol, in terms of titanium atom per liter of polymerization volume. Used. In the organometallic compound catalyst component [II], the metal atom in the catalyst component [II] is usually about 1 to 2000 mol, based on 1 mol of the titanium atom in the solid titanium catalyst component [I] in the polymerization system, It is preferably used in an amount of about 2 to 500 mol.
The electron donor [III] is an organometallic compound catalyst component [II]
Usually about 0.001 mol to 10 mol of the metal atom of
It is used in a molar amount, preferably from 0.01 mol to 5 mol. The polymerization temperature is usually about 20 to 300 ° C., preferably about 50 to 150 ° C., and the polymerization pressure is normal pressure to 100 kg /
cm ² , preferably about ² to 50 kg / cm ² . In the present invention, the polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further polymerization,
It is also possible to carry out the reaction in two or more steps by changing the reaction conditions.

When a vanadium-based catalyst is used as the catalyst, the concentration of the soluble vanadium compound in the polymerization system is usually 0.01 to 5 mmol / liter (polymerization volume), preferably 0.05 to 3 It is mmol / liter. It is desirable that the soluble vanadium compound is supplied at a concentration of 10 times or less, preferably 1 to 7 times, and more preferably 1 to 5 times the concentration of the soluble vanadium compound present in the polymerization system. The organoaluminum compound has a molar ratio (Al / V) of aluminum atom to vanadium atom in the polymerization system of usually 2 or more, preferably 2
~ 50, more preferably 3-20.

The soluble vanadium compound and the organoaluminum compound are usually supplied after being diluted with the above-mentioned hydrocarbon solvent and / or liquid propylene. At this time, the soluble vanadium compound is preferably diluted to the above-mentioned concentration, but the organoaluminum compound is supplied to the polymerization system after being adjusted to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization system. Is desirable.

When ethylene, an α-olefin having 3 to 20 carbon atoms and, if necessary, another monomer are copolymerized in the presence of a vanadium catalyst, the copolymerization reaction is usually carried out at a temperature of -50 ° C. ~ 100 ° C, preferably -30 ° C ~
It is carried out at a temperature of 80 ° C., more preferably −20 ° C. to 60 ° C., and a pressure of more than 0 and 50 kg / cm ² or less, preferably more than 0 and 20 kg / cm ² or less. The above-mentioned polymerization conditions are preferably constant in the continuous polymerization method.

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours. Ethylene and 3 to 2 carbon atoms
The α-olefin of 0, and optionally other monomers, are supplied to the polymerization system in an amount such that an ethylene / α-olefin copolymer having the above-mentioned specific composition is obtained. Further, in the copolymerization, a molecular weight modifier such as hydrogen can be used.

As described above, ethylene and carbon number 3
When an .alpha.-olefin of .about.20 and, if necessary, another monomer are copolymerized, an ethylene / .alpha.-olefin copolymer is usually obtained as a polymerization liquid containing the same. This polymerization liquid is treated by a conventional method to obtain the ethylene / α-olefin copolymer used in the present invention. Further, as will be described later, this polymerization liquid can be directly used when preparing a lubricating oil viscosity modifier.

Composition of Lubricating Oil Viscosity Adjusting Agent The lubricating oil viscosity adjusting agent of the present invention comprises the above-mentioned ethylene / α
-The weight ratio ([A] / [B]) of the olefin copolymer [A] and the ethylene / α-olefin copolymer [B] is preferably 99 /
1 to 1/99, preferably 90/10 to 10/90, more preferably 80/20 to 20/80, and further preferably 70/30 to 30/70.

[A] is ethylene-α-having 4 or more carbon atoms
In the case of an olefin copolymer and [B] is an ethylene / propylene copolymer, [A] / [B] is 70 /
30 to 30/70 is particularly excellent in specific low temperature. In addition, the weight average molecular weight (Mw-A) of the ethylene / α-olefin copolymer [A] and the ethylene / α-olefin copolymer [B]
Ratio (Mw-B) / (Mw-A) to the weight average molecular weight (Mw-B) of
Is more than 1, preferably 1.1 or more.

The fact that (Mw-B) / (Mw-A) is larger than 1 means that the ethylene / α-olefin copolymer [B] having a lower ethylene content has a lower ethylene content. It shows that the weight average molecular weight is larger than that of the α-olefin copolymer [A]. Like this (Mw-
When B) / (Mw-A) is larger than 1, the lubricating oil obtained when blended with the lubricating oil base material has excellent low-temperature fluidity, high shear stability of lubricating oil viscosity, and phase separation. Hateful. Also,
When ethylene / α-olefin copolymer (A) is used as a viscosity modifier, GF- which is the next-generation North American lubricating oil standard
It is possible to obtain a lubricating oil that can meet the low temperature characteristic standards of the three standards. Whether or not the lubricating oil satisfies the GF-3 standard can be determined by measuring CCS and MRV described later.

Such a viscosity modifier for lubricating oil is prepared, for example, by the following method. (1) A method of melt-kneading the above-mentioned ethylene / α-olefin copolymers [A] and [B]. (2) The ethylene / α-olefin copolymer containing a solvent
A method of mixing [A] and [B] and kneading them while removing the solvent. (3) A method of removing the solvent after mixing the polymer solutions in which the ethylene / α-olefin copolymers [A] and [B] are dissolved in the solvent.

In the preparation methods (2) and (3), the polymer solution immediately after polymerization may be used as it is. By doing so, the number of processing steps after polymerization can be reduced, and thus the manufacturing cost can be reduced. In the lubricating oil viscosity adjusting agent according to the present invention, without preparing the lubricating oil viscosity adjusting agent by melting and kneading as described above,
Direct ethylene / α-olefin copolymer [A] and [B]
May be blended in the lubricating base oil and mixed in the lubricating oil.

Lubricating Oil Composition Some lubricating oil compositions according to the present invention contain the above-mentioned lubricating oil viscosity modifier [I] and a lubricating oil base material [II]. Some contain a viscosity modifier [I], a lubricating oil base [II] and a pour point depressant [III].

First, each component forming the lubricating oil composition according to the present invention will be described. [II] Lubricating Oil Base Materials The lubricating oil base materials used in the present invention include mineral oils and synthetic oils such as poly α-olefins, polyol esters, and polyalkylene glycols. Mineral oils or mineral oils and synthetic oils A blend with is preferably used. Mineral oil is generally used after undergoing a purification process such as dewaxing,
There are several grades depending on the purification method, but generally 0.5
Mineral oil with a wax content of -10% is used. Further, those having a kinematic viscosity at 40 ° C. of 10 to 200 cSt are generally used.

[III] Pour Point Depressant As the pour point depressant used in the present invention, alkylated naphthalene, (meth) alkyl methacrylate (co) polymer, (co) polymer of alkyl acrylate, and alkyl fumarate are used. Examples thereof include copolymers with vinyl acetate, α-olefin polymers, and copolymers with α-olefins and styrene. Among them, alkyl methacrylate (co) polymers and alkyl acrylate (co) polymers Coalescence is preferably used.

The lubricating oil composition of the present invention contains the above-mentioned viscosity adjusting agent for lubricating oil [I] and a lubricating oil base material [II], and the lubricating oil composition contains the lubricating oil composition for lubricating oil. 1 for viscosity modifier [I]
-20% by weight, preferably 5-10% by weight (the balance is the lubricating oil base material [II] and the compounding agent described below). Such a lubricating oil composition comprises a lubricating oil base [II],
The lubricating oil base material [II] is 80 to 99% by weight and the lubricating oil viscosity modifier [I] is 1 to 20% by weight based on the total amount of 100% by weight of the lubricating oil viscosity adjusting agent [I]. Is more preferable.

A viscosity adjusting agent for lubricating oil [I] and a lubricating oil base material [I]
The lubricating oil composition containing [I] and [I] has low temperature dependence and excellent low temperature characteristics. This lubricating oil composition can be used as it is for lubricating oil applications, or can be used for lubricating oil applications by further adding a lubricating oil base material, pour point depressant, etc. to this lubricating oil composition. The lubricating oil composition according to the present invention contains the above-described viscosity adjusting agent for lubricating oil [I], a lubricating oil base material [II], and a pour point depressant [III]. In the composition, ethylene / α-olefin copolymer [I]
In an amount of 0.1 to 5% by weight, preferably 0.3 to 2% by weight, and the pour point depressant [III] in an amount of 0.05 to 5% by weight, preferably 0.1 to 2% by weight ( The balance may be contained in the lubricating oil base material [II] and the compounding agent described below).

Lubricating oil base material [II] and viscosity adjusting agent for lubricating oil
A lubricating oil composition containing [I] and a pour point depressant [III] has a small temperature dependence and a viscosity adjusting agent [I] for lubricating oil.
And the pour point depressant [III] interact little to increase the pour point, and it has excellent low temperature properties in all shear rate regions. Further, this lubricating oil composition can satisfy the standard of low temperature characteristics of the GF-3 standard.

The lubricating oil composition according to the present invention comprises, in addition to the above components, a (co) polymer of alkyl methacrylate and hydrogenated S.
Compounding agents such as BR and SEBS having a viscosity index improving effect, detergents, rust preventives, dispersants, extreme pressure agents, foam inhibitors, antiwear agents, antioxidants, metal deactivators, etc. You may mix. As the extreme pressure agent, sulfur-based extreme pressure agents such as sulfides, sulfoxides, sulfones, thiophosphinates, thiocarbonates, fats and oils, sulfurized fats and oils, sulfurized olefins; phosphoric acid esters, phosphorous acid esters, phosphoric acid Examples thereof include phosphoric acids such as ester amine salts and phosphite amines; and halogen compounds such as chlorinated hydrocarbons.

Examples of the antiwear agent include inorganic or organic molybdenum compounds such as molybdenum disulfide, organic boron compounds such as alkylmercaptyl borate; graphite, antimony sulfide, boron compounds, polytetrafluoroethylene and the like. Examples of the detergent include metal sulfonates such as calcium sulfonate, magnesium sulfonate and barium sulfonate, thiophosphonates, phenates, salicylates, succinimides, benzylamines, succinic acid esters and the like.

As the antioxidant, 2,6-di-t-butyl-4-
Examples thereof include amine compounds such as methylphenol and sulfur or phosphorus compounds such as zinc dithiophosphate. Examples of the antirust agent include carboxylic acids such as oxalic acid and salts thereof; sulfonates; esters; alcohols; phosphoric acid and salts thereof; benzotriazole and derivatives thereof; thiazole compounds and the like.

Examples of the foam suppressor include dimethyl siloxane, silicone type compounds such as silica gel dispersion, alcohol type or ester type compounds and the like. The blending amount of these additives varies depending on the required lubricating performance, but is usually 0.01 to 50 parts by weight, preferably 0.05 to 100 parts by weight of the lubricating oil composition.
˜30 parts by weight may be included.

Method for Preparing Lubricating Oil Composition In the lubricating oil composition according to the present invention, the lubricating oil base material [II] is mixed or dissolved with the viscosity adjusting agent for lubricating oil [I] and, if necessary, the compounding agent. Alternatively, a lubricant base material [II] is prepared by a conventionally known method by mixing or dissolving a viscosity adjusting agent for lubricant [I], a pour point depressant [III] and, if necessary, a compounding agent. can do.

In the present specification, all numerical values such as the amount of materials, reaction conditions, molecular weight, and the number of carbon atoms are "about" unless technically unclear unless otherwise specified. Is preferred to be understood by supplementing the word

[0110]

EFFECTS OF THE INVENTION By using the viscosity modifier for lubricating oil according to the present invention, the lubricating oil is excellent in low-temperature characteristics and lubricating characteristics at high temperatures, and is well balanced with thickening effect, and is hard to undergo phase separation. A composition can be obtained.

[0111]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. In this example, various physical properties were measured as follows. Ethylene content Using a JEOL LA500 type nuclear magnetic resonance apparatus, a mixed solvent of ortho-dichlorobenzene and benzene-d6 (ortho-dichlorobenzene / benzene-d6 = 3/1 to 4/1)
(Volume ratio), 120 ° C., pulse width 45 ° pulse, pulse repetition time 5.5 seconds.

Sαβ / Sαα Sαβ and Sαα are determined by ¹³ C-NMR spectrum. Viscosity at 100 ° C. (KV) Measurements were made according to ASTM D 445. In this example, the KV was adjusted to be about 10 mm ² / sec.

Cold Cranking Simulator (CCS) Viscosity Measured at −20 ° C. according to ASTM D 2602. CCS is used to evaluate the slidability (startability) of the crankshaft at low temperatures, and the smaller the value, the better the low temperature characteristics of the lubricating oil. Mini-Rotary (MR) Viscosity Based on ASTM D 3829, D 4684, -3
The measurement was performed at 0 ° C. MRV is used for evaluation for pumping an oil pump at a low temperature, and the smaller the value, the better the low temperature characteristics of the lubricating oil.

Shear Stability Index (SSI) Measurements were made according to ASTM D 3945. SSI
Is a measure of the loss of kinematic viscosity due to shearing of the copolymer component in the lubricating oil under sliding and breaking of the molecular chain,
The larger the SSI, the larger the loss. HTHS viscosity (High Temperature High Shear Viscosit
y) The HTHS viscosity was evaluated by the ASTM D4684 test method (evaluation based on SAE J300 viscosity classification) at 150 ° C./10 ⁶ s ⁻¹ . The higher this value, the better the lubricating oil performance at high temperature.

Low Temperature Fluidity (Low Temperature Storage Stability) After cooling the lubricating oil composition at −18 ° C. for 2 weeks, the lubricating oil composition was observed for fluidity (appearance) and evaluated as follows. ○: Flowing ×: Gelled

[0116]

[Polymerization Example 1] of ethylene / α-olefin copolymer [A-1]
Polymerization 900 ml of heptane was inserted at 23 ° C. into a SUS autoclave with a stirring blade having a capacity of 2 liters, which was sufficiently replaced with nitrogen. Into this autoclave, 5Nl of propylene and 150 ml of hydrogen were inserted while rotating a stirring blade and cooling with ice.
Next, the autoclave was heated to 60 ° C. and further pressurized with ethylene so that the total pressure became 6 KG. When the internal pressure of the autoclave reached 6 KG, 1.0 ml of a 1.0 mM / ml hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. Subsequently, triphenylcarbenium (tetrakispentafluorophenyl) borate prepared in advance was converted into B in an amount of 0.016 mM,
Dimethyl (t-butylamido) (tetramethyl-η5-cyclopentadienyl) silane] titanium dichloride
3 ml of a toluene solution containing an amount of 0004 mM was injected into the autoclave with nitrogen to initiate polymerization. After that, the temperature of the autoclave was adjusted to 70 ° C. for 5 minutes, and ethylene was directly supplied so that the pressure became 6 kg. Five minutes after the initiation of polymerization, 5 ml of methanol was inserted into the autoclave by a pump to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. 3 l of methanol was poured into the reaction solution while stirring. The polymer containing the obtained solvent is dried at 130 ° C. for 13 hours at 600 torr and 3
2 g of ethylene / propylene copolymer was obtained.

The properties of the obtained polymer are shown in Table 1.

[0118]

[Polymerization Example 2] Ethylene / α-olefin copolymer [B-1]
Polymerization 900 ml of heptane was inserted at 23 ° C. into a SUS autoclave with a stirring blade having a capacity of 2 liters, which was sufficiently replaced with nitrogen. Into this autoclave, 13Nl of propylene and 100 ml of hydrogen were inserted while cooling the stirring blade and cooling with ice. Next, the autoclave was heated to 70 ° C. and further pressurized with ethylene so that the total pressure became 6 KG. When the internal pressure of the autoclave reached 6 KG, 1.0 ml of a 1.0 mM / ml hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. Subsequently, triphenylcarbenium (tetrakispentafluorophenyl) borate prepared in advance was converted into B in an amount of 0.02 mM,
Dimethyl (t-butylamido) (tetramethyl-η5-cyclopentadienyl) silane] titanium dichloride
3 ml of a toluene solution containing an amount of 0005 mM was pressed into the autoclave with nitrogen to initiate polymerization. After that, the temperature of the autoclave was adjusted to 70 ° C. for 5 minutes, and ethylene was directly supplied so that the pressure became 6 kg. Five minutes after the initiation of polymerization, 5 ml of methanol was inserted into the autoclave by a pump to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. 3 l of methanol was poured into the reaction solution while stirring. The polymer containing the obtained solvent is dried at 130 ° C. for 13 hours at 600 torr and 3
1 g of ethylene / propylene copolymer was obtained.

The properties of the obtained polymer are shown in Table 1.

[0120]

[Polymerization Examples 3 to 8] Ethylene and α-in the amounts shown in Table 1
Olefin (comonomer) was copolymerized. The ethylene / α-olefin copolymers [A-3] and [B-2] were polymerized by using a metallocene catalyst in the same manner as in Polymerization Example 2. In addition, ethylene / α-olefin copolymers [A-2], [A
-4], [A-5] and [B-3] were polymerized using a vanadium-based catalyst.

The properties of the obtained polymer are shown in Table 1.

[0122]

[Table 1]

[0123]

Examples 1 to 5 A sheet-like ethylene / propylene copolymer [B-1] having an ethylene content of 47% by weight and a polystyrene-equivalent weight average molecular weight of 200,000 was cooled with liquid nitrogen and pulverized. A pulverized product of the copolymer [B-1] thus molded and an ethylene / propylene copolymer having an ethylene content of 72% by weight and a polystyrene-converted weight average molecular weight of 190,000.
Mix the pellets of [A-1] with the ratio shown in Table 2, and mix L / D
Kneading was performed under the following conditions in a nitrogen atmosphere with a 30 mm twin-screw extruder of 40 mm.

[Kneading conditions] Set temperature: C1 / C2 / C3 / C4 / C5 / H / D = 1
60/180/200/220/220/220/20
0 ° C. Screw rotation speed: 100 rpm The lubricant viscosity adjusting agent prepared as described above was added to the base oil according to the composition shown in Table 2 to prepare a lubricating oil composition, and the physical properties of the lubricating oil were determined.

Mineral oil 15 is used as the base oil (lubricating oil base material).
0 Neutral (manufactured by EESO) is used, and PPD (manufactured by Sanyo Kasei Co., Ltd., Acrope 13) is used as a pour point depressant.
3) was used, and a detergent dispersant (manufactured by Exxon) was used. The results are shown in Table 2.

[0126]

[Comparative Example 1] As a viscosity adjusting agent for lubricating oil, an ethylene-propylene copolymer [B-1] alone was used without using the ethylene-propylene copolymer [A-1]. A lubricating oil composition was prepared and evaluated in the same manner as in Example 1 except that it was used as. The results are shown in Table 2.

[0127]

Examples 6 to 9 In Examples 1 to 5, ethylene / α-olefin copolymers [B-2] and [B-3] were used instead of the ethylene / propylene copolymer [B-1]. In addition, instead of ethylene-propylene copolymer [A-1], ethylene
The α-olefin copolymers [A-2] to [A-5] were used.

Then, in the proportions shown in Table 2, kneading was carried out in the same manner as in Example 1 to prepare a viscosity adjusting agent for lubricating oil. The obtained viscosity modifier for lubricating oil was blended with the base oil in the same manner as in Examples 1 to 5, and the lubricating oil properties of the lubricating oil composition were evaluated. The results are shown in Table 2.

[0129]

[Comparative Example 2] As a viscosity modifier for lubricating oil, an ethylene / propylene copolymer [A-1] alone was used without using the ethylene / propylene copolymer [B-1]. A lubricating oil composition was prepared and evaluated in the same manner as in Example 1 except that it was used as. The results are shown in Table 2.

[0130]

[Table 2]

As is clear from Table 2, a lubricating oil composition containing a lubricating oil viscosity modifier comprising two ethylene / α-olefin copolymers having a specific ethylene content has low temperature characteristics and high temperature lubrication. It has excellent properties and a good balance with the thickening effect, and also has excellent properties that phase separation is difficult.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10N 20:04 C10N 20:04 30:02 30:02 30:08 30:08 (71) Applicant 591131338 The Lubrisol Corporation THE LUBRIZOL CORPOR ATION United States of America Ohio 44092, Wycliffe Lakeland Boulevard 29400 29400 Lakeland Boulevard, Wickliffe, Ohra Ohta 44092, Uniteda Oka Ohta loc. Mitsui Chemicals Co., Ltd. In-house (72) Inventor Ryosuke Kinshige 3 Chikusaigan, Ichihara-shi, Chiba Mitsui Chemicals Co., Ltd. Internal F-term (reference) 4H104 CA03C CA04C CA05C EA01C EA03C EA04 EA21 C EB05 LA01 LA04

Claims (15)

[Claims] 1. A copolymer of [A] ethylene and an α-olefin having 3 to 20 carbon atoms, wherein the ethylene content (E) is 65.
~ 79% by weight of ethylene / α-olefin copolymer,
[B] A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein the ethylene content (E) is 40 to 55% by weight.
A viscosity modifier for a lubricating oil, which comprises the ethylene / α-olefin copolymer of 2. The ethylene / α-olefin copolymer
Sαα determined by ¹³ C-NMR spectrum of [A]
The intensity ratio D (Sαβ / Sαα) of Sαβ to
5 or less, ¹³ C-N of the ethylene / α-olefin copolymer [B]
Sαβ for Sαα obtained from the MR spectrum
The viscosity ratio for lubricating oil according to claim 1, wherein the strength ratio D (Sαβ / Sαα) of is larger than 0.5. 3. The ethylene / α-olefin copolymer
Sαα determined by ¹³ C-NMR spectrum of [A]
The intensity ratio D (Sαβ / Sαα) of Sαβ to 0.
5, ¹³ C-N of the ethylene / α-olefin copolymer [B]
Sαβ for Sαα obtained from the MR spectrum
The viscosity ratio for lubricating oil according to claim 1, wherein the strength ratio D (Sαβ / Sαα) is 0.5 or less. 4. The ethylene / α-olefin copolymer
Sαα determined by ¹³ C-NMR spectrum of [A]
The intensity ratio D (Sαβ / Sαα) of Sαβ to 0.
5 or less, ¹³ C-N of the ethylene / α-olefin copolymer [B]
Sαβ for Sαα obtained from the MR spectrum
The viscosity ratio for lubricating oil according to claim 1, wherein the strength ratio D (Sαβ / Sαα) is 0.5 or less. 5. The ethylene / α-olefin copolymer
The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of [A] is 70,000.
The viscosity modifier for lubricating oil according to any one of claims 1 to 4, which is in a range of 0 to 400,000. 6. The ethylene / α-olefin copolymer
The viscosity modifier for lubricating oil according to any one of claims 1 to 5, wherein Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) of [A] is 2.4 or less. 7. The ethylene / α-olefin copolymer
The melting point (Tm) of [A] is in the range of 15 to 60 ° C. 7. The viscosity modifier for lubricating oil according to claim 1, wherein 8. The ethylene / α-olefin copolymer
The ethylene content (E) and melting point (Tm) of [A] are calculated by the following formula
The viscosity adjusting agent for lubricating oil according to any one of claims 1 to 7, which satisfies the relational expression represented by (1). 3.31 × E-186 ≧ Tm (1) 9. The ethylene / α-olefin copolymer
The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of [B] is 70,000.
The viscosity modifier for lubricating oil according to any one of claims 1 to 8, which is in the range of 0 to 400,000. 10. The ethylene / α-olefin copolymer
Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) of [B] is 2.4 or less, The viscosity modifier for lubricating oil according to any one of claims 1 to 9, wherein 11. The ethylene / α-olefin copolymer
[B] has a melting point (Tm) of -15 ° C or lower,
Alternatively, the crystalline portion is not included.
The viscosity modifier for lubricating oil according to any one of 10. 12. The ethylene / α-olefin copolymer
The ethylene content (E) and melting point (Tm) of [B] are calculated by the following formula
The viscosity adjusting agent for lubricating oil according to any one of claims 1 to 11, which satisfies the relational expression represented by (1). 3.31 × E-186 ≧ Tm (1) 13. A weight ratio of [A] ethylene / α-olefin copolymer to [B] ethylene / α-olefin copolymer.
([A] / [B]) is in the range of 99/1 to 1/99, The viscosity modifier for lubricating oil according to claim 1, wherein 14. [I] The viscosity adjusting agent for lubricating oil according to any one of claims 1 to 13 and [II] a lubricating oil base material, wherein the viscosity adjusting agent [I] for lubricating oil is 1 A lubricating oil composition, characterized in that it is contained in an amount of -20% by weight. 15. A lubricating oil viscosity modifier according to any one of claims 1 to 13, [II] a lubricating oil base material, and [III] a pour point depressant. Lubrication, characterized in that the viscosity modifier [I] for use is contained in a proportion of 0.1 to 5% by weight, and the pour point depressant [III] is contained in an amount of 0.05 to 5% by weight. Oil composition.