JPH0491106A - Solid catalyst component, catalyst containing the same solid catalyst component for polymerizing olefin and production of ethylene-alpha-olefin copolymer using the same catalyst for polymerizing olefin - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer having a high melt tension by prepolymerizing a monomer in the presence of a catalyst containing a solid composed of a specific Mg.Al complex, a liquid Ti compound and a transition metallic compound and an organoaluminum compound and then copolymerizing ethylene with an alpha-olefin in the presence of the resultant prepolymerized catalyst. CONSTITUTION:Ethylene in an amount of 1-1000g based on 1g of (A) a solid catalyst component, containing a solid Mg.Al complex, obtained by bringing a solution, etc., composed of a halogen-containing Mg compound, an alcohol and a hydrocarbon solvent into contact with an organoaluminum compound and containing Mg, a halogen, Al and alkoxy groups into contact with a tetravalent Ti compound in a liquid state and one transition metallic compound such as a V compound, a Zr compound and an Hf compound, etc., in a liquid state, containing the Mg, halogen, Al, Ti and transition metal as essential components and having 1-200mu particle diameter thereof is polymerized in the presence of a polymerization catalyst composed of the component (A) and (B) an organoaluminum compound. Ethylene is copolymerized with an alpha-olefin in the presence of the aforementioned prepolymerized catalyst.

Description

Detailed Description of the Invention Technical Field of the Invention The present invention relates to a solid catalyst component capable of providing an ethylene/α-olefin copolymer with high melt tension, and a catalyst for olefin polymerization containing the solid catalyst component. , and a method for producing an ethylene/α-olefin copolymer using the olefin polymerization catalyst.

Technical Background of the Invention Ethylene/α-olefin copolymers are molded by various molding methods and used for a wide variety of purposes. The properties required of the ethylene/α-olefin copolymer also vary depending on the molding method and application. For example, when trying to form blown film at high speed,
In order to perform stable high-speed molding without bubble fluctuation or breakage, it is necessary to select an ethylene/α-olefin copolymer that has a high melt tension relative to its molecular weight.

First, in order to increase the melt tension of an ethylene/α-olefin copolymer, the present inventors prepared a prepolymerized catalyst made by prepolymerizing high molecular weight polyethylene, and then used the prepolymerized catalyst. proposed that it would be preferable to carry out copolymerization of ethylene and α-olefin (Japanese Patent Application No. 166394/1999).

However, in preparing the prepolymerized catalyst, it was necessary to perform the prepolymerization at a low temperature (50 to -50'C). From an industrial standpoint, it is important to raise the temperature of the prepolymerization as high as possible to facilitate heat removal.

Purpose of the Invention The present invention aims to improve the above-mentioned problems, and even at a high prepolymerization temperature, a prepolymerization containing an ethylene polymer with a higher molecular weight can be obtained, and then carried out. A solid catalyst component capable of producing an ethylene/α-olefin copolymer with high melt tension by copolymerization of ethylene and α-olefin, a catalyst for olefin polymerization containing the solid catalyst component, and a catalyst for olefin polymerization containing the solid catalyst component; The object of the present invention is to provide a method for producing an ethylene/α-olefin copolymer using an olefin polymerization catalyst.

Summary of the Invention The solid catalyst component according to the present invention includes a solution (a-1) formed from a halogen-containing magnesium compound, an alcohol, and a hydrocarbon solvent, or a solid particle (a-2) formed from a halogen-containing magnesium compound and an alcohol. solid magnesium containing magnesium, halogen, aluminum and alkoxy groups obtained by contacting ) with an organoaluminum compound.
An aluminum complex (A), a liquid tetravalent titanium compound (B), and at least one liquid transition metal compound selected from vanadium compounds, zirconium compounds, and hafnium compounds (C
), which contains magnesium, halogen, aluminum, titanium and the above transition metals as essential components, and whose particle size is 1 to 1.
It is characterized by being 200 μm.

The catalyst for olefin polymerization according to the present invention is a solution (a-1) formed from a halogen-containing magnesium compound, an alcohol, and a hydrocarbon solvent, or a solid particle (a-1) formed from a halogen-containing magnesium compound and an alcohol.
a-2) with an organoaluminum compound (A), a solid magnesium-aluminum complex containing magnesium, halogen, aluminum, and an alkoxy group, a liquid tetravalent titanium compound (B), and vanadium. At least one liquid transition metal compound (C
), which contains magnesium, halogen, aluminum, titanium, and the above transition metals as essential components, and whose particle size is 1 to 1.
It is characterized by consisting of a solid catalyst component [I] with a diameter of 200 μm and an organoaluminum compound [II].

The first method for producing an ethylene/α-olefin copolymer according to the present invention includes a solution (a-1) formed from a halogen-containing magnesium compound, an alcohol, and a hydrocarbon solvent, or a solution (a-1) formed from a halogen-containing magnesium compound and an alcohol. solid particles (a-2) containing magnesium, halogen, aluminum and alkoxy groups obtained by contacting solid particles (a-2) with an organoaluminum compound.
An aluminum complex (A), a liquid tetravalent titanium compound (B), and at least one liquid transition metal compound selected from vanadium compounds, zirconium compounds, and hafnium compounds (C
), which contains magnesium, halogen, aluminum, titanium and the above transition metals as essential components, and whose particle size is 1 to 1.
It is characterized in that ethylene and α-olefin are copolymerized in the presence of an olefin polymerization catalyst consisting of a solid catalyst component [I] having a diameter of 200 μm and an organoaluminum compound [II].

The second method for producing an ethylene/α-olefin copolymer according to the present invention includes a solution (a-1) formed from a halogen-containing magnesium compound, an alcohol, and a hydrocarbon solvent, or a solution (a-1) formed from a halogen-containing magnesium compound and an alcohol. solid particles (a-2) containing magnesium, halogen, aluminum and alkoxy groups obtained by contacting solid particles (a-2) with an organoaluminum compound.
An aluminum complex (A), a liquid tetravalent titanium compound (B), and at least one liquid transition metal compound selected from vanadium compounds, zirconium compounds, and hafnium compounds (C
), which contains magnesium, halogen, aluminum, titanium and the above transition metals as essential components, and whose particle size is 1 to 1.
In the presence of an olefin polymerization catalyst consisting of a solid catalyst component [■] having a diameter of 200 μm and an organoaluminum compound [II], 1 to 1000 g per Ig of the solid catalyst component [I].
The method is characterized in that after a prepolymerization catalyst is prepared by prepolymerizing ethylene, ethylene and an α-olefin are copolymerized in the presence of the prepolymerization catalyst.

The solid catalyst component, the olefin polymerization catalyst containing the solid catalyst component, and the method for producing an ethylene/α-olefin copolymer using the olefin polymerization catalyst according to the present invention will be specifically described below.

In addition, FIG. 1 is an explanatory drawing showing an example of the manufacturing process of the ethylene/α-olefin copolymer according to the present invention.

[Solid catalyst component]

The solid catalyst component according to the present invention is a solution (a-1) formed from a halogen-containing magnesium compound, an alcohol, and a hydrocarbon solvent, or a solid particle (a-2) formed from a halogen-containing magnesium compound and an alcohol. Solid magnesium containing magnesium, halogen, aluminum and alkoxy groups obtained by contacting with aluminum compounds.
An aluminum complex (A), a liquid tetravalent titanium compound (B), and at least one liquid transition metal compound selected from vanadium compounds, zirconium compounds, and hafnium compounds (C
).

In the present invention, the halogen-containing magnesium compound used when preparing the solution (a-1) includes, for example, the formula % formula % (wherein R is hydrogen or an alkyl group having 1 to 20 carbon atoms,
Mention may be made of halogen-containing magnesium compounds, which are an aryl group or a cycloalkyl group, where n is 0, the two R's may be the same or different, and X is a halogen.

Such halogen-containing magnesium compounds include:
Specifically, ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Alkylmagnesium halides such as amylmagnesium chloride, magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, methoxymagnesium chloride, octoxymagnesium chloride Examples include alkoxymagnesium halide, phenoxymagnesium chloride, methylphenoxymagnesium chloride, and alkoxymagnesium halide.

These magnesium compounds can be used alone or in combination. Moreover, these halogen-containing magnesium compounds may be liquid or solid.

To obtain a solution (a-1) formed from a halogen-containing magnesium compound, an alcohol and a hydrocarbon solvent,
It also depends on the type of compound and solvent used.
The alcohol is preferably used in an amount of about 1 mole or more, preferably about 1 to about 20 moles, per mole of halogen-containing magnesium compound.
The amount used is particularly preferably in the range of about 1.5 to about 12 moles. When an aliphatic hydrocarbon and/or an alicyclic hydrocarbon is used as the hydrocarbon, the alcohol is used in the above ratio, and the alcohol is used in an amount of about 1 mol or more, preferably about 1.5 mol or more, per 1 mol of the halogen-containing magnesium compound. It is preferable to use the alcohol in an amount of mol or more because the halogen-containing magnesium compound can be solubilized with a small total amount of alcohol and the catalyst component has a good shape. On the other hand, if an aromatic hydrocarbon is used as the hydrocarbon, the halogen-containing magnesium compound can be solubilized with the amount of alcohol used as described above, regardless of the type of alcohol.

The contact between the halogen-containing magnesium compound and the alcohol is preferably carried out in a hydrocarbon medium, usually at room temperature or above, depending on the type thereof, at about 65°C or above, preferably at about 80-300°C. Approximately 100 to 200
This is carried out by contacting at a temperature of °C for about 15 minutes to 5 hours, more preferably about 30 minutes to 2 hours.

Suitable alcohols include alcohols having 6 or more carbon atoms, such as 2-methylpentanol, 2-ethylbutanol, n-heptatool, n-octanol,
2-ethylhexanol, decanol, dodecanol,
Aliphatic alcohols such as tetradecyl alcohol, undecenol, oleyl alcohol, stearyl alcohol, alicyclic alcohols such as cyclohexanol, methylcyclohexanol, benzyl alcohol, methylhensyl alcohol, isopropylpencyl alcohol, α-methylbenzyl alcohol, Examples include aromatic alcohols such as α,α-dimethylbenzyl alcohol, aliphatic alcohols containing alkoxy groups such as n-butyl cellosolve, and 1-butoxy-2-propatol.

In addition, the hydrocarbon solvents used at this time include propane,
Butane, n-pentane, isopentane, n-hexane,
Aliphatic hydrocarbons such as isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, Examples include aromatic hydrocarbons such as Hensen, toluene, and xylene, methylene chloride, ethyl chloride, and hydrogen ethyl chloride, among others, aliphatic hydrocarbons, especially aliphatic hydrocarbons having 3 to 10 carbon atoms. Or preferable.

The halogen-containing magnesium compound used in preparing the solid particles (a-2) formed from a halogen-containing magnesium compound and alcohol may be the same as the halogen-containing magnesium compound used in preparing the solution (a-1) above. I can use things.

The alcohol used for preparing the solid particles (a-2) includes methanol, ethanol, propatool,
Examples include alcohols having 5 or less carbon atoms such as butanol, ethylene glycol, and methylcarpitol.

In preparing the solid particles (a-2), the alcohol is preferably used per mole of the halogen-containing magnesium compound,
The amount used is about 0-21 to about 15 mol, preferably about 0.2 to about 10 mol, particularly preferably about 0.5 to about 8 mol. The solid particles (a-2) can be prepared from the above-mentioned halogen-containing magnesium compound and alcohol, for example, as follows.

The contact between the halogen-containing magnesium compound and the alcohol is preferably carried out in a hydrocarbon medium, usually at O'C or higher, preferably from about 20-150'C1 to about 30
It can be prepared by contacting at a temperature of ~100[deg.] C. for about 15 minutes to about 5 hours, more preferably about 80 minutes to about 2 hours.

The solid magnesium-aluminum composite (A) constituting the solid catalyst component [I] according to the present invention is prepared from the above solution (
It is obtained by bringing a-1) or solid particles (a-2) into contact with an organoaluminum compound.

Here, the solid magnesium-aluminum composite has the following empirical formula: Mg, A f bR2c (OR'), X 2 (
X2 is a halogen, 2a+3b=C+d+e),
In some cases, other compounds or electron donors may be further bonded. Preferably Al/Mg (atomic ratio) is 0.
05-1, -layer preferably 0.08-0.5, more preferably 0.12-0.3, the R'O group is preferably 0.5-15 parts by weight, more preferably 0.5-15 parts by weight per 1 part by weight of magnesium. Preferably 1 to 10 parts by weight, more preferably 2 to 6 parts by weight, the hydrocarbon group R2 (or R') is magnesium 1
per atom, preferably 0.01 to 0.5 equivalents, preferably 0.03 to 0.3 equivalents, more preferably 0.0
5 to 0.2 equivalent, and X2/Mg (atomic ratio) is preferably 1 to 3, preferably 1.5 to 2.5. The particle size is 1 to 200 μm, preferably 2 to 100 μm.
It is desirable that it is m.

Specifically, as the organoaluminum compound used for preparing the solid magnesium-aluminum composite (A), for example, the following aluminum compounds are preferably used.

Ra,,A IX 3-n In the formula, R" is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1 to 3.

In the above formula, Ro 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. , pentyl group,
Examples include hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Specific examples of such organoaluminum compounds include the following compounds.

Trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkyl aluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide.

Alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminium sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide.

Alkylaluminum cybarides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dichloride.

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

Further, a compound represented by the following formula can also be used.

Ro. AIYs-,.

In the formula, R1 is the same as above, Y is 10Rb group, OS
iRc3 groups, OA IR'2 groups, NR'2 groups,
-S iR'2 group- or N A IRh2 group, n is 1 to 2, and Rb Rc Ro and Rh are a methyl group, an ethyl group, an isopropyl group, an isobutyl group,
Cyclohexyl group, phenyl group, Ro is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group,
It is a trimethylsilyl group, and R' and Ro are a methyl group or an ethyl group.

Specifically, the following compounds are used as such organoaluminum compounds.

(+) R', A I (ORb) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, (iD R'ffA 1(OS iR'3) 3-
,.

Et2A1 (○SiMes) (iso-B IJ)2A l (OS iMe3) (i
so-Bυ)2A l(OS jE L), (ij
i) R', A I (○A IR'□), -.

E hA 10 A, IE L2 (jso-B u)zA I○A 1 (iso-B L
l) 2 nato, (iy) R”, A l(N R”
2) 3-.

Me2A tN E t2 E t 2 A I N HM e Me2A IN HE t E hA IN (Mess 1) 2 (iso-B U) 2A IN (Me3s i) 2 etc., (v) R”, A I (S iR '3):l
−.

(iso-Bu)2A]siMe3, (vi)
R''', A I (NA IRh2) 3-E t2A
INA IE t2 e (iso-B u)2A IN A I(iso-B
u), Nato.

t As the above organoaluminum compound, R”3A
1. , R',, A I(ORb) 3-1R", A
An organoaluminum compound represented by I(OAIR'2)3-n can be cited as a suitable example.

■As complex alkylated products of group metals and aluminum,
-Arson% formula% (However, Ml is Li, Na, and R1 is carbon number 1
~15 hydrocarbon groups) can be exemplified, specifically, compounds represented by L IAl
(C2H5) 4, L! Examples include A I(C7Hl 5)4.

The above compounds can be used alone or in combination of two or more.

When bringing the solution (a-1) or the solid particles (a-2) into contact with the existing aluminum compound, the solution (al)
Or, if the ROH used to prepare the solid particles (a-2) and the aluminum atoms contained in the organoaluminum compound are A
l/ROH (molar ratio), about 0.5 to 5, preferably 1
Contact is made at a ratio of ~3.

The contact temperature is -50 to 150°C, preferably -30 to 1
The contact method is not particularly limited, but is preferably carried out as follows.

In the case of (a, -1), the Mg concentration is 0. ．． 005~2 mol/
I! 0.2 of an organic Af compound was added to (a-1) under stirring.
The method of dropping the mixture dropwise over 2 hours is preferred because it yields a solid magnesium-aluminum composite (A) with good particle properties.

In the case of (a-2), (a-2) has an Mg concentration of 0.005 to
A preferred method is to suspend the suspension in hydrocarbon water or an elementary solvent at a concentration of 2 mol/l, and to contact it with the existing Affi compound under stirring.

Ultimately, the composition in the solid magnesium-aluminum composite may be adjusted to fall within the above-mentioned range. For this purpose, it is preferable to use an appropriate amount of the alkyl aluminum compound in the contact.

In the contacting, it is preferable to use trialkylaluminum as the organoaluminum compound because a well-shaped catalyst can be easily obtained. Other preferred organoaluminum compounds include dialkyl aluminum halides, dialkyl aluminum hydrides, dialkyl aluminum alkoxides, and the like.

The solid catalyst component [I] according to the present invention brings the solid magnesium-aluminum composite (A), the tetravalent titanium compound (B) in a liquid state, and the transition metal compound (C) in a liquid state into contact with each other. It can be obtained by

As a titanium compound used for preparing such a solid catalyst component [I], for example, a tetravalent titanium compound represented by the following formula can be mentioned.

Ti(OR), X4-8 R is a hydrocarbon group,
< , titanium tetrahalide with TiI4, T'(OCH3)C13, T'(OC2Hs)c13, Ti(On-C4Hi)CI3, T'(OC2H5)Br2, T'(0-1so- Trihalogenated alkoxytitanium such as C4Hs)Br3, dihalogenated titanium such as T I(OCH3)zc12, Ti(OC2HS)2C]□, Ti(On C4H1)2C12, Ti(○C2H6)2B r2 Alkoxytitanium, Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(On-C4HS')3C1, Monohalogenated trialkoxytitanium with Ti(○C2H5:hBr, TI○CH3)4, T' Examples include tetraalkoxytitanium such as (QC2H5)4, T゛(on C4H9)4, T1(0-iso-C4H9)4, and T'(0-2-ethylhexyl)4.

These tetravalent titanium compounds (B) are Ti/(M
g+Aβ) (atomic ratio) is used in an amount of 0.03 to 0.5, preferably 0.05 to 0.4.

Examples of the liquid transition metal compound (C) constituting the solid catalyst component [I] of the present invention include compounds represented by the following formula.

M.L.

In the formula, M is a transition metal selected from the group consisting of Zr, Hf and V, L is a ligand that coordinates to the transition metal, and at least two of the ligands have a cycloalkagenyl skeleton. and the ligand other than the one having a cycloalkagenyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen or hydrogen,
X is the valence of the transition metal.

Examples of the ligand having a cycloalkagenyl skeleton include a cyclopentagenyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, a t-butylcyclopentagenyl group, a dimethylcyclopentagenyl group, Examples include indenyl group and 4,5.6.7-tetrahydroindenyl group.

The ligand other than the ligand having a cycloalkagenyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halokene, or hydrogen.

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. , isopropyl group, and butyl group; examples of cycloalkyl group include cyclopentyl group and cyclohexyl group; examples of aryol group include phenyl group and tolyl group; examples of aralkyl group include: Examples include benzyl group and neophyll group.

Examples of the alkoxy group include a methoxy group, ethoxy group, and butoxy group, and examples of the aryloxy group include a phenoxy group.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

Such a transition metal compound containing a ligand having a cycloalkagenyl skeleton used in the present invention, for example, when the valence of the transition metal is 4, more specifically, the transition metal compound has the following formula: R2, R3, R ', R! i, M (where M is the above transition metal, R2 is a group having a cycloalkagenyl skeleton, R3R4 and R5 are a group having a cycloalkagenyl skeleton, an alkyl group, a cycloalkyl group, an aryl group) , an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or hydrogen, k is an integer of 1 or more, and k+l0m+n=4).

Preferably used transition metal compounds include the above formula % and at least two of R5, that is, R2 and R3, are groups having a cycloalkagenyl skeleton, and these two groups having a cycloalkagenyl skeleton are lower Alkylene is bonded via ethylene, propylene, etc., and R4 and R5 are a group having a cycloalkagenyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or hydrogen. It is.

Hereinafter, specific examples of transition metal compounds containing a ligand having a cycloalkagenyl skeleton of M or zirconium will be exemplified.

His(cyclopentagenyl)zirconium monochloride monohytrite, Bis(cyclopentagenyl)zirconium monopromide monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, His(cyclopentagenyl) phenylzirconium hydride, Bis(cyclopentagenyl)benzylzirconium hydride, Bis(cyclopentagenyl)neopentylzirconium hydride, Bis(methylcyclopentagenyl)zirconium monochloride hydride, His(indenyl) ) Zirconium monochloride monohydride, His(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)methylzirconium monochloride, His(cyclopentagenyl)ethylzirconium monochloride , Bis(cyclopentagenyl)cyclohexylzirconium monochloride, His(cyclopentagenyl)phenylsilconium monochloride, Bis(cyclopentagenyl)benzylzirconium monochloride, His(methylcyclopentagenyl)zirconium dichloride, Bis (t-Butylcyclopentagenyl)zirconium dichloride, bis(indenyl)zirconium dichloride, his(indenyl)zirconium dichloride, his(cyclopentagenyl)zirconium dimethyl, his(cyclopentadienyl)zirconium diphenyl, his(cyclopentadienyl)zirconium dichloride his(cyclopentajenyl)zirconium dibenzyl, his(cyclopentajenyl)zirconium methoxychloride, his(cyclopentagenyl)zirconium ethoxychloride, his(methylcyclopentagenyl)zirconium ethoxychloride, bis(cyclopentagenyl)zirconium phenoxy Chloride, bis(fluorenyl)zirconium dichloride.

In addition, it contains at least two or more ligands having a cycloalkagenyl skeleton of M or zirconium, and the at least two ligands having a cycloalkagenyl skeleton are bonded via a lower alkylene group. Specific examples of transition metal compounds are shown below.

Ethylenebis(indenyl)dimethylzirconium, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium, Ethylenebis(indenyl)methylzirconiumEthylenebis(indenyl)ethylzirconium monocuchloride, Ethylenebis(indenyl)methylzirconium monopropylene ethylene bis(indenyl) zirconium dichloride, ethylene bis(indenyl) zirconium dibromide, ethylene bis(indenyl) zirconium methoxy monochloride, ethylene bis(indenyl) zirconium methoxy monochloride, ethylene bis(indenyl) zirconium phenoxy monochloride, Ethylenebis(cyclopentagenyl)zirconium dichloride, Propylenebis(cyclopentagenyl)zirconium dichloride, Ethylenebis(t-butylcyclopentagenyl)zirconium monochloride, Ethylenebis(4,5,6,7-terolahydro 1) -indenyl)dimethylzirconium, ethylenebis(4,5,6,7-telorahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-telorahydro-1-indenyl)zirconium dichloride, ethylenebis(4 ,5,6,7-terolahydro-1-indenyl) zirconium dichloride, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-1-indenyl)zirconium dichloride, -indenyl) zirconium dichloride, ethylenebis(7-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, Ethylenebis(4,7-simethyl-1-indenyl)zirconium dichloride, Ethylenebis(4,7-simethoxy-1-indenyl)
Zirconium dichloride.

Furthermore, in the above zirconium compounds, compounds in which zirconium is replaced with hafnium or vanadium can also be used.

In addition to the above, as the transition metal compound (C),
When the transition metal is vanadium, -arson% formula %) (However, R is a hydrocarbon group, 0≦a≦3.0≦b≦3.
2≦a+b≦3.0≦C≦4.0≦d≦4.3≦C1d
A vanadium compound represented by ≦4) or an electron donor adduct thereof can be used.

More specifically, vocI! ,, VO(OC2H5') C12, VO(OC2H5)zcf, VO(0-iso-C+H7) Cβ2, VO(○-n
-C4Hs) C12, VO(OC2H5) 2, VOBrs, VCl4,
V OCji' 2, V O(On C4H9) 2,
VC! ! , .2C, H, 708 and the like can be exemplified.

These compounds may be used alone or in combination of two or more. Further, it may be used after being diluted with hydrocarbon or halogenated hydrocarbon.

These transition metal compounds (C) are used in a TM/Ti (atomic ratio) of 0.05 to 20, preferably 0.1 to 10, relative to the tetravalent titanium compound. Note that TM represents a transition metal atom.

Further, when preparing the solid catalyst component [I] of the present invention, an electron donor may be used as necessary.

C Olefin Polymerization Catalyst] The olefin polymerization catalyst of the present invention is formed from the solid catalyst component [I] and an organoaluminum compound [■].

Examples of the organoaluminum compound [II] include those similar to those used in preparing the solid catalyst component [I]. The organoaluminum compound [II] is used in an amount of 1 to 1000 mol, preferably 2 to 500 mol, per 1 g of Ti atom in the solid catalyst component [I].

The catalyst for reflex polymerization as described above may further contain an electron donor if necessary.

As such an electron donor, the electron donor used in preparing the solid catalyst component [I] described above can be used, and furthermore, the organosilicon compound shown in the following - Arson can be used. Ru.

R, S i (OR' ) 4 (wherein R and R' are hydrocarbon groups, and 0<n<4
Specifically, the organosilicon compounds represented by the above general formula include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis-0-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, Bis p-)lyldiethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane , n-propyltriethoxysilane,
Decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-lylorpropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-
Butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltriethoxysilane Methoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy(a)
l 1yloxy)silane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2.3-dimethylcyclopentyltrimethoxysilane, cyclopentyl)・Liethoxysilane, dicyclopentyldimethoxysilane, his(2methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethyl Methoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldiethylmethoxysilane, or cyclopentyldimethylethoxysilane is used.

Of these, ethyltriethoxysilane, propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane , p-tolylmethyldimethoxysilane,
Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, Schiff white pentyltriethoxysilane, tricyclopentylmethoxysilane, Cyclopentyldimethylmethoxysilane and the like are preferably used.

Two or more of these organosilicon compounds can also be used in combination.

In addition, examples of electron donors that can be used in addition to these organosilicon compounds include nitrogen-containing compounds, other oxygen-containing compounds, and phosphorus-containing compounds.

As such a nitrogen-containing compound, specifically, the following compounds can be used.

2.6-substituted piperidines, 2.5-substituted piperidines, N, N, N', N'-tetramethylmethylenediamine,
Substituted methylene diamines such as N, N, N'', N'-tetraethylmethylene diamine; (2) Substituted methylene diamines such as 3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine; .

As the phosphorus-containing compound, specifically, phosphite esters as shown below can be used.

Triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n
- Phosphite esters such as butyl phosphite and diethylphenyl phosphite.

Further, as the oxygen-containing compound, the following compounds can be used.

2.6-substituted tetrahydropyrans, 2.5-substituted tetrahydropyrans.

Note that the olefin polymerization catalyst obtained as described above can be further supported on the following carrier compound. Such carrier compounds include Teha, Al2O3,
5102, B 203, MgO, CaO, T i O2
, ZnO1Z n 02, S n O2, BaO, Th
Examples include resins such as ○ and styrene-divinylbenzene copolymer.

[Production method of ethylene/α-olefin copolymer] In the production method according to the present invention, the above-mentioned solid catalyst component [
[I], an organoaluminum compound [II], and an electron donor if necessary, to copolymerize ethylene/α-olefin, or to copolymerize ethylene and α-olefin in advance to the olefin polymerization catalyst. It is preferable to prepolymerize. At this time, an α-olefin other than ethylene as described below may be copolymerized with ethylene.

Prepolymerization is carried out at 1 to 1000 g per 1 g of solid catalyst component,
Preferably 5-500g, particularly preferably 10-200g
This is done by polymerizing ethylene in an amount of g.

In the preliminary polymerization, a catalyst can be used at a higher concentration than the catalyst concentration in the system in the next step, the main polymerization.

The concentration of the solid catalyst component [I] in the prepolymerization is usually about 0.001 to 200 per liquid medium 11 in terms of atoms of the sum of transition metals in titanium and transition metal compound EC].
Millimoles, preferably about 0.01 to 50 millimoles, particularly preferably 0.1 to 20 millimoles are desirable.

The amount of the organoaluminum compound [II] is 1 to 1000 g, preferably 5 to 1000 g per 1 g of the solid catalyst component [I].
The amount may be such that 500 g of polymer is produced, and it is usually about 0.5 g per mole of the sum of the titanium atoms in the solid catalyst component [I] and the transition metal in the transition metal compound [C].
Desirably amounts are from 1 to 300 mol, preferably from about 0.5 to 100 mol, particularly preferably from 1 to 50 mol.

Prepolymerization can be carried out under mild conditions by adding ethylene and the catalyst components described above to an inert hydrocarbon medium.

Specifically, the inert hydrocarbon medium used in this case includes propane, n-butane, 1so-butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, etc. , alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorhenzene; and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Prepolymerization can be carried out either batchwise or continuously. It is also possible to carry out prepolymerization substantially in the absence of a solvent. In this case, it is preferable to carry out the prepolymerization continuously.

The reaction temperature during prepolymerization is usually about -40 to 160°C.
1 Preferably about -30 to 50°C 1 More preferably 0 to
It is desirable that the temperature be within the range of 40°C.

Incidentally, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such a molecular weight modifier is 1
The intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 35°C is about 20 dl/g or more, preferably about 25 to 100 dl/g, particularly preferably 30
It is desirable to use it in an amount of ~60 dl/g.

Prepolymerization was carried out using 1 g of solid titanium catalyst component as described above.
It is desirable to carry out the process so that about 1 to 1000 g, preferably about 5 to 500 g, particularly preferably 10 to 200 g of prepolymerized catalyst are produced per reaction.

In the production method according to the present invention, the solid catalyst component [I] as described above and the organoaluminum compound [II] as described above are used.
] using an olefin polymerization catalyst consisting of
Copolymerization of α-olefins is carried out. The above-mentioned electron donor can be added to this catalyst for reflex polymerization, if necessary.

In carrying out the copolymerization, if the solid catalyst component [I] is prepolymerized, the main polymerization is preferably performed so that the amount of polymer produced in the prepolymerization does not exceed 5000 times, and more preferably The magnification is preferably carried out within a range of 100 to 1000 times, so as not to exceed 3000 times.

The α-olefin according to the present invention has 3 to 27 carbon atoms.
α-olefins such as propylene,
2-methylpropylene, 1-butene, 1-hexene, 1-
Pentene, 4-methyl-1~Pentene, 3-methyl-1~
Examples include pentene, 1-octene, nonene-1, decene-1, undecene-1, dodecene-1, etc. In addition to α-olefins, for example, polyenes can also be copolymerized. Examples of such polyenes include butadiene, isoprene, 1,4-hexanene, dicyclopentatsuene, and 5-ethylidene-2-norbornene.

During copolymerization, when introducing the solid catalyst component [I] into the polymerization vessel, it is preferable to supply the solid catalyst component [I] in a powdered state or as a suspension in the above-mentioned hydrocarbon solvent. . Especially if the polymerization is carried out in the gas phase,
It may be supplied by suspending it in a low boiling point solvent such as propane, 1so-butane, n-butane, 1so-pentane or the like.

The solid catalyst component [I] contains titanium and a transition metal, and the solid catalyst component [I] contains Ti atoms and the transition metal in the transition metal compound [C] per 11 polymerization reaction volumes. It is preferable to use it in an amount of 0,00001 to about 1 mmol, preferably about 0.001 to about 0.1 mmol in terms of the total amount.

When ethylene is prepolymerized in the solid catalyst component [I], 1, . 000~100
．． ooog, preferably 3.000-50.000g
.

More preferably, 5.000 to 30.000 g of ethylene/alpha fin copolymer is produced by copolymerization.

In a polymerization vessel, 1 gram of the organoaluminum compound [II] is added per 1 gram atom of the sum of titanium in the solid catalyst component [I] and the transition metal in the transition metal compound [C].
-1000 mol, preferably 2-500 mol, particularly preferably 2-100 mol, other compounds, such as electron donor components, may also be added, in which case in the organoaluminum compound [II] It is preferred to use up to 10 mol, preferably up to 1 mol, particularly preferably from 0,001 to 0.1 mol, per gram atom of aluminum.

Polymerization temperature is 20 to 130°C, preferably 50 to 120°C.
The temperature is preferably 70 to 110°C. Polymerization pressure is 1-100kg7cm2, preferably 2-40kg
/cm”.

Furthermore, an inert gas that forms a gaseous state within the polymerization system, such as methane, ethane, propane, butane, or nitrogen, may be supplied as appropriate.

Further, the above copolymerization can also be carried out in two or more stages.

This polymerization is preferably carried out by gas phase polymerization or solvent suspension polymerization using propane, isobutane, n-butane, hexane, heptane or the like as a solvent, with gas phase polymerization being particularly preferred.

Hereinafter, the ethylene/α-olefin copolymer obtained by the production method of the present invention will be specifically explained.

The ethylene/α-olefin copolymer obtained by the present invention is a random copolymer obtained by copolymerizing ethylene and α-olefin in the presence of the above-mentioned olefin polymerization catalyst. This ethylene/α-olefin copolymer may contain polyene or the like in addition to ethylene and α-olefin as described above.

This ethylene/α-olefin copolymer is ASTM
Melt flow rate measured by D1238E (
MFR) is 0.01 to 100 g/10 minutes, preferably 0.05 to 50 g/10 minutes.

Note that the melt tension (MT) is a value measured as follows.

[MT Measurement Measurement After inserting the orifice, 7 g of polymer, and the piston in this order into a cylinder maintained at 190°C using a new MT measurement device manufactured by Toyo Seiki, preheat for about 5 minutes.

After preheating, the piston is pushed down at a speed of 10 mm/min to extrude the molten polymer through the orifice at the bottom of the cylinder. The extruded strand is drawn into a filament, passed through a pulley of a load detector, and pulled by a take-up roller at a speed of 2.5 m/min.

The stress applied to the pulley at that time was defined as the melt tension (MT) of the polymer.

Melt tension (MT) (-0,6Qlog MFR+,
When a film is formed using ethylene/α-olefin with a value of 0.40) or more, i) neck-in is suppressed in the cast molding method, and as a result, the amount of removal at both ends of the film can be reduced, and the thin-walled film can be formed. In addition, it also improves high-speed molding properties.In the inflation molding method, bubbles are stabilized, which reduces unevenness in film thickness, and improves folding diameter accuracy, increasing product yield. Furthermore, it not only becomes possible to form thin films, but also improves high-speed formability.

The ethylene/α-olefin copolymer obtained by the present invention has a density of 0.88-0.95 g/cm 3 , preferably 0.89-0.94 g/cm'. Note that the density here is a value measured according to ASTM D 1505.

In the ethylene/α-olefin copolymer obtained by the present invention, the number of structural units derived from α-olefin is 2 to 2.
5% by weight, preferably 4-23% by weight, particularly preferably 6-20% by weight, the structural units derived from ethylene being present in an amount of 75-98% by weight, preferably 77-96% by weight, particularly preferably Present in an amount of 80-94% by weight.

As mentioned above, this ethylene/α-olefin copolymer contains 10% by weight or less, preferably 5% by weight or less, particularly preferably 5% by weight or less, of structural units derived from, for example, polyene in addition to ethylene and α-olefin. It can be included in an amount of up to 3% by weight.

Ethylene/α-olefin copolymers with the above properties have excellent transparency, impact resistance, tear resistance, blocking resistance, low temperature heat sealability, heat resistance, and stress crack resistance. Because it has a good balance of excellent properties, it is particularly suitable as a packaging film, and is not limited to being used as a film. It can be processed into various molded products such as , daily necessities, pipes, and tubes. In addition, various composite films can be made by extrusion coating or coextrusion with other films, and steel pipe coating materials,
It is also used for applications such as wire covering materials and foam molded products. Alternatively, other thermoplastic resins such as high density polyethylene, medium density polyethylene, low density polyethylene,
Polypropylene, poly1-butene, poly4-methyl-1
~Pentene, low-crystalline or amorphous copolymer of ethylene and propylene or 1-butene, propylene.
It can also be used in blends with polyolefins such as 1 to butene copolymers.

Furthermore, the ethylene/α-olefin copolymer obtained as described above may contain heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, antipro-knocking agents, lubricants, nucleating agents,
Pigments, dyes, inorganic or organic fillers, etc. can also be blended.

Effects of the Invention According to the present invention, even at a high prepolymerization temperature, a prepolymer containing an ethylene polymer with a higher molecular weight can be obtained, and the subsequent copolymerization of ethylene and α-olefin reduces the melt tension. A solid catalyst component capable of producing a high ethylene/α-olefin copolymer, an olefin polymerization catalyst containing the solid catalyst component, and an ethylene/α-olefin copolymer using the olefin polymerization catalyst It becomes possible to provide a manufacturing method for.

[Examples] Hereinafter, the present invention will be explained using specific examples, but the present invention is not limited to these examples.

Example 1 [Preparation of solid catalyst component] 2.98 g of commercially available anhydrous magnesium chloride, 14.5 rnl of 2-ethylhexyl alcohol, and 140 i of decane were placed in a glass flask with an internal volume of 400 mm under a nitrogen atmosphere.
was added, and a heating reaction was carried out at 140°C for 3 hours to obtain a homogeneous solution containing magnesium chloride. While stirring this solution,
At 20°C, a mixed solution of 4,45 mm triethylaluminum and 27.5 ml of decane was added dropwise over 30 minutes, then the temperature was raised to 80°C over 1 hour, and the reaction was heated at 80°C for 1 hour. went. Next, a mixed solution consisting of 4.69 mff of diethylaluminium chloride and 4.73 ml of decane was added over 30 minutes, and the reaction was carried out again at 80°C for 11 hours. Next, the solid portion was separated by filtration, and the solid component was synthesized.

After resuspending the solid component thus obtained in 125 ml of decane, 4.7 mmol of 2-ethylhexoxytitanium trichloride and 2.4 mmol of vanadyl trichloride were added and heated at 80°C for 1 hour. After performing the reaction,
A solid catalyst component was prepared by washing with decane. On the other hand, a portion of the slurry was taken, decane was removed, the slurry was replaced with hexane, and then dried, and the catalyst composition was determined using this dried catalyst.

The composition of the solid catalyst component is 1.0% by weight of titanium, 0.9% by weight of vanadium, 11% by weight of magnesium, and 36% by weight of chlorine.
% by weight.

[Pre-polymerization] 400mI! After adding 200 yd of purified hexane, 0.8 mmol of ethylaluminum chloride, and 0.2 mmol of the catalyst component (in terms of titanium atoms) to a cylindrical flask with a stirrer, ethylene was added at 30°C to 8Nβ/ Prepolymerization of ethylene was carried out by feeding at a rate of 3 hours. After polymerization, solid and liquid were separated by filtration, and the solid portion was thoroughly washed with hexane, and then made into a hexane suspension again.

The amount of polyethylene produced was 31 g/g of catalyst. Further, after deashing a portion with an isobutanol-hydrochloric acid solution, the intrinsic viscosity [η] in Decali at 130°C was measured and found to be 29.3 dl/g.

[Polymerization] Add 150 g of sodium chloride as a dispersant to an autoclave with an internal volume of 21 that was sufficiently purged with nitrogen, and heat at 90°C.
After heating, the autoclave was depressurized for 2 hours using a vacuum pump so that the internal pressure of the autoclave was 50 mmHg or less.

Next, the temperature of the autoclave was lowered to room temperature, and after replacing the inside of the autoclave with ethylene, 0.5 mmol of triethylaluminum, 0.5 mmol of diethylaluminum chloride, and 19ml of hexene were added.
After sealing the system, raise the temperature and add 1.5k hydrogen at 60°C.
g/crl, and while further pressurizing with ethylene, the prepolymerized catalyst component was heated to 0.00 in terms of titanium atoms.
3 mmol was added. During the polymerization, the temperature was 80 °C and the pressure was 8 kg/crl with ethylene gas supplementation.
I kept it in G. Also, after adding the catalyst component, hexene-136
rId! was pumped for 1 hour. Polymerization was completed 1 hour after the addition of the catalyst.

After the polymerization was completed, the contents of the autoclave were poured into approximately IA of water. After stirring for about 5 minutes, almost all of the chlorinated slum was dissolved in the water, and only the polymer floated on the water surface. This floating polymer was collected, thoroughly washed with methanol, and then dried at 80°C under reduced pressure overnight. The yield of the obtained copolymer was 125 g, the density was 0.919 g/cm, V
FR is 0.97g/10rnin, MT is 5.4g
Met.

Example 2 "Preparation of solid catalyst component" In Example 1, 4.7 mmol of 2-ethylhexoxytitanium trichloride,
Instead of using 2.4 mmol of vanadyl trichloride, 4.7 mmol of 2-ethylhexoxytitanium trichloride was used.
It was prepared in exactly the same manner as in Example 1 except that 4.7 mmol of ethylene bisindenyl zirconium dichloride was used.

The composition of the solid catalyst component thus obtained was 0.6% by weight of titanium, 0.4% by weight of zirconium, 11% by weight of magnesium, and 36% by weight of chlorine.

[Prepolymerization] Prepolymerization was carried out in exactly the same manner as in Example 1 except that the above solid catalyst component was used.

The amount of polyethylene produced was 22 g/g of catalyst. Further, the intrinsic viscosity [η] was 34.0c11/g.

1 Polymerization] Polymerization was carried out in the same manner as in Example 1 except that the above prepolymerization catalyst was used. The yield of the obtained copolymer was 130 g,
Density is 0.922 g/cnf, MFR is 1.17 g,
,/10m1n, MT was 5.4g.

Comparative Examples 1 to 2 [Preparation of solid catalyst component] In Example 1, 4.7 mmol of 2-ethylhexoxytitanium trichloride was used as the transition metal compound component;
It was prepared in exactly the same manner as in Example 1 except that 4.7 mmol of 2-ethylhexoxytitanium trichloride was used instead of 2.4 mmol of vanadyl trichloride.

The composition of the solid catalyst component thus obtained was 1.3% by weight of titanium, 11% by weight of magnesium, and 37% by weight of chlorine.

[Prepolymerization] Using the solid catalyst component obtained above, in Comparative Example 2,
Prepolymerization was carried out in the same manner as in Example 1 except that the prepolymerization temperature was changed as shown in Table 1.

[Polymerization] Polymerization was carried out in the same manner as in Example 1, except that the prepolymerized catalyst obtained as described above was used.

The polymerization results are shown in Table 1.

From the above results, when only a titanium compound is used as a transition metal compound component, the [η] of polyethylene produced in prepolymerization is low (and the final copolymer has a low melt tension (MT)).
You can only get a low value.

Furthermore, in order to increase [η] of polyethylene obtained by prepolymerization to a substantially useful value, it is necessary to select a low temperature condition of -5°C, which is extremely disadvantageous from an industrial standpoint. These are the conditions.

[Brief explanation of drawings]

No. The figure shows ethylene according to the present invention. α Orefi FIG.

Claims (4)

[Claims] (1) Obtained by contacting a solution (a-1) formed from a halogen-containing magnesium compound, alcohol and a hydrocarbon solvent or solid particles (a-2) formed from a halogen-containing magnesium compound and alcohol with an organoaluminum compound. a solid magnesium-aluminum complex (A) containing magnesium, halogen, aluminum, and an alkoxy group; a liquid tetravalent titanium compound (B); and at least one member selected from vanadium compounds, zirconium compounds, and hafnium compounds. is obtained by contacting the transition metal compound (C) in a liquid state, contains magnesium, halogen, aluminum, titanium, and the above transition metals as essential components, and has a particle size of 1 to 1.
A solid catalyst component having a diameter of 200 μm. (2) Obtained by contacting a solution (a-1) formed from a halogen-containing magnesium compound, alcohol and a hydrocarbon solvent or solid particles (a-2) formed from a halogen-containing magnesium compound and alcohol with an organoaluminum compound. a solid magnesium-aluminum complex (A) containing magnesium, halogen, aluminum, and an alkoxy group; a liquid tetravalent titanium compound (B); and at least one member selected from vanadium compounds, zirconium compounds, and hafnium compounds. is obtained by contacting the transition metal compound (C) in a liquid state, contains magnesium, halogen, aluminum, titanium, and the above transition metals as essential components, and has a particle size of 1 to 1.
An olefin polymerization catalyst comprising a solid catalyst component [I] having a diameter of 200 μm and an organoaluminum compound [II]. (3) Obtained by contacting a solution (a-1) formed from a halogen-containing magnesium compound, alcohol and a hydrocarbon solvent or solid particles (a-2) formed from a halogen-containing magnesium compound and alcohol with an organoaluminum compound. a solid magnesium-aluminum complex (A) containing magnesium, halogen, aluminum, and an alkoxy group; a liquid tetravalent titanium compound (B); and at least one member selected from vanadium compounds, zirconium compounds, and hafnium compounds. is obtained by contacting the transition metal compound (C) in a liquid state, contains magnesium, halogen, aluminum, titanium, and the above transition metals as essential components, and has a particle size of 1 to 1.
Ethylene/α-olefin characterized in that ethylene and α-olefin are copolymerized in the presence of an olefin polymerization catalyst consisting of a solid catalyst component [I] having a diameter of 200 μm and an organoaluminum compound [II]. Method for producing copolymer. (4) Obtained by contacting a solution (a-1) formed from a halogen-containing magnesium compound, alcohol and a hydrocarbon solvent or solid particles (a-2) formed from a halogen-containing magnesium compound and alcohol with an organoaluminum compound. a solid magnesium-aluminum complex (A) containing magnesium, halogen, aluminum, and an alkoxy group; a liquid tetravalent titanium compound (B); and at least one member selected from vanadium compounds, zirconium compounds, and hafnium compounds. is obtained by contacting the transition metal compound (C) in a liquid state, contains magnesium, halogen, aluminum, titanium, and the above transition metals as essential components, and has a particle size of 1 to 1.
In the presence of an olefin polymerization catalyst consisting of a solid catalyst component [I] with a diameter of 200 μm and an organoaluminum compound [II], 1 to 1000 g per 1 g of the solid catalyst component [I].
A method for producing an ethylene/α-olefin copolymer, which comprises preparing a prepolymerization catalyst by prepolymerizing ethylene, and then copolymerizing ethylene and an α-olefin in the presence of the prepolymerization catalyst. .