JP2022183105A - Catalyst for olefinic polymerization, and method for producing ethylenic polymer - Google Patents

Abstract

To provide a catalyst for olefinic polymerization that makes it possible to produce an ethylenic polymer having moldability, strength and durability in a balanced manner.SOLUTION: A catalyst for olefinic polymerization contains a component (A): a specific uncrosslinked metallocene compound, a component (B): a specific crosslinked metallocene compound, a component (C): a compound that makes the component (A) and the component (B) cationic compounds, and a component (D): particulate carrier.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst useful for producing olefin polymers and copolymers, and a method for producing an ethylene polymer using the olefin polymerization catalyst.

Olefinic polymers such as polyethylene and polypropylene are widely used as plastic molding materials. Olefin polymers as molding materials have moldability such as fluidity in the molten state, melt tension, elongation viscosity, etc., and molding properties such as hardness, rigidity, impact strength, heat resistance, durability, and transparency after molding. Physical properties suitable for use on the body are required.
Under these circumstances, polyolefins produced with metallocene catalysts for olefin polymerization have high uniformity in polymer molecular structure, such as molecular weight distribution and copolymerization composition distribution, and are excellent in various mechanical properties such as impact strength and long life. Therefore, its usage has increased in recent years. However, although metallocene polyolefins are excellent in various mechanical properties, they are inferior in properties important for polyolefin molding, such as melt tension and melt fluidity, due to their narrow molecular weight distribution. was not fulfilling.

As a method for improving the moldability of metallocene-based polyolefins, in Patent Document 1, as a catalyst component for olefin polymerization or as a polymerization catalyst for producing metallocene-based polyethylene in which a sufficient number and appropriate length of long-chain branches are introduced, , disclose catalysts that combine multiple bridged metallocene complexes of specific structures.
Patent Document 2 also discloses that the introduction of long-chain branches for the purpose of improving moldability may reduce mechanical properties. - A method for improving elongational flow properties and moldability by controlling the molecular weight distribution through two-stage polymerization using a two-way catalyst in which a fluorenyl complex and a phenoxyimine complex are combined is disclosed.

Patent Document 3 discloses that a two-way catalyst combining a specific bridged cyclopentadienyl-fluorenyl complex and a non-bridged biscyclopentadienyl complex improves moldability, mechanical properties and product appearance. ing.
In Patent Document 4, a two-way catalyst in which a specific bridged biscyclopentadienyl complex and a bridged cyclopentadienyl-fluorenyl complex are combined, or a specific bridged biscyclopentadienyl complex and a bridged indenyl-fluorenyl complex are used. A method is disclosed for producing polymers with specific amounts of long chain branching through a combined two-way catalyst.
Patent Document 5 discloses a method for producing a polymer having a wide molecular weight distribution by carrying out multistage polymerization in the presence of a two-way catalyst in which a specific non-crosslinked biscyclopentadienyl complex and a specific crosslinked bisindenyl complex are combined. disclosed.
In Patent Document 6, a film is formed by using a catalyst in which a specific non-bridged biscyclopentadienyl complex, a specific bridged metallocene complex or a non-bridged biscyclopentadienyl complex, and a specific solid oxide are combined. It is disclosed that a polyethylene polymer having improved moldability, mechanical properties and transparency was obtained.

Japanese Unexamined Patent Application Publication No. 2012-214780 JP 2017-25160 A Japanese Patent Publication No. 2009-527636 Japanese Patent Application Laid-Open No. 2006-321991 Japanese translation of PCT publication No. 2002-504958 JP 2011-140658 A

Thus, many metallocene catalyst technologies have been developed, but polymers obtained using conventional metallocene catalysts still have an insufficient balance of moldability, strength and durability. There is a request for

An object of the present invention is to provide an olefin polymerization catalyst capable of producing an ethylene polymer having an excellent balance of moldability, strength and durability.
Another object of the present invention is to provide a method for producing an ethylene-based polymer having an excellent balance of moldability, strength and durability using the olefin polymerization catalyst as described above.

The olefin polymerization catalyst of the present invention is characterized by containing the following component (A), component (B), component (C) and component (D).
Component (A): a metallocene compound represented by the following general formula (1) Component (B): a metallocene compound represented by the following general formula (2) Component (C): the component (A) and the component (B) is a cationic compound Component (D): microparticle carrier

[In formula (1),
^M1 represents a titanium atom, a zirconium atom or a hafnium atom.
X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom. It represents a hydrocarbon group or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; , an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and an alkyl group having 1 carbon atom Alkyl group having 1 to 6 carbon atoms substituted with trialkylsilyl group of 1 to 3, substituted silyl group substituted with hydrocarbon group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms, substituted with halogen atom represents an aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. ]

[In formula (2),
^M2 represents a titanium atom, a zirconium atom or a hafnium atom.
X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom having 3 to 20 carbon atoms. It represents a hydrocarbon group or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.
Y represents a carbon atom, silicon atom or germanium atom.
R ¹¹ and R ²¹ each independently represent an optionally substituted furyl group or an optionally substituted thienyl group.
^R12 , ^R13 , ^R14 , ^R15 , ^R16 , R17, ^{R18 , R19} , R22, ^R23 , ^R24 , ^R25 , ^R26 , ^R27 , ^R28 and ^{R29 are} each independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom C1-6 alkyl group substituted with C1-3 trialkylsilyl group, substituted silyl group substituted with C1-6 hydrocarbon group, C6-18 aryl group, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. Adjacent groups among R ¹² to R ¹⁹ and R ²² to R ²⁹ may combine to form a 6- to 7-membered ring, and the 6- to 7-membered ring may contain an unsaturated bond.
R ³¹ and R ³² each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, or an alkyl group. an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group having 1 to 3 carbon atoms, a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, It represents an aryl group having 6 to 18 carbon atoms substituted with a halogen atom or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. R ³¹ and R ³² may contain Y to form a 4- to 7-membered ring, and when at least one of R ³¹ and R ³² has a cyclic structure, it is composed of R ³¹ , R ³² and Y The 4- to 7-membered ring may form a condensed ring in which R ³¹ and R ³² share some of the constituent atoms of the cyclic structure. ]

In the olefin polymerization ^catalyst of the present invention, it is easy to obtain an ethylene polymer having an excellent balance of moldability, strength and durability. R ²¹ may be a group represented by the following general formula (3).

［式（３）中、Ｚは酸素原子または硫黄原子であり、
Ｒ^３３、Ｒ^３４は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～８のアルケニル基、ハロゲン原子で置換された炭素数１～６のアルキル基、炭素数６～１８のアリール基、ハロゲン原子で置換された炭素数６～１８のアリール基、アルキル基が炭素数１～３のトリアルキルシリル基で置換された炭素数１～３のアルキル基、又は炭素数１～６の炭化水素基で置換された置換シリル基であり、Ｒ^３３及びＲ^３４は互いに結合して６～７員環を構成してもよく、６～７員環が不飽和結合を含んでいてもよい。］

[In the formula (3), Z is an oxygen atom or a sulfur atom,
R ³³ and R ³⁴ are each independently substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a halogen atom. an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, and a trialkylsilyl group having 1 to 3 carbon atoms substituted for the alkyl group. an alkyl group having 1 to 3 carbon atoms, or a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, and R ³³ and R ³⁴ may combine with each other to form a 6- to 7-membered ring. Alternatively, the 6- to 7-membered ring may contain an unsaturated bond. ]

In the olefin polymerization catalyst of the present invention, an ethylene polymer having an excellent balance of moldability, strength ^and durability can be easily obtained. R ⁶ is each independently an alkyl group having 3 to 6 carbon atoms, R ³ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ may be hydrogen atoms.

In the olefin polymerization catalyst of the present invention, it is easy to obtain an ethylene-based polymer ^having an excellent balance of moldability, strength and durability. R ⁶ is each independently an alkyl group having 3 to 6 carbon atoms, R ³ and R ⁸ are each independently a hydrogen atom or a methyl group, R ² , R ⁴ , R ⁵ , R ⁷ , ^R9 and ^R10 may be hydrogen atoms.

In the olefin polymerization catalyst of the present invention, an ethylene polymer having an excellent balance of moldability, strength ^and durability can be easily obtained. R ⁶ is each independently an alkyl group having 3 to 6 carbon atoms, R ³ and R ⁸ are hydrogen atoms, and R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are hydrogen It can be an atom.

In the olefin polymerization catalyst of the present invention, the component (C) may be methylaluminoxane in terms of industrial availability and polymer particle properties.

The method for producing an ethylene polymer of the present invention is characterized by polymerizing ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms in the presence of the olefin polymerization catalyst of the present invention.

In the method for producing the ethylene-based polymer of the present invention, the slurry polymerization method may be used from the viewpoint of controlling the properties of the polymer particles.

According to the present invention, there is provided an olefin polymerization catalyst capable of producing an ethylene polymer having high melt tension, excellent moldability, high strength and durability, and excellent balance between moldability, strength and durability. can be done.
Further, by using the olefin polymerization catalyst of the present invention, it is possible to provide a method for producing an ethylene-based polymer having an excellent balance among moldability, strength and durability.

1 is a GPC chart of the ethylene-based polymers obtained in Example 1 and Comparative Example 1. FIG. 2 is a GPC chart of the ethylene-based polymers obtained in Reference Examples 1, 2 and 3. FIG. FIG. 3 shows the results of viscoelasticity measurements of the blends obtained in Reference Examples 1 and 3. FIG.

The present invention will be described below.
In the present invention, "polymerization" is a general term for homopolymerization of one type of monomer and copolymerization of a plurality of types of monomers. polymerization”.
Further, in the present invention, the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.
In the present invention, "i-" means iso, "n-" means normal, "s-" means secondary, and "t-" means tertiary isomeric structure. In some cases, it is used in the sense of normal structure.

I. Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention includes a metallocene compound (component (A)) represented by the general formula (1) described later, a metallocene compound represented by the general formula (2) described later (component (B )), a compound (component (C)) that converts the component (A) and the component (B) into cationic compounds (component (C)), and a fine particle carrier (component (D)).

Polymers obtained using conventional metallocene catalysts still have an unsatisfactory balance of moldability, strength and durability. For example, in the method of producing a polymer with a wide molecular weight distribution using a two-way catalyst described in Patent Document 5, a copolymer having an excessive number of high-molecular-weight long-chain branches is likely to be obtained, so a high-viscosity polymer is produced. As shown in Comparative Example 1, when adjusted to a desired viscosity suitable for moldability, there was a problem that a large amount of low molecular weight components was included and mechanical strength and durability tended to be inferior.
On the other hand, when the olefin polymerization catalyst of the present invention is used, melt tension is high while maintaining high impact strength, and durability is also high. Therefore, it is possible to obtain a polymer having excellent balance between moldability, strength and durability. can be done. It is believed that this is due to the structures of the metallocene complex components (A) and (B) contained in the olefin polymerization catalyst of the present invention. In the polymerization carried out in the presence of the olefin polymerization catalyst of the present invention, the component (A) mainly produces a polymer containing a relatively low molecular weight macromonomer, and at the same time, the component (B) produces an olefin monomer and A relatively high molecular weight copolymer is produced in which the macromonomer is copolymerized. At the same time, a relatively high-molecular-weight macromonomer is also produced from the component (B) that promotes copolymerization, albeit at a low frequency, and as a result, copolymerization with this high-molecular-weight macromonomer also occurs. That is, copolymerization occurs with relatively low molecular weight macromonomers from component (A) and with relatively high molecular weight macromonomers from component (B). Among them, a copolymer obtained by copolymerization with a high-molecular-weight macromonomer is not preferable because if it contains an excessive number of high-molecular-weight long-chain branches, it leads to an excessive increase in viscosity. In the component (B) used in the present invention, the heteroatom in the furyl group or thienyl group contained in the 2-position substituent of the indene skeleton interacts with the central metal, which is the polymerization active species, to form a macromolecule to the central metal. It is thought that the copolymerization frequency with relatively high molecular weight macromonomers moderately decreases because the coordination of the monomer is moderately hindered. On the other hand, in conventional complexes that do not have the specific substituent of the present invention on the 2-position substituent of the indene skeleton, high-molecular-weight macromonomers are easily coordinated to the central metal, and copolymerization with high-molecular-weight macromonomers is moderate. It is considered that a polymer containing many long-chain branches with a high molecular weight is obtained. Thus, in the polymerization carried out in the presence of the olefin polymerization catalyst of the present invention, the molecular weight distribution is moderate while suppressing the formation of an excessive number of high-molecular-weight long-chain branches, which leads to an increase in the viscosity of the polymer. It is possible to produce polymers of high molecular weight over a wide range. Therefore, the polymer obtained is expected to have high melt tension and high durability while maintaining high impact strength because the amount of low-molecular-weight components contained in the polymer produced is relatively small corresponding to HLMFR. Conceivable.

Hereinafter, each component contained in the olefin polymerization catalyst of the present invention and the method for producing the olefin polymerization catalyst of the present invention will be described.

1. Component (A)
Component (A) used in the present invention is a metallocene compound represented by the following general formula (1).

[In formula (1),
^M1 represents a titanium atom, a zirconium atom or a hafnium atom.
X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom. It represents a hydrocarbon group or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; , an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and an alkyl group having 1 carbon atom Alkyl group having 1 to 6 carbon atoms substituted with trialkylsilyl group of 1 to 3, substituted silyl group substituted with hydrocarbon group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms, substituted with halogen atom represents an aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. ]

M ¹ is a titanium atom (Ti), a zirconium atom (Zr) or a hafnium atom (Hf), with a zirconium atom being preferred from the viewpoint of molecular weight and activity.

X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom. It is a hydrocarbon group or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.
Specific examples of halogen atoms include chlorine, bromine, iodine and fluorine atoms.
Specific examples of hydrocarbon groups having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t- Alkyl groups or cycloalkyl groups such as butyl group, n-pentyl group, neopentyl group, n-hexyl group, octyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group; vinyl group, propenyl group, butenyl group, hexenyl group, cyclo Alkenyl groups such as hexenyl group; Alkyl groups having alicyclic substituents such as cyclopentylmethyl group and 2-cyclohexylethyl group; Phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3 ,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, 4-vinylphenyl group, 3-allylphenyl group, 4 - Monocyclic or condensed ring aryl group optionally substituted with saturated or unsaturated hydrocarbon group such as (3-butenyl)phenyl group and naphthyl group; aromatic substitution such as benzyl group and 2-phenylethyl group and an alkyl group having a group.
Specific examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy and phenoxy groups. can be mentioned.
The hydrocarbon group having 3 to 20 carbon atoms containing an oxygen atom or a nitrogen atom may be a hydrocarbon group having 3 to 20 carbon atoms containing at least one oxygen atom or nitrogen atom. there is something ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, 4 -alkoxyalkyl groups such as methoxybutyl group, 3-ethoxybutyl group and 6-methoxyhexyl group; alkoxy groups such as 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group and 2,4-dimethoxyphenyl group; aryl group, acetyl group, 1-oxopropyl group, 1-oxo-n-butyl group, 2-methyl-1-oxopropyl group, 2,2-dimethyl-1-oxo-propyl group, phenylacetyl group, diphenylacetyl groups, oxo group-containing hydrocarbon groups such as benzoyl group, cyclic ether groups such as 2-furyl group, 2-tetrahydrofuryl group, and 2-methylfuryl group; diethylaminomethyl group, di-i-propylaminomethyl group, bis(dimethylamino)methyl group, bis(di-i-propylamino)methyl group, (dimethylamino)(phenyl)methyl group, aminoethyl group, dimethylaminoethyl group, diethylaminoethyl group, 1-(methylimino)ethyl group, 1-(phenylimino)ethyl group, 1-[(phenylmethyl)imino]ethyl group, amino-substituted alkyl groups such as dimethylaminohexyl group, 4-aminophenyl group, Examples include amino-substituted aryl groups such as 4-dimethylaminophenyl group.
The substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms may be a substituted amino group substituted with at least one hydrocarbon group having 1 to 20 carbon atoms, and a specific example thereof is a dimethylamino group. , diethylamino group, di-n-propylamino group, di-i-butylamino group, di-t-butylamino group, diphenylamino group and the like.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; , an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and an alkyl group having 1 carbon atom Alkyl groups having 1 to 6 carbon atoms substituted with trialkylsilyl groups of up to 3, substituted silyl groups substituted with hydrocarbon groups having 1 to 6 carbon atoms, aryl groups having 6 to 18 carbon atoms, substituted with halogen atoms is an aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent.
Specific examples of the halogen atom are the same as the specific examples of the halogen atom described above for ^X1 and ^X2 .
Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n -pentyl group, neopentyl group, n-hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.
Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy and phenoxy groups. can be done.
Alkoxyalkyl groups having 2 to 6 carbon atoms include, for example, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, 4-methoxybutyl group, 3-ethoxybutyl group and the like.
Examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, propenyl group, butenyl group, hexenyl group, cyclohexenyl group and the like.
The alkyl group having 1 to 6 carbon atoms substituted with a halogen atom may be an alkyl group having 1 to 6 carbon atoms substituted with at least one halogen atom, such as bromomethyl group, chloromethyl group, trifluoro methyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 2-bromopropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl group, 4-chlorobutyl group, 3-fluorobutyl group, 4,4,4-trifluorobutyl group, and the like.
Examples of the alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group having 1 to 3 carbon atoms include a trimethylsilylmethyl group, a trimethylsilylethyl group and a 2-trimethylsilylpropyl group.
The substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms may be a substituted silyl group substituted with at least one hydrocarbon group having 1 to 6 carbon atoms, such as trimethylsilyl group, t- A butyldimethylsilyl group and the like can be mentioned.
Examples of the aryl group having 6 to 18 carbon atoms include phenyl group, naphthyl group and biphenyl group.
The aryl group having 6 to 18 carbon atoms substituted with a halogen atom may be an aryl group having 6 to 18 carbon atoms substituted with at least one halogen atom, such as a 2-chlorophenyl group and a 4-chlorophenyl group. , 3,5-dichlorophenyl group and 2,3,4,5,6-pentafluorophenyl group.
The heterocyclic group constituting a 5- or 6-membered ring which may have a substituent is a heterocyclic group which constitutes a 5- or 6-membered ring which may have at least one substituent For example, nitrogen-containing heterocyclic groups such as a pyrrole group and a pyridine group, oxygen-containing heterocyclic groups such as a furan group and a pyran group, sulfur-containing heterocyclic groups such as a thiophene group, and these heterocyclic groups A group substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30 carbon atoms can be mentioned.

From the viewpoint that it is easy to obtain an ethylene-based polymer having an excellent balance of moldability, strength and durability, R ¹ and R ⁶ are each independently an alkyl group having 3 to 6 carbon atoms, and R ³ and R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ may be hydrogen atoms, and R ¹ and R ⁶ are each independently an alkyl group having 3 to 6 carbon atoms, R ³ and R ⁸ are each independently a hydrogen atom or a methyl group, and R ² , R ⁴ and R ⁵ , R ⁷ , R ⁹ and R ¹⁰ may be hydrogen atoms, R ¹ and R ⁶ are each independently an alkyl group having 3 to 6 carbon atoms, R ³ and R ⁸ are hydrogen atoms Yes, and R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ may be hydrogen atoms.

Specific examples of the metallocene compound represented by formula (1) include:
biscyclopentadienyl zirconium dichloride,
bis(methylcyclopentadienyl)zirconium dichloride,
bis(n-propylcyclopentadienyl)zirconium dichloride,
bis(i-propylcyclopentadienyl)zirconium dichloride,
bis(n-butylcyclopentadienyl)zirconium dichloride,
bis(s-butylcyclopentadienyl)zirconium dichloride,
bis(t-butylcyclopentadienyl)zirconium dichloride,
bis(n-hexylcyclopentadienyl)zirconium dichloride,
bis(cyclohexylcyclopentadienyl)zirconium dichloride,
bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,
bis(1,3-di-n-propylcyclopentadienyl)zirconium dichloride,
bis(1,3-di-i-propylcyclopentadienyl)zirconium dichloride,
bis(1,3-di-n-hexylcyclopentadienyl)zirconium dichloride,
bis(1,2-di-n-propylcyclopentadienyl)zirconium dichloride,
bis(1,2-di-i-propylcyclopentadienyl)zirconium dichloride,
bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride,
bis(pentamethylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-ethylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-n-propylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-i-propylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-i-butylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-s-butylcyclopentadienyl)zirconium dichloride,
bis(1-methyl-3-t-butylcyclopentadienyl)zirconium dichloride,
bis(1-ethyl-3-n-propylcyclopentadienyl)zirconium dichloride,
bis(1-ethyl-3-i-propylcyclopentadienyl)zirconium dichloride,
(methylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride,
(methylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride,
(methylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride,
(methylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride,
(n-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride,
(n-propylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride,
(n-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride,
(n-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride,
(i-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride,
(i-propylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride,
(i-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride,
(i-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride,
bis(4-methoxybutylcyclopentadienyl)zirconium dichloride,
bis(butoxycyclopentadienyl)zirconium dichloride,
bis(butenylcyclopentadienyl)zirconium dichloride,
bis(trifluoromethylcyclopentadienyl)zirconium dichloride,
bis(trimethylsilylcyclopentadienyl)zirconium dichloride,
Bis(phenylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)hafnium dichloride and the like can be mentioned.
Among these, bis(n-propylcyclopentadienyl)zirconium dichloride and bis(n-butylcyclopentadienyl) are preferred because it is easy to obtain an ethylene polymer having an excellent balance of moldability, strength and durability. At least one selected from the group consisting of zirconium dichloride, bis(1-methyl-3-n-propylcyclopentadienyl)zirconium dichloride and bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride It is preferable to use
The metallocene compound represented by the formula (1) can be appropriately produced by a conventionally known production method, and a commercially available one can also be used.

2. Component (B)
Component (B) used in the present invention is a metallocene compound represented by the following general formula (2).

[In formula (2),
^M2 represents a titanium atom, a zirconium atom or a hafnium atom.
X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom having 3 to 20 carbon atoms. It represents a hydrocarbon group or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.
Y represents a carbon atom, silicon atom or germanium atom.
R ¹¹ and R ²¹ each independently represent an optionally substituted furyl group or an optionally substituted thienyl group.
^R12 , ^R13 , ^R14 , ^R15 , ^R16 , R17, ^R18 , ^R19 , R22 ^{, R23} , ^R24 , ^R25 , ^R26 , ^R27 , ^R28 and ^{R29 are} each independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom C1-6 alkyl group substituted with C1-3 trialkylsilyl group, substituted silyl group substituted with C1-6 hydrocarbon group, C6-18 aryl group, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. Adjacent groups among R ¹² to R ¹⁹ and R ²² to R ²⁹ may combine to form a 6- to 7-membered ring, and the 6- to 7-membered ring may contain an unsaturated bond.
R ³¹ and R ³² each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, or an alkyl group. an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group having 1 to 3 carbon atoms, a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, It represents an aryl group having 6 to 18 carbon atoms substituted with a halogen atom or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. R ³¹ and R ³² may contain Y to form a 4- to 7-membered ring, and when at least one of R ³¹ and R ³² has a cyclic structure, it is composed of R ³¹ , R ³² and Y The 4- to 7-membered ring may form a condensed ring in which R ³¹ and R ³² share some of the constituent atoms of the cyclic structure. ]

^M2 is a titanium atom (Ti), a zirconium atom (Zr) or a hafnium atom (Hf), and among them, a zirconium atom is preferable from the viewpoint of high activation of the catalyst.

X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom. It is a hydrocarbon group or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.
As specific examples of X ³ and X ⁴ , the specific examples described for X ¹ and X ² in formula (1) can also be cited for X ³ and X ⁴ .

Y is a carbon atom, a silicon atom or a germanium atom, preferably a silicon atom from the viewpoint of complex synthesis.

R ¹¹ and R ²¹ are each independently a furyl group optionally having a substituent or a thienyl group optionally having a substituent, and optionally having at least one substituent It may be a furyl group or a thienyl group optionally having a substituent.
The substituents that the furyl group or thienyl group may have include, for example, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a 1 carbon atom substituted with a halogen atom. -6 alkyl groups, alkyl groups of 1 to 6 carbon atoms substituted with trialkylsilyl groups of 1 to 3 carbon atoms, and 6 carbon atoms optionally substituted by alkyl groups of 1 to 6 carbon atoms 18 to 18 aryl groups, halogen-substituted C6-C18 aryl groups, and C1-C6 hydrocarbon-substituted substituted silyl groups. a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, or a trialkylsilyl group having 1 to 3 carbon atoms; Specific examples of the substituted alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 18 carbon atoms substituted with a halogen atom, and the substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms are: The same can be mentioned as above.
The aryl group having 6 to 18 carbon atoms optionally substituted by a hydrocarbon group having 1 to 6 carbon atoms is an aryl group having 6 to 18 carbon atoms optionally substituted by at least one hydrocarbon group having 1 to 6 carbon atoms. Specific examples include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4,6-trimethylphenyl group, 2,3,4- trimethylphenyl group, 2,4,5-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2-i-propylphenyl group, 3-i-propylphenyl group and 4-i-propylphenyl group, 2- t-butylphenyl group, 3-t-butylphenyl group, 4-t-butylphenyl group, 2,4-di-t-butylphenyl group, 2,5-di-t-butylphenyl group, 2,6-di-t -butylphenyl group, 3,5-di-t-butylphenyl group, biphenylyl group, 1-naphthyl group, 2-naphthyl group, acenaphthyl group, phenanthryl group, anthryl group and the like.
Furthermore, the substituents that the furyl group or the thienyl group may have, the adjacent substituents may be bonded to each other to form a 6- to 7-membered ring, and the 6- to 7-membered ring contains an unsaturated bond. You can stay.

R ¹¹ and R ²¹ are preferably groups represented by the following formula (3) from the viewpoint of easily obtaining an ethylene-based polymer having an excellent balance of moldability, strength and durability.

[In the formula (3), Z is an oxygen atom or a sulfur atom,
R ³³ and R ³⁴ are each independently substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a halogen atom. an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, and a trialkylsilyl group having 1 to 3 carbon atoms substituted for the alkyl group. an alkyl group having 1 to 3 carbon atoms, or a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, and R ³³ and R ³⁴ may combine with each other to form a 6- to 7-membered ring. Alternatively, the 6- to 7-membered ring may contain an unsaturated bond. ]

Z is an oxygen atom or a sulfur atom, and is preferably an oxygen atom from the viewpoint of easily obtaining an ethylene-based polymer having an excellent balance of moldability, strength and durability.

R ³³ and R ³⁴ are each independently substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a halogen atom. an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, and a trialkylsilyl group having 1 to 3 carbon atoms substituted for the alkyl group. an alkyl group having 1 to 3 carbon atoms, or a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, and R ³³ and R ³⁴ may combine with each other to form a 6- to 7-membered ring. Alternatively, the 6- to 7-membered ring may contain an unsaturated bond.
Specific examples of the halogen atom include, for example, the same specific examples of the halogen atom as described for X ¹ and X ² above. an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, an aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, and carbon Specific examples of the substituted silyl group substituted with a hydrocarbon group of number 1 to 6 include the same specific examples as those described above for R ¹ to R ¹⁰ .
Specific examples of the alkenyl group having 2 to 8 carbon atoms include the specific examples of the alkenyl group having 2 to 6 carbon atoms described above for R ¹ to R ¹⁰ , heptenyl group, and octenyl group. .
Specific examples of the alkyl group having 1 to 3 carbon atoms substituted with a trialkylsilyl group having 1 to 3 carbon atoms include, for example, a trimethylsilylethyl group, a triethylsilylethyl group, a 2-trimethylsilylpropyl group, a 2- A triethylsilylpropyl group and the like can be mentioned.

R ³³ is preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or or a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms It is a substituted silyl group substituted with a group. R ³⁴ is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. .

Specific examples of optionally substituted furyl groups include a 2-furyl group, a 2-(5-methylfuryl) group, a 2-(5-ethylfuryl) group, and a 2-(5-n-propylfuryl) group. , 2-(5-i-propylfuryl) group, 2-(5-t-butylfuryl) group, 2-(5-trimethylsilylfuryl) group, 2-(5-triethylsilylfuryl) group, 2-(5- phenylfuryl) group, 2-(5-tolylfuryl) group, 2-(5-fluorophenylfuryl) group, 2-(5-chlorophenylfuryl) group, 2-(4,5-dimethylfuryl) group, 2-( 3,5-dimethylfuryl) group, 2-benzofuryl group, 3-furyl group, 3-(5-methylfuryl) group, 3-(5-ethylfuryl) group, 3-(5-n-propylfuryl) group , 3-(5-i-propylfuryl) group, 3-(5-t-butylfuryl) group, 3-(5-trimethylsilylfuryl) group, 3-(5-triethylsilylfuryl) group, 3-(5- phenylfuryl) group, 3-(5-tolylfuryl) group, 3-(5-fluorophenylfuryl) group, 3-(5-chlorophenylfuryl) group, 3-(4,5-dimethylfuryl) group, 3-benzofuryl and the like.
Specific examples of optionally substituted thienyl groups include a 2-thienyl group, a 2-(5-methylthienyl) group, a 2-(5-ethylthienyl) group, and a 2-(5-n-propylthienyl) group. , 2-(5-i-propylthienyl) group, 2-(5-t-butylthienyl) group, 2-(5-trimethylsilylthienyl) group, 2-(5-triethylsilylthienyl) group, 2-(5 -phenylthienyl) group, 2-(5-tolylthienyl) group, 2-(5-fluorophenylthienyl) group, 2-(5-chlorophenylthienyl) group, 2-(4,5-dimethylthienyl) group, 2 -(3,5-dimethylthienyl) group, 2-benzothienyl group, 3-thienyl group, 3-(5-methylthienyl) group, 3-(5-ethylthienyl) group, 3-(5-n-propyl thienyl) group, 3-(5-i-propylthienyl) group, 3-(5-t-butylthienyl) group, 3-(5-trimethylsilylthienyl) group, 3-(5-triethylsilylthienyl) group, 3 -(5-phenylthienyl) group, 3-(5-tolylthienyl) group, 3-(5-fluorophenylthienyl) group, 3-(5-chlorophenylthienyl) group, 3-(4,5-dimethylthienyl) groups, 3-benzothienyl groups, and the like.

^R12 , ^R13 , ^R14 , ^R15 , ^R16 , R17, ^{R18 , R19} , R22, ^R23 , ^R24 , ^R25 , ^R26 , ^R27 , ^R28 and ^{R29 are} each independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom C1-6 alkyl group substituted with C1-3 trialkylsilyl group, substituted silyl group substituted with C1-6 hydrocarbon group, C6-18 aryl group, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. Adjacent groups among R ¹² to R ¹⁹ and R ²² to R ²⁹ may combine to form a 6- to 7-membered ring, and the 6- to 7-membered ring may contain an unsaturated bond.
Specific examples of the halogen atom include, for example, the same specific examples of the halogen atom as described for X ¹ and X ² above. an alkenyl group with 2 to 6 carbon atoms, an alkyl group with 1 to 6 carbon atoms substituted with a halogen atom, an alkyl group with 1 to 6 carbon atoms in which the alkyl group is substituted with a trialkylsilyl group with 1 to 3 carbon atoms, It may have a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms substituted by a halogen atom, or a substituent. Specific examples of the heterocyclic group constituting a 5-membered ring or 6-membered ring include the same specific examples as those described above for R ¹ to R ¹⁰ .

Specific examples of the metallocene compound represented by the above formula (2) include, for example,
[1,1′-dimethylsilylenebis{2-(2-furyl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(2-thienyl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-diphenylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-dimethylgermylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-dimethylgermylenebis{2-(5-methyl-2-thienyl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-trimethylsilyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-phenyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(4,5-dimethyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride dichloride,
[1,1′-dimethylsilylenebis{2-(2-benzofuryl)-4-phenyl-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trifluoromethylphenyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(2-furyl)-4-(1-naphthyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(2-furyl)-4-(2-naphthyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(2-furyl)-4-(2-phenanthryl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(2-furyl)-4-(9-phenanthryl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(1-naphthyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-phenanthryl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(9-phenanthryl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(1-naphthyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(2-naphthyl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(2-phenanthryl)-indenyl}]zirconium dichloride,
[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(9-phenanthryl)-indenyl}]zirconium dichloride and the like can be mentioned.

Among these, from the point that it is easy to obtain an ethylene polymer having an excellent balance of moldability, strength and durability, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4 -Phenyl-indenyl}]zirconium dichloride, [1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride, [1,1′-dimethyl Silylenebis{2-(5-trimethylsilyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride, [1,1′-dimethylsilylenebis{2-(5-phenyl-2-furyl)-4-phenyl -indenyl}]zirconium dichloride, [1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]zirconium dichloride, and [1, It is preferable to use at least one selected from the group consisting of 1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}]zirconium dichloride.

When synthesizing the metallocene compound represented by formula (2), for example, Synthesis Example 1 in JP-A-2012-149160 can be referred to.

3. Component (C)
The component (C) used in the present invention is a compound that converts the above-described components (A) and (B) into cationic compounds, that is, a co-catalyst. Component (A) and component (B) contained in the olefin polymerization catalyst of the present invention may react with component (C) to form a cationic compound.
Examples of component (C) that can be used include organoaluminumoxy compounds, borane compounds, borate compounds, and later-described layered silicates. Of these, organoaluminum oxy compounds are preferably used because they are easily immobilized on fine particle carriers.

(1) Organoaluminum oxy compound The organoaluminum oxy compound is a compound having an Al—O—Al bond in the molecule, and the number of Al—O—Al bonds is usually 1 to 100, preferably 1 to 50. in the range.
Typically, an organoaluminum oxy compound containing a chain structure of —(O—Al)— units as represented by the following formula (4) or formula (5) is used.

[In each of the above formulas, each R ⁴¹ is independently a hydrogen atom or a hydrocarbon group, preferably an alkyl group, an alkenyl group, an aryl group having 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, It is a hydrocarbon group such as an aralkyl group, and at least part of R ⁴¹ is a hydrocarbon group. p represents an integer of 0-40, preferably 2-30. ]

Such an organoaluminumoxy compound is generally obtained by reacting an organoaluminum compound with water.
The reaction between the organoaluminum compound and water is usually carried out in an inert hydrocarbon (solvent). As inert hydrocarbons, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. It is preferred to use aromatic hydrocarbons.

As the starting organic aluminum compound, a compound represented by the following formula (6) can be used, but trialkylaluminum is preferably used.
R ⁴¹ _t AlX ⁶ _3-t formula (6)
[In formula (6), R ⁴¹ is the same as in formulas (4) and (5) above, X ⁶ represents a hydrogen atom or a halogen atom, and t represents an integer of 1 ≤ t ≤ 3 . ]

The alkyl group of trialkylaluminum is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n A -decyl group, an n-dodecyl group or the like may be used, but a methyl group is particularly preferred. Two or more of the organoaluminum compounds may be used in combination.

The reaction ratio between water and the organoaluminum compound (water/Al molar ratio) is preferably 0.25/1 to 1.2/1, particularly preferably 0.5/1 to 1/1, and the reaction temperature is , usually -70°C to 100°C, preferably -20°C to 20°C. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours.
As the water required for the reaction, not only water but also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., and components capable of producing water in the reaction system can be used.

An organoaluminum oxy compound using trimethylaluminum as the starting organoaluminum compound is called methylaluminoxane (MAO). Methylaluminoxane (MAO) is particularly preferably used as component (C) from the viewpoint of industrial availability and control of polymer particle properties. MAO can also be used as component (C) in a form containing unreacted trimethylaluminum. This unreacted trimethylaluminum may be present at 1 mol% to 30 mol% with respect to the total aluminum atoms of trimethylaluminum and methylaluminoxane, and within this range MAO is difficult to precipitate in the solution, The danger during handling is reduced and it is easy to handle. An MAO solution containing 10 mol % to 15 mol % of trimethylaluminum is preferred. In addition, when the concentration of MAO is within this range, the danger during handling is reduced, the storage stability is good, and it is suitable from the viewpoint of handling. The concentration of MAO used is preferably 10% by mass to 20% by mass. Furthermore, since the MAO solution tends to precipitate at room temperature, low-temperature storage below -10°C is preferable.
Of course, as the organoaluminum oxy compound, two or more of the above organoaluminum oxy compounds can be used in combination. You can use what you have.

(2) Borane compounds Examples of borane compounds include the following compounds: triphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane, tri(m-tolyl)borane, tri(o -fluorophenyl)borane, tris(p-fluorophenyl)borane, tris(m-fluorophenyl)borane, tris(2,5-difluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4- trifluoromethylphenyl)borane, tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris (perfluorobiphenyl)borane, tris(perfluoroanthryl)borane, tris(perfluorobinaphthyl)borane.

Among these, the following compounds are preferred: tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl). Borane, tris(perfluorobiphenyl)borane, tris(perfluoroanthryl)borane, tris(perfluorobinaphthyl)borane.
Among these, the following compounds are more preferred: tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, and tris(perfluorobiphenyl)borane.

(3) Borate compound A first example of the borate compound is a compound represented by the following formula (7).
[L ¹ -H] ⁺ [BR ⁴² R ⁴³ X ⁷ X ^7′ ] ^- formula (7)

In formula (7), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium or phosphonium.
Examples of ammonium include trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tri(n-propyl)ammonium and tri(n-butyl)ammonium, and dialkylammonium such as di(n-propyl)ammonium and dicyclohexylammonium.
Examples of anilinium include N,N-dialkylanilinium such as N,N-dimethylanilinium, N,N-diethylanilinium, and N,N-2,4,6-pentamethylanilinium.
Furthermore, phosphonium includes triarylphosphonium and trialkylphosphonium such as triphenylphosphonium, tri(n-butyl)phosphonium, tri(methylphenyl)phosphonium, and tri(dimethylphenyl)phosphonium.

In formula (7), R ⁴² and R ⁴³ each independently have an optionally substituted carbon number of 6 to 20, preferably an optionally substituted carbon number of 6 to 16. which may be linked to each other by a bridging group, and the substituents include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, alkyl groups, fluorine, and chlorine. Halogens such as , bromine, and iodine are preferred.
Furthermore, each of X ⁷ and X ^7′ is independently a hydride group, a halide group, a hydrocarbon group having 1 to 20 carbon atoms, or a It is a hydrocarbon group.

Specific examples of the compound represented by the general formula (7) include the following compounds: tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate. , tributylammonium tetra(3,5-ditrifluoromethylphenyl)borate, tributylammonium tetra(2,6-difluorophenyl)borate, tributylammonium tetra(perfluoronaphthyl)borate, dimethylaniliniumtetra(pentafluorophenyl)borate, Dimethylanilinium tetra(2,6-ditrifluoromethylphenyl)borate, Dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl)borate, Dimethylaniliniumtetra(2,6-difluorophenyl)borate, Dimethylaniliniumtetra (perfluoronaphthyl)borate, triphenylphosphoniumtetra(pentafluorophenyl)borate, triphenylphosphoniumtetra(2,6-ditrifluoromethylphenyl)borate, triphenylphosphoniumtetra(3,5-ditrifluoromethylphenyl)borate, triphenylphosphonium tetra(2,6-difluorophenyl)borate, triphenylphosphonium tetra(perfluoronaphthyl)borate, trimethylammonium tetra(2,6-ditrifluoromethylphenyl)borate, triethylammonium tetra(pentafluorophenyl)borate, triethylammonium tetra(2,6-ditrifluoromethylphenyl)borate, triethylammonium tetra(perfluoronaphthyl)borate, tripropylammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra(perfluoronaphthyl)borate, di(1-propyl)ammonium tetra(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate.

Among these, the following compounds are preferred: tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl)borate, Tributylammonium tetra(perfluoronaphthyl)borate, dimethylaniliniumtetra(pentafluorophenyl)borate, dimethylaniliniumtetra(2,6-ditrifluoromethylphenyl)borate, dimethylaniliniumtetra(3,5-ditrifluoromethylphenyl) ) borate, dimethylanilinium tetra(perfluoronaphthyl)borate.

A second example of the borate compound includes, for example, a compound represented by the following formula (8).
[L ² ] ⁺ [BR ⁴² R ⁴³ X ^7' X ^7' ] ^- formula (8)

In formula (8), ^L2 is methyl cation, ethyl cation, n-propyl cation, i-propyl cation, n-butyl cation, i-butyl cation, t-butyl cation, n-pentyl cation, tropynium cation, benzyl cation, trityl cation, sodium cation, proton and the like. Also, R ⁴² , R ⁴³ , X ⁷ and X ^7′ are the same as defined in the above formula (7).

Specific examples of the compound represented by the formula (8) include the following compounds: trityltetraphenylborate, trityltetra(o-tolyl)borate, trityltetra(p-tolyl)borate, trityltetra (m-tolyl)borate, trityltetra(o-fluorophenyl)borate, trityltetra(p-fluorophenyl)borate, trityltetra(m-fluorophenyl)borate, trityltetra(3,5-difluorophenyl)borate, trityl Tetra(pentafluorophenyl)borate, Trityltetra(2,6-ditrifluoromethylphenyl)borate, Trityltetra(3,5-ditrifluoromethylphenyl)borate, Trityltetra(perfluoronaphthyl)borate, Tropinium tetraphenylborate , tropinium tetra(o-tolyl)borate, tropinium tetra(p-tolyl)borate, tropinium tetra(m-tolyl)borate, tropinium tetra(o-fluorophenyl)borate, tropiniumtetra(p-fluorophenyl ) borate, tropinium tetra(m-fluorophenyl)borate, tropinium tetra(3,5-difluorophenyl)borate, tropiniumtetra(pentafluorophenyl)borate, tropiniumtetra(2,6-ditrifluoromethylphenyl) Borate, tropinium tetra(3,5-ditrifluoromethylphenyl)borate, tropinium tetra(perfluoronaphthyl)borate, NaBPh ₄ , NaB(o-CH ₃ -Ph) ₄ , NaB(p-CH ₃ -Ph) ₄ , NaB(m—CH ₃ —Ph) ₄ , NaB(o—F—Ph) ₄ , NaB(p—F—Ph) ₄ , NaB(m—F—Ph) ₄ , NaB(3,5-F ₂ -Ph) ₄ , NaB(C ₆ F ₅ ) ₄ , NaB(2,6-(CF ₃ ) ₂ -Ph) ₄ , NaB(3,5-(CF ₃ ) ₂ -Ph) ₄ , NaB(C ₁₀ F ₇ ) ₄ , HBPh _4. (Et ₂ O) ₂ , HB(3,5-F ₂ -Ph) _4. (Et ₂ O) ₂ , HB(C ₆ F ₅ ) _4. (Et ₂ O) ₂ , HB(2,6-( _CF3 ) ₂ -Ph) _4. ( _Et2O ) ₂ , HB(3,5-( _CF3 ) _2- Ph) _4. ( _Et2O ) ₂ , H B _{( C10H7} ) _4. ( _Et2O ) ₂ .
In addition, in this specification, Et represents ethyl and Ph represents phenyl.

Among these, the following compounds are preferred: trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra( perfluoronaphthyl)borate, tropinium tetra(pentafluorophenyl)borate, tropiniumtetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, tropiniumtetra( perfluoronaphthyl)borate, NaB( _{C6F5 ) 4} , NaB(2,6-( _CF3 ) ₂ -Ph) ₄ , NaB(3,5-( _CF3 ) _2- Ph) ₄ , NaB(C ₁₀ F ₇ ) ₄ , HB(C ₆ F ₅ ) _4. (Et ₂ O) ₂ , HB(2,6-(CF ₃ ) ₂ -Ph) _4. (Et ₂ O) ₂ , HB(3,5 -(CF ₃ ) ₂ -Ph) _4. (Et ₂ O) ₂ , HB(C ₁₀ H ₇ ) _4. (Et ₂ O) ₂ .

Among these, the following compounds are more preferable: trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(pentafluorophenyl)borate, tropiniumtetra(2, 6-ditrifluoromethylphenyl)borate, NaB( _{C6F5 ) 4} , NaB(2,6-( _CF3 ) _{2 -} Ph) ₄ , HB( _C6F5 ) _4. ( _Et2O ) ₂ , HB(2,6-(CF ₃ ) ₂ -Ph) _4. (Et ₂ O) ₂ , HB(3,5-(CF ₃ ) ₂ -Ph) _4. (Et ₂ O) ₂ , HB(C _{10 H7} ) _4. ( _Et2O ) ₂ .

As the component (C), a mixture of the above organoaluminumoxy compound and the above borane compound or borate compound can also be used. Further, two or more kinds of the above borane compounds and borate compounds can be mixed and used.

4. Component (D)
Component (D), the particulate carrier, includes inorganic carriers, particulate polymeric carriers, or mixtures thereof. As the inorganic carrier, metals, metal oxides, metal chlorides, metal carbonates, carbonaceous substances, or mixtures thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.

Metal oxides include single oxides and composite oxides of elements of Groups 1 to 14 of the periodic table, such as SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , _{ZrO2 , Fe2O3 , Al2O3.MgO , Al2O3.CaO , Al2O3.SiO2 , Al2O3.MgO.CaO , Al2O3.MgO.SiO2 , Al 2} O ₃ ·CuO, Al ₂ O ₃ ·Fe ₂ O ₃ , Al ₂ O ₃ ·NiO, SiO ₂ ·MgO and other various natural or synthetic single oxides or complex oxides can be exemplified. Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited. Moreover, the metal oxide used in the present invention may absorb a small amount of water and may contain a small amount of impurities.

As metal chlorides, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ , CaCl ₂ and the like are particularly preferable. As metal carbonates, carbonates of alkali metals and alkaline earth metals are preferable, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate, and the like.
Examples of carbonaceous substances include carbon black and activated carbon.
Any of the above inorganic carriers can be suitably used in the present invention, but metal oxides, silica and alumina are preferably used, and silica is more preferably used. As silica, it is preferable to use small particle size silica having an average particle size of about 10 μm to 150 μm. Here, the average particle diameter is a value indicated as a median diameter from data expressed on a volume basis by a generally used measurement method using laser diffraction.

These inorganic supports are usually calcined at 200° C. to 800° C., preferably 400° C. to 600° C. in air or in an inert gas such as nitrogen or argon to reduce the amount of surface hydroxyl groups to 0.8 mmol/g to 1 It is preferably used after being adjusted to 0.5 mmol/g. Although the properties of these inorganic carriers are not particularly limited, they usually have an average particle diameter of 5 μm to 200 μm, preferably 10 μm to 150 μm, an average pore diameter of 20 Å to 1000 Å, preferably 50 Å to 500 Å, and a specific surface area of 150 m ^{2 /} . g to 1000 m ² /g, preferably 200 m ² /g to 700 m ² /g, pore volume 0.3 m ^{3 /} g to 2.5 cm ³ /g, preferably 0.5 m ^{3 /} g to 2.0 cm ³ /g and an apparent specific gravity of 0.20 g/cm ³ to 0.50 g/cm ³ , preferably 0.25 g/cm ³ to 0.45 g/cm ³ .

Of course, the above-mentioned inorganic carriers can be used as they are. , tri-n-octylaluminum, tri-n-decylaluminum, di-i-butylaluminum hydride, or an organoaluminum oxy compound containing an Al—O—Al bond.

5. Method for Producing Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention can be produced by mixing or contacting component (A), component (B), component (C) and component (D).
The method for producing the olefin polymerization catalyst of the present invention is not particularly limited, but, for example, the following method can be arbitrarily adopted.
Method (1):
Components (A) and (B) are contacted first with component (C) and then with component (D). More specifically, after contacting component (A) and component (B) with one component (C), or component (A) and component (B) each separately separated and contacted with component (C) After that, the resulting contact-treated product is brought into contact with component (D).
When component (A) and component (B) are contacted with one component (C), a mixture of component (A) and component (B) may be contacted with component (C), or component (A) and Component (B) may be contacted with component (C) simultaneously or sequentially.
When component (A) and component (B) are contacted with separately separated component (C), the contact-treated product of component (A) and the contact-treated product of component (B) are combined into one component (D). Alternatively, after contacting the component (A) contact-treated product and the component (B) contact-treated product with separately separated component (C), the resulting two contact-treated products are May be mixed.
Method (2):
Components (A) and (B) are contacted first with component (D) and then with component (C). More specifically, after contacting component (A) and component (B) with one component (D), or contacting component (A) and component (B) separately with component (D). Then, the resulting contact-treated product is brought into contact with component (C).
When component (A) and component (B) are contacted with one component (D), a mixture of component (A) and component (B) may be contacted with component (D), or component (A) and Component (B) may be contacted with component (D) simultaneously or sequentially.
When component (A) and component (B) are brought into contact with separately separated component (D), the contact-treated product of component (A) and the contact-treated product of component (B) are combined into one component (C). Alternatively, after contacting the component (A) contact-treated product and the component (B) contact-treated product with separately separated component (C), the resulting two contact-treated products are May be mixed.
Method (3):
Components (C) and (D) are first brought into contact with each other to obtain a contact treatment, and then components (A) and (B) are brought into contact with the contact treatment. More specifically, after contacting the component (C) and the component (D) to obtain a contact treated product, the component (A) and the component (B) are contacted with one contact treated product, or the component (A ) and component (B) are each contacted with separate contact treatments and the resulting two contact treatments are mixed.
When the component (A) and the component (B) are brought into contact with one contact treatment product, a mixture of the component (A) and the component (B) may be brought into contact with the contact treatment product, or the component (A) and the component ( B) may be brought into contact simultaneously or sequentially with the contact treatment.

Among these contacting methods are the method of (1) in which components (A) and (B) are first contacted with component (C), and the method of (1) in which components (A) and (B) are first contacted with component (C). The method (3) of contacting with the contact-treated product (D) is preferred, and the method (1) is most preferred. Furthermore, it is preferable to contact the mixture of component (A) and component (B) with component (C), component (D), or the contact-treated product of component (C) and component (D).

In either contacting method, an aromatic hydrocarbon (generally having 6 to 12 carbon atoms), typically benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, dodecane, is usually reacted in an inert atmosphere such as nitrogen or argon. , cyclohexane, and other aliphatic or alicyclic hydrocarbons (generally having 5 to 12 carbon atoms) in the presence of a liquid inert hydrocarbon, with or without stirring, each component is brought into contact.
This contact is usually carried out at a temperature of -100°C to 200°C, preferably -50°C to 100°C, more preferably 0°C to 50°C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably is preferably carried out for 30 minutes to 12 hours.
Specific examples of the contact method include a mixture of component (A) and component (B), or a liquid obtained by dissolving or dispersing component (A) and component (B) in an inert solvent as described above, and component (C ) is dissolved or dispersed in an inert solvent, and the obtained mixture is mixed with the slurry of component (D).

In addition, when the components (A), (B), (C) and (D) are brought into contact with each other, an aromatic hydrocarbon solvent in which certain components are soluble or sparingly soluble and a solvent in which certain components are insoluble are used. or sparingly soluble aliphatic or alicyclic hydrocarbon solvents can be used.

When the contact reaction between each component is carried out in stages, the solvent used in the former step may be used as it is as the solvent for the contact reaction in the latter step without removing it. In addition, after the initial contact reaction using a soluble solvent, some components are insoluble or sparingly soluble in liquid inert hydrocarbons (e.g., aliphatics such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, and xylene). after adding a hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon) and recovering the desired product as a solid matter, or once part or all of the soluble solvent is removed by drying or other means to obtain the desired product. After removing the product as a solid, subsequent catalytic reaction of the desired product can be carried out using any of the inert hydrocarbon solvents described above. In the present invention, the contact reaction of each component may be carried out multiple times.

In the present invention, the ratio of use of component (A), component (B), component (C) and component (D) is not particularly limited, but the following ranges are preferred.
The molar ratio of component (A) to component (B) (component (A):component (B)) is arbitrarily adjusted to determine the shape of the molecular weight distribution of the resulting polymer, and is usually 1:500 to 500: 1, preferably 1:100 to 100:1, more preferably 1:10 to 10:1, and may range from 1.2:1 to 5:1.
When an organoaluminumoxy compound is used as the component (C), the molar ratio (Al/M) of the aluminum atoms in the organoaluminumoxy compound to the total amount of the transition metal (M) contained in the components (A) and (B). is usually in the range of 1 to 100,000, preferably 5 to 1000, more preferably 50 to 200. Further, when a borane compound or a borate compound is used, the molar ratio (B/M) of boron atoms to the total amount of transition metals (M) contained in components (A) and (B) is usually 0.01. ~100, preferably 0.1-50, more preferably 0.2-10.
Furthermore, when a mixture of an organoaluminumoxy compound, a borane compound, and a borate compound is used as component (C), the transition metal contained in component (A) and component (B) for each compound in the mixture It is desirable to select the ratio of use similar to the above with respect to the total amount of (M).

The amount of component (D) used is such that the total amount of transition metals contained in component (A) and component (B) is 0.0001 mmol to 5 mmol, preferably 0.001 mmol to 0, per 1 g of component (D). 0.5 mmol, more preferably 0.01 mmol to 0.1 mmol.

An olefin polymerization catalyst can be obtained by contacting component (A), component (B), component (C) and component (D) with each other by any of the contact methods (1) to (3). Following the steps, the solvent may be removed after performing a washing step to remove unreacted materials and unwanted products.
In the washing process, the catalyst for olefin polymerization is allowed to settle, then the unnecessary supernatant liquid is extracted, and then a new solvent is added to homogenize with stirring; the above-mentioned stirring and homogenization are repeated; method is used. Solvents that can be used in contacting components (A) to (D) are used in the washing step. Also, the solvent can be changed during the washing process.
As the step of removing the solvent, a distillation method of evaporating the solvent at a pressure corresponding to the boiling point of the solvent, a method of vaporizing the solvent with a dry inert gas stream, or the like can be used. It is desirable to remove the solvent under normal pressure or reduced pressure at 0° C. to 200° C., preferably 20° C. to 150° C., for 1 minute to 50 hours, preferably 10 minutes to 10 hours.
The olefin polymerization catalyst obtained after the washing step can be handled or stored in a slurry state, and the olefin polymerization catalyst obtained in the step of removing the solvent can be handled or stored as a powdery solid catalyst.

The olefin polymerization catalyst of the present invention can also be obtained by the following method.
Method (4):
Components (A) and (B) are brought into contact with component (D), which is a fine particle carrier, to remove the solvent, and this is used as a solid catalyst component, which is brought into contact with component (C), which is a co-catalyst, under polymerization conditions. .
Method (5):
Component (C), which is a promoter, is brought into contact with Component (D), which is a fine particle carrier, to remove the solvent. B).
Also in the case of the method (4) and the method (5), the same conditions as those described above can be adopted for the component ratio, contact conditions and solvent removal conditions.

A layered silicate can also be used as a component that serves both as the component (C) that is a co-catalyst and the component (D) that is a fine particle carrier. A layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with weak bonding force. Most of the layered silicates are naturally produced mainly as a main component of clay minerals, but these layered silicates are not particularly limited to naturally occurring ones, and may be artificially synthesized ones.
Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite, and other smectites, vermiculites, and micas are preferred.

In general, natural products are often non-ion-exchangeable (non-swelling). It is preferable to carry out a treatment for imparting. Particularly preferred among such treatments are the following chemical treatments. Here, the chemical treatment can be any of surface treatment for removing impurities adhering to the surface and treatment for influencing the crystal structure and chemical composition of the layered silicate.
Specifically, (a) acid treatment using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment using NaOH, KOH, _NH3 , etc., (c) periodic table groups 2 to 14 Salt treatment using a salt consisting of at least one anion selected from the group consisting of a cation containing at least one selected atom and an anion derived from a halogen atom or an inorganic acid, (d) alcohol, carbonization Treatment with organic substances such as hydrogen compounds, formamide, aniline, and the like can be mentioned. These treatments may be performed alone, or two or more treatments may be combined.

The particle properties of the layered silicate can be controlled by pulverization, granulation, sizing, fractionation, or the like before, during, or after all steps. The method can be any sensible one. In particular, granulation methods include spray granulation, tumbling granulation, compression granulation, stirring granulation, briquetting, compacting, extrusion granulation, and fluid bed granulation. method, emulsion granulation method and submerged granulation method. Particularly preferred granulation methods are spray granulation, tumbling granulation and compression granulation.

The layered silicates described above can of course be used as they are, but these layered silicates can be used as trimethylaluminum, triethylaluminum, tri-i-butylaluminum, tri-n-propylaluminum, tri-n-butylaluminum and tri-n-hexylaluminum. , tri-n-octylaluminum, tri-n-decylaluminum and di-i-butylaluminum hydride, and organoaluminum oxy compounds containing an Al—O—Al bond.

In order to support the components (A) and (B), which are catalytically active components, on the layered silicate, the components (A) and (B) and the layered silicate are brought into contact with each other, or the components (A) and (B) are brought into contact with each other. Component (B), the organoaluminum compound or organoaluminumoxy compound, and the layered silicate may be brought into contact with each other.
The method of contacting each component is not particularly limited, and for example, the following method can be optionally adopted.
Method (6):
After contacting component (A) and component (B) with the organoaluminum compound or organoaluminumoxy compound, they are brought into contact with the layered silicate support.
Method (7):
After contacting component (A) and component (B) with the layered silicate support, contact is made with an organoaluminum compound or an organoaluminumoxy compound.
Method (8):
After contacting the organoaluminum compound or organoaluminumoxy compound with the layered silicate support, component (A) and component (B) are contacted.

Among these contact methods, method (6) and method (8) are preferred. In any of the contact methods, an aromatic hydrocarbon (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, n-heptane, n-hexane, or In the presence of liquid inert hydrocarbons such as n-decane, n-dodecane, cyclohexane, and other aliphatic or alicyclic hydrocarbons (usually having 5 to 12 carbon atoms), each component is brought into contact with stirring or without stirring. method is adopted.
When the component (A) and the component (B) are supported on the layered silicate, the same conditions as those for the inorganic support can be employed for the method of supporting, solvent washing and solvent removal.

The proportions of the catalytically active components (A) and (B), the organoaluminum compound or organoaluminum oxy compound, and the layered silicate support are not particularly limited, but are preferably within the following ranges.
The amount of component (A) and component (B) supported is preferably such that the total amount of the transition metal (M) contained in component (A) and component (B) is 0.0001 mmol to 5 mmol per 1 g of the layered silicate support. is 0.001 mmol to 0.5 mmol, more preferably 0.01 mmol to 0.1 mmol.
When using an organoaluminum compound or an organoaluminumoxy compound, the ratio of aluminum atoms contained in the organoaluminum compound or organoaluminumoxy compound to the total amount of the transition metal (M) contained in the component (A) and the component (B) is The molar ratio (Al/M) is desirably in the range of 0.01-100, preferably 0.1-50, more preferably 0.2-10.

The olefin polymerization catalyst thus obtained may be prepolymerized in the presence of an olefin either inside the polymerization vessel or outside the polymerization vessel. Olefin refers to a hydrocarbon containing at least one carbon-carbon double bond, exemplified by ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene and the like. Mixtures of these with other olefins may also be used without limitation. Ethylene and propylene are preferred. Ethylene is more preferred.

The method of supplying olefin during prepolymerization can be any method, such as a method of supplying olefin to the reactor at a constant rate, a method of maintaining a constant pressure, a combination of these methods, or a stepwise change. be.
Although the prepolymerization time is not particularly limited, it is preferably in the range of 5 minutes to 24 hours.
The prepolymerization amount is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, per 1 part by weight of the polyolefin polymerization catalyst. After completing the preliminary polymerization, the catalyst can be used as it is depending on the type of use of the catalyst, but if necessary, it may be dried.

The prepolymerization temperature is not particularly limited, but is preferably 0°C to 100°C, more preferably 10°C to 70°C, particularly preferably 20°C to 60°C, further preferably 30°C to 50°C.
This range is considered to promote the activation reaction without lowering the reaction rate. In addition, it is thought that deterioration of the particle shape caused by dissolution of the prepolymerized polymer or excessive prepolymerization rate and deactivation of active sites due to side reactions can be suppressed.

Prepolymerization can also be carried out in a liquid such as an organic solvent, and is preferred. The concentration of the solid catalyst during prepolymerization is not particularly limited, but is preferably 50 g/L or more, more preferably 60 g/L or more, and particularly preferably 70 g/L or more. The higher the concentration, the more active the component (A) and the component (B) are, resulting in a highly active catalyst.

Furthermore, it is also possible to coexist with polymers such as polyethylene, polypropylene and polystyrene, and inorganic oxide solids such as silica and titania during the contact between the olefin polymerization catalyst and the olefin or in the contact mixture after the contact. .

The catalyst may be dried after prepolymerization. The drying method is not particularly limited, but examples include drying under reduced pressure, drying by heating, and drying by circulating a dry gas. These methods may be used alone or two or more methods may be used in combination. good too. In the drying step, the catalyst may be stirred, vibrated, fluidized, or allowed to stand still.
The olefin polymerization catalyst of the present invention may be one after pre-polymerization, or may be one before pre-polymerization.

II. Method for Producing Ethylene Polymer The method for producing an ethylene polymer of the present invention comprises polymerizing ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms in the presence of the olefin polymerization catalyst of the present invention described above. characterized by
In the method for producing an ethylene polymer of the present invention, by using the olefin polymerization catalyst of the present invention described above, an ethylene polymer having an excellent balance of moldability, strength and durability can be obtained.

In the method for producing an ethylene-based polymer of the present invention, the monomer used may be ethylene alone, or a combination of ethylene and an α-olefin having 3 to 10 carbon atoms.
Examples of α-olefins having 3 to 10 carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7-octadiene, cyclopentene, norbornene, ethylidenenorbornene, and the like. and preferably α-olefins having 3 to 8 carbon atoms, more preferably α-olefins having 4 to 6 carbon atoms.

Any manner of polymerization can be adopted as long as the catalyst component and each monomer are efficiently brought into contact with each other. Specifically, the slurry polymerization method using an inert solvent, the bulk polymerization method using propylene as a solvent without substantially using an inert solvent, the solution polymerization method, or the gaseous polymerization of each monomer without substantially using a liquid solvent. A vapor phase polymerization method or the like can be employed to maintain the A method of performing continuous polymerization, batchwise polymerization, or prepolymerization is also applicable. Among these, the slurry polymerization method is preferred from the viewpoint of control of polymer particle properties.
In addition, a method of performing multistage polymerization in two or more stages in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure and polymerization temperature are different from each other is also applied.
In the case of the slurry polymerization method, a saturated aliphatic or aromatic hydrocarbon such as isobutane, hexane, heptane, pentane, cyclohexane, benzene, toluene, etc. is used singly or as a mixture as a polymerization solvent. The polymerization temperature is from 0° C. to 150° C., and hydrogen can be used as an auxiliary molecular weight modifier. A suitable polymerization pressure is 0 MPa to 200 MPa, preferably 0 MPa to 6 MPa.
In the case of copolymerization, the amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio. It is also possible to change over time. In addition, one of the monomers can be added in portions in consideration of the copolymerization reaction ratio.

In general, when polymerizing an ethylene-based polymer, in order to suppress static electricity adhesion of the polymer to the polymerization reactor, for example, static electricity such as Stadis (product name Stadis, product name STATSAFE) manufactured by Innospec Co., Ltd. (agency Maruwa Bussan) It is also possible to use inhibitors. An antistatic agent such as Stadis or STATSAFE may be diluted in an inert hydrocarbon medium and added to the polymerization reactor by means of a pump or the like.
The addition method includes a method of adding in advance to the olefin polymerization catalyst, a method of adding to the polymerization reactor, and the like, but the amount to be added is 0.1 ppm or more relative to the solvent in the case of slurry polymerization. 500 ppm or less is preferable, and 1 ppm or more and 50 ppm or less is more preferable. In the case of the gas phase method, the amount of the ethylene polymer produced per unit time is preferably 1 ppm or more and 500 ppm or less, more preferably 10 ppm or more and 100 ppm or less.

The molecular weight of the polymer to be produced can be adjusted by changing the polymerization temperature or by adding hydrogen into the polymerization reactor, and the method of adjusting by adding hydrogen is preferably used.
A chain transfer reaction occurs when hydrogen is inserted into the bond between the transition metal and the polymer chain, and the polymer chain is detached from the transition metal. Therefore, increasing the amount of hydrogen added to increase the hydrogen concentration in the reactor reduces the molecular weight, and decreasing the amount of addition to lower the hydrogen concentration increases the molecular weight.
The susceptibility of the chain transfer reaction to occur due to hydrogen varies depending on the type and content ratio of the transition metal compound contained in the olefin polymerization catalyst.

Olefin polymerization catalysts containing only component (A) as the transition metal compound are suitable for producing polymers containing relatively small amounts of macromonomers. On the other hand, the olefin polymerization catalyst containing only the component (B) as the transition metal compound copolymerizes the α-olefin and the macromonomer while also producing a macromonomer to produce a high-molecular-weight copolymer having a branched structure. suitable to generate. Furthermore, a combination of component (A) and component (B) is preferred in which component (B) has higher copolymerization reactivity with respect to α-olefins (comonomers) having 3 to 10 carbon atoms than component (A).
In the present invention, the olefin polymerization catalyst is a copolymer complex that copolymerizes the component (A) that produces relatively low-molecular-weight macromonomers at a relatively low frequency with the macromonomer derived from component (A). By including, as a transition metal compound, a combination of component (B) which produces a (co)polymer having a higher molecular weight than component (A) and which is difficult to polymerize the self-produced relatively high molecular weight macromonomer as a transition metal compound, An ethylene-based polymer having a wide molecular weight distribution can be produced while suppressing the formation of an excessive number of high-molecular-weight long-chain branches.
In addition, the shape of the molecular weight distribution, that is, whether the low-molecular-weight polymer component is predominant or the high-molecular-weight polymer is predominant, can be controlled by changing the amounts of component (A) and component (B).

In polymerization, in addition to using one reactor, a multi-stage polymerization method using a plurality of reactors is also used. It connects reactors with the same or different reaction conditions, continuously or intermittently feeds the polymer produced in the first reactor with or without solvent into the second reactor, The first is to continue the production of the polymer under the reaction conditions. Although there is no restriction on the number of reactors, preferably two or three stage reactors are used. By changing various conditions such as polymerization temperature, polymerization pressure, monomer concentration, comonomer concentration, and hydrogen concentration between the first reaction condition and the second and subsequent reaction conditions, A mixture of polymers is obtained. By changing the hydrogen concentration, it becomes possible to widen the molecular weight distribution, and by using both the hydrogen concentration and the comonomer concentration, it is possible to produce polymers with different comonomer contents for each molecular weight. Furthermore, by changing the monomer concentration and the polymerization temperature to change the amount of polymer produced in each reactor, it is possible to control the amount ratio of the polymer produced in each reactor.
In the case of multi-stage polymerization, an olefin polymerization catalyst different from or the same as that in the first stage may be added in the second and subsequent stages, and a device for removing unreacted gas may be provided while the reactors are connected. .

In addition, a so-called scavenger may be added to the polymerization system for the purpose of removing moisture. Such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum and tri-i-butylaluminum, the organoaluminum oxy compounds, modified organoaluminum compounds containing branched alkyl, and organozinc compounds such as diethylzinc and dibutylzinc. , organomagnesium compounds such as diethylmagnesium, dibutylmagnesium and ethylbutylmagnesium; and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride. Among these, triethylaluminum, tri-i-butylaluminum and ethylbutylmagnesium are preferred, and triethylaluminum is particularly preferred.

III. Physical Properties of Obtained Ethylene Polymer The ethylene polymer obtained by polymerizing ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms in the presence of the olefin polymerization catalyst of the present invention has a melt tension of Not only is it high and excellent in moldability, but it can also be made to have high strength and durability. The ethylene-based polymer thus obtained has an excellent balance of moldability, strength and durability. The ethylene-based polymer obtained using the olefin polymerization catalyst of the present invention is suitable for use as a plastic molding material, particularly as a plastic molding material for hollow containers.
The ethylene polymer produced using the olefin polymerization catalyst of the present invention may be used by mixing with another polymer. The ethylene-based polymer can also be used after being melt-kneaded after being mixed with various additives other than the polymer.

In the present invention, an ethylene-based copolymer having the following physical properties and suitable for hollow containers can be obtained.
(1) MFR (190°C, 2.16 kg load)
The melt flow rate of the ethylene-based polymer obtained in the present invention, that is, MFR (190° C., 2.16 kg load) may be 0.001 g/10 min to 1000 g/10 min, and may be 0.005 g/10 min. ~200g/10min, 0.01g/10min to 50g/10min, 0.02g/10min to 5.0g/10min, preferably 0.10g /10 minutes to 1.0 g/10 minutes.
When the MFR is in the above range, it is easy to reduce the load on the extruder motor during molding and to suppress the increase in the amount of heat generated by the resin due to shearing, so it is possible to suppress the occurrence of unstable flow phenomena such as shark skin and melt fracture. Keep your appearance good. In addition, the molded product has good drop impact resistance and long-term durability.

(2) HLMFR (190°C, 21.6 kg load)
The high load melt flow rate of the ethylene polymer obtained in the present invention, that is, HLMFR (190° C., 21.6 kg load) may be 0.01 g/10 minutes to 1000 g/10 minutes, and 0.1 g/ 10 min to 500 g/10 min, 1.0 g/10 min to 300 g/10 min, 2.0 g/10 min to 200 g/10 min, preferably 40 g/10 min. min to 60 g/10 min.
Since HLMFR is within the above range, it is considered that performance similar to that of MFR described in (1) is exhibited.
MFR and HLMFR can be adjusted mainly by the amount of hydrogen and the polymerization temperature during the polymerization of the ethylene polymer. In addition, it is believed that the ratio of component (A) and component (B) in the preparation of the olefin polymerization catalyst can also be varied.

(3) Density The density of the ethylene-based polymer obtained in the present invention may be from 0.850 ^g /cm ³ to 0.980 g/cm 3 and from 0.935 g/cm ³ to 0.970 g/cm ³ . preferably 0.945 g/cm ³ to 0.965 g/cm ³ .
When the density is within the above range, environmental stress crack resistance and rigidity are improved.
The density can be controlled mainly by the amount of α-olefin when polymerized using a conventionally well-known catalyst for olefin polymerization. In addition, it is believed that the ratio of component (A) and component (B) in the preparation of the olefin polymerization catalyst can also be varied.

(4) Bulk Density The bulk density of the ethylene-based polymer obtained in the present invention may be 0.20 g/cm ³ to 0.50 g/cm ³ , and may be 0.30 g/cm ³ to 0.50 g/cm ³ . and more preferably 0.35 g/cm ³ to 0.45 g/cm ³ .
When the bulk density is within the above range, it leads to an improvement in the productivity of the polymer and an improvement in the stability of the transportation process of the produced ethylene-based polymer.
The bulk density can be adjusted mainly by controlling the properties of the component (D), the catalyst production method, and the suppression of aggregation of polyethylene particles in the polymerization reactor by adding an antistatic agent.

(5) molecular weight distribution (Mw/Mn)
The molecular weight distribution (Mw/Mn) of the ethylene polymer obtained in the present invention may be 6.0 to 60, may be 8.0 to 50, may be 10 to 40, may be 10 to 30 and preferably 12 to 20.
When the molecular weight distribution is in the above range, flow instability phenomena such as sharkskin are less likely to occur, and melt tension is good, and compatibility and impact resistance are also good.
When the molecular weight distribution is widened within a suitable range, it is suitable for FNCT and melt tension, and it becomes easy to ensure tensile impact strength without excessive low molecular weight components.
In the present invention, the molecular weight distribution (Mw/Mn) is calculated from the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC).
The molecular weight distribution can be adjusted mainly by adjusting the ratio of the components (A) and (B) and, in the case of multistage polymerization, reacting in each stage under different polymerization conditions.

(6) Melt tension (MT)
The melt tension (MT) of the ethylene-based polymer obtained in the present invention is preferably 50 mN or more, more preferably 60 mN or more, still more preferably 70 mN or more at a measurement temperature of 190°C.
Melt tension can be controlled by MFR or HLMFR. The melt tension can also be adjusted by the molecular weight distribution. If the MFR or HLMFR is reduced, the melt tension is increased, and even if the molecular weight distribution is widened, the melt tension is increased. Furthermore, the melt tension is also affected by long chain branching, the greater the amount of long chain branching, the greater the melt tension. When the melt tension is within the above range, the drawdown resistance is good and molding is facilitated.

(7) Tensile impact strength (TIS)
The tensile impact strength (TIS) of the ethylene polymer obtained in the present invention is preferably 130 kJ/m ² or more, more preferably 150 kJ/m ² or more, still more preferably 170 kJ/m ² or more, Even more preferably, it is 200 kJ/m ² or more.
In the present invention, the tensile impact strength (TIS) is measured according to JIS K 7160-1996 B method using a test piece in the form of ASTM D1822 Type-S.
Tensile impact strength (TIS) can be controlled by weight average molecular weight, molecular weight distribution, and density. Increasing the molecular weight, narrowing the molecular weight distribution, and decreasing the density lead to an increase in impact strength, but there is a trade-off relationship with moldability.

(8) Environmental stress crack resistance The ethylene polymer obtained in the present invention preferably has a rupture time of 100 hours or more in a full circumference notch creep test (FNCT) performed in accordance with ISO 16770, and more preferably. is 200 hours or more, more preferably 600 hours or more, and even more preferably 1000 hours or more.
Environmental stress crack resistance (FNCT) can be controlled by weight average molecular weight, molecular weight distribution, and density. An increase in molecular weight and a decrease in density lead to an increase in environmental stress cracking resistance (FNCT), but there is a trade-off relationship with formability. Therefore, in order to prolong the rupture time of FNCT while maintaining moldability, it is necessary to suppress the formation of an excessive number of high-molecular-weight long-chain branches that lead to high viscosity, while maintaining a high molecular weight distribution with a moderately broadened molecular weight distribution. For example, it is controlled so as to obtain a polymer having a molecular weight.

The present invention will be described in more detail in the following Examples and Comparative Examples, but the present invention is not limited by these.
In the examples, the following evaluation methods were carried out, the catalyst synthesis process and the polymerization process were all carried out under a purified nitrogen atmosphere, and the solvent used was dehydrated with Molecular Sieve 4A (trade name, manufactured by Union Showa Co., Ltd.). A purified product was used.

1. Evaluation method (1) MFR (190°C, 2.16 kg load)
MFR was measured under conditions of a temperature of 190° C. and a load of 2.16 kg according to JIS K6760.
(2) HLMFR (190°C, 21.6 kg load)
HLMFR was measured in accordance with JIS K6922-2:1997 under conditions of a temperature of 190° C. and a load of 21.6 kg.
(3) Density Density was measured according to JIS K6922-1,2:1997.
(4) Bulk Density According to the method described in JIS K6730, the obtained ethylene-based polymer is allowed to fall freely using a funnel, collected in a container with a known volume, and then the weight of the polymer in the container is determined. The weight (g) of the ethylene-based polymer per 1 ml was taken as the bulk density.

(5) molecular weight distribution (Mw/Mn)
A gel permeation chromatography (GPC) method is performed under the conditions shown below, and the number average molecular weight (Mn) and weight average molecular weight (Mw) are measured by converting the retention volume to the molecular weight, and the molecular weight distribution (Mw/Mn ) was calculated.
[GPC device, measurement conditions]
Apparatus: Waters GPC (ALC/GPC 150C)
Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M/S (3 columns)
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140°C
Flow rate: 1.0 ml/min Injection volume: 0.2 ml
[Sample preparation]
The sample was dissolved in ODCB (containing 0.5 mg/mL BHT) at 140° C. for about 1 hour to prepare a sample solution with a concentration of 1 mg/mL.
[Conversion from retention capacity to molecular weight]
Conversion from the retention volume to the molecular weight was carried out using a previously prepared standard polystyrene calibration curve. The standard polystyrene used is the following brand manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve was prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg/mL of BHT) so that each standard polystyrene was 0.5 mg/mL. A cubic equation obtained by approximation by the method of least squares was used for the calibration curve. The following numerical values were used for the viscosity formula [η]=K×Mα used for conversion to molecular weight.
PS: K=1.38×10 ⁻⁴ , α=0.7
PE: K=3.92×10 ⁻⁴ , α=0.733
PP: K=1.03×10 ⁻⁴ , α=0.78

(6) Melt tension (MT)
It was determined by measuring the stress when the molten ethylene polymer was stretched at a constant speed, and was measured under the following conditions.
[Measurement condition]
Model used: Capilograph 1B manufactured by Toyo Seiki Seisakusho
Nozzle diameter: 2.095mm
Nozzle length: 8.0mm
Inflow angle: 180° (flat)
Extrusion speed: 15mm/min
Take-up speed: 6.5m/min
Measurement temperature: 190°C

(7) Tensile impact strength (TIS)
[Method for preparing tensile impact strength test sample]
The sample is placed in a heat press mold with a thickness of 1 mm, preheated for 5 minutes in a heat press with a surface temperature of 230° C., and then pressurized and depressurized repeatedly to melt the sample and deaerate the residual gas in the sample. Then, the pressure was further increased to 4.9 MPa and held for 5 minutes. After that, it was gradually cooled at a rate of 10° C./min under a pressure of 4.9 MPa, and when the temperature dropped to around room temperature, the molded plate was taken out from the mold. The resulting molded plate was conditioned for 48 hours or longer in an environment of 23±2° C. temperature and 50±5° C. humidity. A test piece having the shape of ASTM D1822 Type-S was punched out from the press plate after conditioning, and used as a tensile impact strength test sample.
[Tensile impact strength test conditions (TIS)]
Using the above test piece, the tensile impact strength was measured according to JIS K 7160-1996 B method. The only difference from JIS K 7160-1996 is the shape of the test piece.
As for other measurement conditions, etc., the test was carried out by a method according to JIS K 7160-1996.

(8) Environmental stress crack resistance (FNCT)
A full circumference notch creep test (FNCT) was performed according to ISO 16770.
For the sample, a 6 mm × 6 mm × 11 mm prism with a notch of 1 mm around the entire circumference with a razor blade was prepared, and a test piece having a cross section of 4 mm × 4 mm was prepared and treated with pure water at 80 ° C. Inside, a tensile stress equivalent to 3.7 MPa was applied to the test piece, and the time required for the test piece to break was measured and used as the FNCT breaking time.

(9) Viscoelasticity Viscoelasticity was measured under the following conditions using MCR302 manufactured by Anton Paar.
[Viscoelasticity measurement conditions]
- Test piece: A pressed sheet with a thickness of 1 mm was prepared by pressing at a pressing temperature of 180°C, cut into an appropriate size, and measured.
・Using jig: 25φ parallel plate ・Measurement temperature: 170℃
・Distortion: 1 to 10%
・Frequency: 100 to 0.01rad/sec

2. Preparation of Component (A) and Component (B) Bis(n-butylcyclopentadienyl)zirconium dichloride (hereinafter referred to as metallocene A1) was obtained from Fujifilm Wako Pure Chemical Industries, Ltd.

[Synthesis Example 1]
Synthesis of racemic-dimethylsilylenebis{(2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl)}zirconium dichloride (hereafter metallocene B1):
Metallocene B1 is a compound represented by the formula (2). A ligand was synthesized according to the procedure described in Synthesis Example 1 of JP-A-2012-149160, and zirconium tetrachloride (13 mmol) instead of hafnium tetrachloride (13 mmol) was used for complexation, but the same procedure was performed. A complex was synthesized by manipulation to obtain metallocene B1.

[Synthesis Example 2]
Synthesis of racemic-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride (hereafter metallocene B2):
Metallocene B2 is described in Organometallics, 1994, vol. 13, pp. 954-963.

3. Preparation of catalyst and production of ethylene polymer [Example 1]
(1) Preparation of Solid Catalyst As component (D), 86 ml of toluene was added to 3.5 g of silica gel obtained by calcining uncalcined sylopol 2212 of Grace Co. at 400° C. for 7 hours, and the mixture was slurried at room temperature.
Separately from the above step, 28 mg (69 μmol) of metallocene A1 as component (A) and 15 mg (18 μmol) of metallocene B1 as component (B) were weighed in a container, and 18 ml of toluene and methylaluminoxane toluene solution as component (C) were added. 9.5 ml (29 mmol as aluminum) of MAO concentration 20 wt% (purchased from Albemarle) was added and stirred at room temperature for 1 hour.
This solution was added to the toluene slurry of silica gel as the component (D) and stirred at 40° C. for 1 hour. The total amount of metallocene A1 and metallocene B1 per 1 g of silica gel is 25 μmol/g. After stopping the stirring, the supernatant left standing was removed, and 200 ml of hexane was added to remove the supernatant, which was repeated twice to wash the catalyst. The solvent was distilled off under reduced pressure to obtain a dry solid catalyst (MIX-1).

(2) Ethylene/1-hexene Copolymerization In a 2-liter stainless steel autoclave equipped with stirring and temperature control, under nitrogen, 1.0 mmol of triisobutylaluminum, 1 ml of 1-hexene, and reactor fouling were added. As an inhibitor, 1 ml of Statsafe 6000, a product name of Innospec, diluted with hexane to 2 vol %, and 800 ml of purified isobutane were added, and the temperature was raised to 70° C. while stirring. After introducing 38 ml (1.7 mmol) of hydrogen, ethylene was introduced until the partial pressure reached 1 MPa. At this time, the molar ratio of hydrogen and ethylene in the gas phase inside the autoclave was 0.24 mol %. After that, 45 mg of the above solid catalyst (MIX-1) was pressurized with nitrogen gas, and polymerization was carried out for 90 minutes. During the polymerization, the temperature was controlled so as to maintain 70° C., ethylene was continuously supplied so that the total pressure was constant, and 1-hexene and hydrogen were supplied in proportion to the ethylene consumption rate. .
The molar ratio of hydrogen to ethylene in the autoclave gas phase at the end of polymerization was 0.15 mol %. Further, 1-hexene added during polymerization was 1.5 ml.
As a result of polymerization, 186 g of a free-flowing ethylene polymer was obtained. Table 1 summarizes the polymerization results and physical property measurement results. Moreover, the GPC chart of the obtained ethylene-based polymer is shown in FIG.

[Comparative Example 1]
(1) Preparation of solid catalyst In the preparation of the solid catalyst of Example 1, the amount of metallocene A1 was changed from 28 mg (69 μmol) to 21 mg (53 μmol), and the amount of metallocene B1 was changed from 15 mg (18 μmol) to 22 mg (35 μmol). A solid catalyst (MIX-2) was produced in the same manner as in Example 1, except that
(2) Ethylene/1-hexene copolymerization In the ethylene/1-hexene copolymerization of Example 1, 53 mg of the solid catalyst (MIX-2) was used as the solid catalyst instead of 45 mg of the solid catalyst (MIX-1). Polymerization was carried out in the same manner as in Example 1, except that the polymerization time was changed from 90 minutes to 60 minutes. The molar ratio of hydrogen to ethylene in the gas phase inside the autoclave before the start of polymerization was 0.19 mol %, and the molar ratio of hydrogen to ethylene in the gas phase inside the autoclave at the end of polymerization was 0.11 mol %. Further, 1 ml of hexene was added during the polymerization.
As a result of the polymerization, 130 g of a free-flowing ethylene polymer was obtained. Table 1 summarizes the polymerization results and physical property measurement results. Moreover, the GPC chart of the obtained ethylene-based polymer is shown in FIG.

[Comparative Example 2]
Table 1 summarizes the results of measuring the physical properties of Novatec HD HB431 (manufactured by Nippon Polyethylene Co., Ltd.).

[Comparative Example 3]
Table 1 summarizes the results of measuring physical properties of Evolue H SP6505 (manufactured by Prime Polymer Co., Ltd., a polymer obtained by a slurry method multi-stage polymerization process using a metallocene catalyst).

4. Discussion Comparing the melt tension (MT), tensile impact strength (TIS) and FNCT rupture time of Example 1 and Comparative Examples 1 to 3 shown in Table 1, the ethylene polymer of Example 1 is all good. and was shown to be an ethylene polymer with an excellent balance of moldability, strength and durability. The ethylene-based polymer of Example 1, in particular, had a remarkably long FNCT breaking time, and was greatly improved in durability compared to conventional ethylene-based polymers.
The ethylene-based polymer of Comparative Example 1 had a high MT, but was inferior in TIS and FNCT to those of Examples.
The ethylene-based polymer of Comparative Example 2 was inferior to those of Examples in all of MT, TIS and FNCT.
The ethylene-based polymer of Comparative Example 3 had a high TIS, but inferior MT and FNCT compared to those of Examples.

Further, the ethylene polymer of Example 1 and the ethylene polymer of Comparative Example 1 have almost the same HLMFR as shown in Table 1, but the ethylene polymer of Example 1 and Comparative Example 1 shown in FIG. As is clear from the GPC chart, the ethylene polymer of Example 1 had a slightly larger amount of high molecular weight components and a slightly smaller amount of low molecular weight components than the ethylene polymer of Comparative Example 1. As described above, the ethylene-based polymer of Example 1 contains a sufficient amount of high-molecular-weight components even if the HLMFR is combined to improve the fluidity, so the FNCT is improved more than that of Comparative Example 1. I think. Furthermore, metallocene B2 used in Comparative Example 1 is more likely to copolymerize macromonomers with high molecular weight than metallocene B1 used in Example 1. Therefore, even if the weight average molecular weight is the same, the viscosity tends to increase, and when comparing ethylene polymers with HLMFR adjusted to the desired range, it is presumed that the low molecular weight component increased and the strength decreased. .

[Reference example 1]
(1) Preparation of solid catalyst using only metallocene B1 Preparation of the solid catalyst of Example 1 was performed in the same manner as in Example 1, except that metallocene A1 was not used and the amount of metallocene B1 was changed to 74 mg (88 μmol). to obtain a solid catalyst (SC-1).
(2) Ethylene/1-hexene Copolymerization In a 2-liter stainless steel autoclave equipped with stirring and temperature control, under nitrogen, 1.0 mmol of triisobutylaluminum, 6 ml of 1-hexene, and reactor fouling were added. As an inhibitor, 1 ml of Statsafe 6000, a product name of Innospec, diluted with hexane to 2 vol %, and 800 ml of purified isobutane were added, and the temperature was raised to 70° C. while stirring. After introducing 25 ml (1.1 mmol) of hydrogen, ethylene was introduced until the partial pressure reached 1 MPa. At this time, the molar ratio of hydrogen and ethylene in the gas phase inside the autoclave was 0.14 mol %. After that, 25 mg of the solid catalyst (SC-1) was pressurized with nitrogen gas, and polymerization was carried out for 60 minutes. During the polymerization, the temperature was controlled so as to maintain 70° C., ethylene was continuously supplied so that the total pressure was constant, and 1-hexene and hydrogen were supplied in proportion to the ethylene consumption rate. .
The molar ratio of hydrogen to ethylene in the autoclave gas phase at the end of polymerization was 0.16 mol %. Also, 7 ml of 1-hexene was added during the polymerization.
As a result of the polymerization, 176 g of a free-flowing ethylene polymer was obtained. Table 2 summarizes the polymerization results and physical property measurement results. Moreover, the GPC chart of the obtained ethylene-based polymer is shown in FIG.

(3) Production of low molecular weight polyethylene for blending In a 290 L liquid-filled loop reactor, dehydrated purified isobutane, triisobutyl aluminum, and Ziegler-Natta prepolymerization catalyst described in Comparative Example B1 of JP-A-2012-72229. A low molecular weight polyethylene for blending with an MFR of 46 g/10 min was produced by continuously feeding , hydrogen and ethylene to polymerize ethylene at 80°C.
(4) Preparation of blended product In a 300 ml Erlenmeyer flask, 180 ml of xylene, 1.6 g of the ethylene polymer obtained in (2) above, 2.4 g of low molecular weight polyethylene obtained in (3) above and 2,6 - 1.0-1.5 g of di-t-butylhydroxytoluene (BTH) was added. This was stirred at 125 to 130° C. for 45 to 90 minutes to obtain a xylene solution in which the ethylene polymer and low molecular weight polyethylene were completely dissolved in xylene. The xylene solution was poured into 500 mL of ethanol to precipitate an ethylene polymer and low molecular weight polyethylene. The ethylene-based polymer and low-molecular-weight polyethylene recovered by filtration were vacuum-dried at 80° C. to obtain a blended product of the ethylene-based polymer and low-molecular-weight polyethylene. The viscoelasticity of the blend was measured and the results are shown in FIG.

[Reference example 2]
(1) Preparation of solid catalyst using only metallocene B2 The solid catalyst of Comparative Example 1 was prepared in the same manner as in Comparative Example 1, except that metallocene A1 was not used and the amount of metallocene B2 was changed to 55 mg (88 μmol). As a result, a solid catalyst (SC-2) was obtained.
(2) Ethylene/1-hexene copolymerization In the ethylene/1-hexene copolymerization of Reference Example 1, instead of 25 mg of the solid catalyst (SC-1), 33 mg of the solid catalyst (SC-2) was used. Polymerization was carried out analogously to Example 1. The molar ratio of hydrogen to ethylene in the gas phase in the autoclave was 0.16 mol % before the start of polymerization and 0.21 mol % at the end of polymerization. 7 ml of 1-hexene was added during the polymerization.
As a result of the polymerization, 176 g of a free-flowing ethylene polymer was obtained. Table 2 summarizes the polymerization results and physical property measurement results. Moreover, the GPC chart of the obtained ethylene-based polymer is shown in FIG.

[Reference example 3]
(1) Preparation of solid catalyst using only metallocene B2 The solid catalyst of Comparative Example 1 was prepared in the same manner as in Comparative Example 1, except that metallocene A1 was not used and the amount of metallocene B2 was changed to 55 mg (88 μmol). As a result, a solid catalyst (SC-2) was obtained.
(2) Ethylene/1-hexene copolymerization In the ethylene/1-hexene copolymerization of Reference Example 1, 33 mg of the solid catalyst (SC-2) was used instead of 25 mg of the solid catalyst (SC-1), and hydrogen was introduced. Polymerization was carried out in the same manner as in Reference Example 1, except that the amount was changed from 25 ml (1.1 mmol) to 75 ml (3.3 mmol). The molar ratio of hydrogen to ethylene in the gas phase in the autoclave was 0.47 mol % before the start of polymerization and 0.42 mol % at the end of polymerization. 6 ml of 1-hexene was added during the polymerization.
As a result of the polymerization, 146 g of a free-flowing ethylene polymer was obtained. Table 2 summarizes the polymerization results and physical property measurement results. Moreover, the GPC chart of the obtained ethylene-based polymer is shown in FIG.

(3) Production of low-molecular-weight polyethylene for blending A low-molecular-weight polyethylene for blending was produced in the same manner as in Reference Example 1 (3).
(4) Preparation of blended product In the preparation of the blended product of Reference Example 1, the ethylene-based polymer obtained in (2) of Reference Example 3 was replaced with the ethylene-based polymer obtained in (2) of Reference Example 1. A blended product was obtained in the same manner as in (4) of Reference Example 1, except that coalescence was used. The viscoelasticity of the blend was measured and the results are shown in FIG.

In Reference Examples 1 and 2, ethylene polymers were produced under the same polymerization conditions using only metallocene B1 or metallocene B2 as the transition metal compound. As shown in FIG. 2, the molecular weight peaks of the ethylene-based polymers of Reference Example 1 and Reference Example 2 are almost the same, and the ethylene-based polymer of Reference Example 2 has a lower molecular weight component. , as shown in Table 2, the HLMFR of the ethylene-based polymer of Reference Example 2 is smaller than that of the polymer of Reference Example 1. This suggests that the ethylene-based polymer of Reference Example 2 contains more high-viscosity polymer.
In Reference Examples 1 and 3, only metallocene B1 or metallocene B2 was used as the transition metal compound, and the amount of hydrogen introduced was adjusted so that the HLMFR was approximately the same to produce ethylene polymers.
As shown in Table 2, the ethylene polymer of Reference Example 1 and the ethylene polymer of Reference Example 3 have almost the same HLMFR, but the ethylene polymers of Reference Examples 1 and 3 shown in FIG. As is clear from the GPC chart, the ethylene-based polymer of Reference Example 3 contained more low-molecular-weight components than the ethylene-based polymer of Reference Example 1. Further, as is clear from the viscoelasticity results of the blends of Reference Examples 1 and 3 shown in FIG. 3, the viscosity of the blend of Reference Example 1 did not increase at low frequencies.
It is considered that the difference in molecular weight distribution and viscoelasticity of the polymers obtained in Reference Examples 1 and 3 is due to the difference in the amount of the long-term relaxation component. That is, in Reference Example 1 using metallocene B1, the amount of the long-term relaxation component in the obtained ethylene polymer is less than in Reference Example 3 using metallocene B2, and the blend product of Reference Example 1 , it is thought that the viscosity at low frequencies did not increase. This long relaxation component is believed to be derived from long chain branching. In a polymer produced by using metallocene B1 or metallocene B2 alone as a catalytically active component for polymerization, the amount of long chain branching is smaller when metallocene B1 is used than when metallocene B2 is used. That is, it shows that the properties as a catalyst (the amount of long-chain branching) are different between metallocene B1 and metallocene B2.

INDUSTRIAL APPLICABILITY The olefin polymerization catalyst of the present invention can be used to produce an ethylene polymer having an excellent balance of moldability, strength and durability.
The ethylene polymer of the present invention, which is excellent in the balance of moldability, strength and durability, can be widely used as a plastic molding material.

Claims (8)

A catalyst for olefin polymerization comprising the following components (A), (B), (C) and (D).
Component (A): metallocene compound represented by the following general formula (1) Component (B): metallocene compound represented by the following general formula (2) Component (C): the above component (A) and the above component (B) is a cationic compound component (D): microparticle carrier

[In formula (1),
^M1 represents a titanium atom, a zirconium atom or a hafnium atom.
X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom. It represents a hydrocarbon group or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; , an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and an alkyl group having 1 carbon atom Alkyl groups having 1 to 6 carbon atoms substituted with trialkylsilyl groups of up to 3, substituted silyl groups substituted with hydrocarbon groups having 1 to 6 carbon atoms, aryl groups having 6 to 18 carbon atoms, substituted with halogen atoms represents an aryl group having 6 to 18 carbon atoms, or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. ]

[In formula (2),
^M2 represents a titanium atom, a zirconium atom or a hafnium atom.
X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom having 3 to 20 carbon atoms. It represents a hydrocarbon group or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms.
Y represents a carbon atom, silicon atom or germanium atom.
R ¹¹ and R ²¹ each independently represent an optionally substituted furyl group or an optionally substituted thienyl group.
^R12 , ^R13 , ^R14 , ^R15 , ^R16 , R17, ^{R18 , R19} , R22, ^R23 , ^R24 , ^R25 , ^R26 , ^R27 , ^R28 and ^{R29 are} each independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom C1-6 alkyl group substituted with C1-3 trialkylsilyl group, substituted silyl group substituted with C1-6 hydrocarbon group, C6-18 aryl group, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. Adjacent groups among R ¹² to R ¹⁹ and R ²² to R ²⁹ may combine to form a 6- to 7-membered ring, and the 6- to 7-membered ring may contain an unsaturated bond.
R ³¹ and R ³² each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, or an alkyl group. an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group having 1 to 3 carbon atoms, a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, It represents an aryl group having 6 to 18 carbon atoms substituted with a halogen atom or a heterocyclic group constituting a 5- or 6-membered ring which may have a substituent. R ³¹ and R ³² may contain Y to form a 4- to 7-membered ring, and when at least one of R ³¹ and R ³² has a cyclic structure, it is composed of R ³¹ , R ³² and Y The 4- to 7-membered ring may form a condensed ring in which R ³¹ and R ³² share some of the constituent atoms of the cyclic structure. ] The olefin polymerization catalyst according to claim 1, wherein ^R11 and ^R21 in the general formula (2) in the component (B) are groups represented by the following general formula (3).

[In the formula (3), Z is an oxygen atom or a sulfur atom,
R ³³ and R ³⁴ are each independently substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a halogen atom. an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, and a trialkylsilyl group having 1 to 3 carbon atoms substituted for the alkyl group. an alkyl group having 1 to 3 carbon atoms, or a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, and R ³³ and R ³⁴ may combine with each other to form a 6- to 7-membered ring. Alternatively, the 6- to 7-membered ring may contain an unsaturated bond. ] In the general formula (1) for the component (A), R ¹ and R ⁶ are each independently an alkyl group having 3 to 6 carbon atoms, and R ³ and R ⁸ are each independently hydrogen. 3. The olefin polymerization catalyst according to claim 1, wherein the catalyst is an alkyl group having 1 to 6 carbon atoms, and R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are hydrogen atoms. 4. The olefin polymerization catalyst according to claim 3, wherein ^R3 and ^R8 in said general formula (1) in said component (A) are each independently a hydrogen atom or a methyl group. 4. The olefin polymerization catalyst according to claim 3, wherein ^R3 and ^R8 in said general formula (1) in said component (A) are hydrogen atoms. 3. The olefin polymerization catalyst according to claim 1 or 2, wherein said component (C) is methylaluminoxane. A method for producing an ethylene-based polymer, comprising polymerizing ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms in the presence of the olefin polymerization catalyst according to claim 1 or 2. 8. The method for producing an ethylene-based polymer according to claim 7, which is carried out by a slurry polymerization method.

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