JP2016098344A - Catalyst for olefin polymerization and method for olefin polymerization using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for olefin polymerization that makes it possible to produce an olefin polymer having excellent moldability and mechanical strength as well as excellent particle properties with high polymerization activity, and a polymerization method using the catalyst.SOLUTION: A catalyst for olefin polymerization is prepared which comprises a component (A) comprising a crosslinked metallocene compound having a specific chemical structure, a component (B) comprising a crosslinked metallocene compound having a specific chemical structure, and a component (C) comprising a specific compound, and the olefin polymerization catalyst is used to produce an olefin polymer.SELECTED DRAWING: None

Description

  The present invention relates to an olefin polymerization catalyst and an olefin polymerization method using the same, and more specifically, an olefin polymer having excellent molding processability and mechanical strength and excellent particle properties is produced with high polymerization activity. And a polymerization method using the catalyst.

Olefin polymers are molded by various molding methods and used for various purposes.
For example, as a film or sheet used for packaging foodstuffs, liquids, daily commodities, etc., an extruded product of an ethylene polymer is used.

  The properties required for olefin polymers differ depending on the molding method and application. For example, when performing T-die molding, stable molding is possible even at high speed (high-speed film forming processability). It is required to have a processing performance such as small. In addition, when performing inflation molding, it is required to have processing performance such as excellent bubble stability.

Ethylene polymers obtained with Ziegler catalysts and metallocene catalysts have a linear molecular structure and excellent mechanical strength, but have a low melt tension, compared to low-density polyethylene (LDPE) produced by high-pressure radical polymerization. However, there is a problem that molding processability is inferior.
In order to solve these problems, [1] a method of blending an LDPE and an ethylene polymer obtained using a Ziegler catalyst or a metallocene catalyst (Patent Document 1), [2] a method of widening the molecular weight distribution by multistage polymerization ( Patent Document 2), [3] A method for producing a long-chain branched ethylene polymer using a chromium catalyst, [4] A long-chain branched ethylene polymer produced using a specific metallocene catalyst Method (Patent Document 3), [5] A method of producing a long-chain branched ethylene polymer by copolymerizing a macromonomer using a specific metallocene catalyst (Patent Document 4), [6] Using a specific metallocene catalyst A method of producing a long-chain branched ethylene polymer by copolymerizing ethylene and diene (Patent Documents 5 and 6) has been proposed, but sufficient molding processing with a significant cost increase is proposed. Gained Non, such as a gel occurs during molding, it can be said that problems in industrial practice are left.

  In recent years, methods for broadening the molecular weight distribution using two or more kinds of metallocene compounds have been reported (Patent Documents 7 and 8), but it is still difficult to say that the melt tension is sufficient.

WO99 / 046325 pamphlet JP-A-2-053811 JP-A-4-213306 JP-A-8-502303 JP-T-1-501633 JP-T-4-506372 Special Table 2002-515521 WO2006 / 045761 pamphlet

  The present invention has been made in view of the prior art as described above, and is capable of producing an olefin polymer excellent in molding processability and mechanical strength and having excellent particle properties with high polymerization activity. It is an object of the present invention to provide a novel olefin polymerization catalyst and a polymerization method using the catalyst.

As a result of diligent research in view of the above situation, the present inventors have made it possible to efficiently produce an olefin polymer having excellent molding processability by allowing a cross-linked metallocene compound having two specific structures to coexist in the same polymerization system. The inventors have found a catalyst for olefin polymerization and a polymerization method that can be produced well, and have completed the present invention.
That is, the catalyst for olefin polymerization of the present invention is characterized by comprising the component (A), the component (B), and the component (C).

Component (A) : A bridged metallocene compound represented by the following general formula (I).

〔一般式（Ｉ）中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は１価の基であり、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基からばれる基であり、これら基は互いに同一でも異なっていてもよいが、全てが同時に水素原子ではなく、これら基のうち隣接する基は互いに結合して脂肪族環を形成していてもよく、Ｑ¹は２価の基であり、炭素数１以上２０以下の炭化水素基、ハロゲン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、Ｘは１価の基であり、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基およびリン含有基から選ばれる基であり、Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子である。〕

[In the general formula (I), R ¹ , R ² , R ³ and R ⁴ are monovalent groups, a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, Sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and groups containing tin-containing groups, and these groups may be the same or different from each other, but they are not all hydrogen atoms at the same time. Adjacent groups may be bonded to each other to form an aliphatic ring, Q ¹ is a divalent group, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group X is a monovalent group, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , Nitrogen-containing groups and phosphorus A group selected from organic groups, M is a titanium atom, a zirconium atom or a hafnium atom. ]

Component (B) : A bridged metallocene compound represented by the following general formula (II).

〔一般式（II）中、Ｒ⁵、Ｒ⁶、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、およびＲ¹²は１価の基であり、水素原子、炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、それぞれ同一でも異なっていてもよく、これら基のうち隣接する基は互いに結合して環を形成してもよく、Ｒ⁷およびＲ¹¹は、炭素数３以上８以下の二価の飽和炭化水素基であり、互いに同一でも異なっていてもよく、ｎは、それぞれ０またはＲ⁷およびＲ¹¹の炭素数の２倍以下の整数であり、ｎが２以上の整数の場合は複数のＲ⁷およびＲ¹¹は、互いに同一でも異なっていてもよく、Ｑ²は２価の基であり、炭素数１以上２０以下の炭化水素基、ハロゲン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる基であり、Ｘは１価の基であり、それぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基およびリン含有基から選択された基であり、Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子である。〕

[In the general formula (II), R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹² are monovalent groups, a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, nitrogen Group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group and tin-containing group, each of which may be the same or different. R ⁷ and R ¹¹ may be a divalent saturated hydrocarbon group having 3 to 8 carbon atoms, and may be the same or different from each other, and n is 0 Or, when R is an integer not more than twice the carbon number of R ⁷ and R ¹¹ and n is an integer of 2 or more, the plurality of R ⁷ and R ¹¹ may be the same or different, and Q ² is divalent A hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, X is a monovalent group, each independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen A group selected from a containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group, and M is a titanium atom, a zirconium atom or a hafnium atom. ]

Component (C) ; (c-1) an organometallic compound represented by the following general formula (III), (IV) or (V), (c-2) an organoaluminum oxy compound, and (c-3) component ( A) at least one compound selected from the group consisting of compounds that react with component (B) to form ion pairs.
R ^a _m Al (OR ^b ) _n H _p X _q (III)
[In the general formula (III), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a AlR ^a ₄ (IV) [In the general formula (IV), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (V) [In the general formula (V), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, and may be the same or different from each other. even better, M ^b, Mg, selected from Zn and Cd, X is a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]

  The catalyst for olefin polymerization according to the present invention may further contain a solid carrier (S). Examples of such a catalyst include a solid carrier (S), the component (C) and the component (A). A catalyst for olefin polymerization comprising a solid catalyst component (K1) formed, a solid support (S), the component (C) and a solid catalyst component (K2) formed from the component (B), There is an olefin polymerization catalyst comprising a support (S), the above-described component (A), component (B) and solid catalyst component (K3) formed from component (C).

In the present invention, in the general formula (I), at least one of R ¹ , R ² , R ³ and R ⁴ is preferably a hydrocarbon group. In the general formula (II), R ⁷ and R ¹¹ preferably has 4 carbon atoms,
The component (C) is preferably an organoaluminum oxy compound, and the solid support (S) is also preferably a porous oxide.

  An ethylene polymer can be produced by polymerizing ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst.

  According to the present invention, an efficient method for producing an ethylene-based polymer excellent in moldability is provided.

  Hereinafter, the olefin polymerization catalyst according to the present invention and the polymerization method using the catalyst will be specifically described. In the present invention, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers. In some cases.

First, each component used in the olefin polymerization catalyst of the present invention will be described.
The bridged metallocene compound of component (A) used in the present invention is a group 4 metallocene compound represented by the following general formula (I). The metallocene compound of Group 4 of the periodic table represented by the following general formula (I) will be described in detail.

一般式（I）中、Ｍは周期表第４族遷移金属原子を示し、具体的にはチタン、ジルコニウム、ハフニウムであり、好ましくはジルコニウムである。

In the general formula (I), M represents a Group 4 transition metal atom in the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium.

R ¹ , R ² , R ³ and R ⁴ are monovalent groups, hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, These are groups selected from a silicon-containing group, a germanium-containing group and a tin-containing group, and these groups may be the same or different from each other, but they are not all hydrogen atoms at the same time. Further, R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form an aliphatic ring.

  The monovalent hydrocarbon group is preferably an alkyl group composed of carbon and hydrogen having 1 to 20 carbon atoms, a cycloalkyl group composed of carbon and hydrogen having 3 to 20 carbon atoms, and carbon having 2 to 20 carbon atoms. An alkenyl group consisting of carbon and hydrogen, an aryl group consisting of carbon and hydrogen having 6 to 20 carbon atoms, or an arylalkyl group consisting of carbon and hydrogen having 7 to 20 carbon atoms. Examples of the alkyl group composed of carbon and hydrogen having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl. Group, n-pentyl group, neopentyl group, n-hexyl group, n-octyl group, nonyl group, dodecyl group, eicosyl group and the like. Examples of the cycloalkyl group comprising 3 to 20 carbon atoms and hydrogen include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like. Examples of the alkenyl group consisting of carbon having 2 to 20 carbon atoms and hydrogen include a vinyl group, a propenyl group, and a cyclohexenyl group. Examples of the aryl group consisting of carbon and hydrogen having 6 to 20 carbon atoms include phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, Examples thereof include phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Examples of the arylalkyl group composed of carbon having 7 to 20 carbon atoms and hydrogen include benzyl, phenylethyl, phenylpropyl and the like.

  Examples of the monovalent halogen-containing group include groups in which one or more of halogen atoms and one or more hydrogen atoms in the hydrocarbon group are substituted with an appropriate halogen atom, such as a trifluoromethyl group.

  Examples of the monovalent oxygen-containing group include a methoxy group and an ethoxy group. Examples of the monovalent sulfur-containing group include a thiol group and a sulfonic acid group. Examples of the monovalent nitrogen-containing group include dimethylamino. Groups and the like, and the phosphorus-containing group includes a phenylphosphine group. Examples of the monovalent boron-containing group include a boranediyl group, a boranetriyl group, and a diboranyl group.

  Monovalent silicon-containing groups include silyl, methylsilyl, dimethylsilyl, diisopropylsilyl, methyl-t-butylsilyl, dicyclohexylsilyl, methylcyclohexylsilyl, methylphenylsilyl, diphenylsilyl, methylnaphthylsilyl, dinaphthylsilyl, cyclodimethylene Examples include silyl, cyclotrimethylene silyl, cyclotetramethylene silyl, cyclopentamethylene silyl, cyclohexamethylene silyl, cycloheptamethylene silyl and the like, and the monovalent germanium-containing group and the monovalent tin-containing group include the above silicon-containing Examples of the group include a group obtained by converting silicon into germanium or tin.

Examples of the case where adjacent groups of R ¹ , R ² , R ³ and R ⁴ are bonded to each other to form an aliphatic ring include tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,2,4 -Trimethyltetrahydroindenyl, 4-phenyltetrahydroindenyl, 2-methyl-4-phenyltetrahydroindenyl, R ³ and R ⁴ are cyclically linked by a tetramethylene group, and R ¹ and R ² are cyclic by a tetramethylene group And a substituted cyclopentadienyl group bonded to.

Preferably, R ¹ , R ² , R ³ and R ⁴ are selected from a hydrogen atom, a hydrocarbon group and a halogen-containing group, more preferably at least one of R ^{1 to} R ⁴ is a hydrocarbon group, Preferably, ^three of the substituents of R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, and the remaining one is a hydrocarbon group having 1 to 15 carbon atoms, more preferably R ^1. , R ² , R ³ and R ⁴ are hydrogen atoms, and the remaining one is a hydrocarbon group having 3 to 15 carbon atoms, particularly preferably R ¹ , R ² , R ^3. And three of the substituents of R ⁴ are hydrogen atoms and the remaining one is a hydrocarbon group having 3 to 8 carbon atoms, and very preferably the substituents of R ¹ , R ² , R ³ and R ⁴ wherein R ¹ and R ⁴ are hydrogen atom of, R ² and R ³ either the 3 or more carbon atoms 8 The other is a hydrocarbon group having lower is a hydrogen atom.

Q ¹ is a divalent group that binds two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group, an alkylidene group, a halogen-containing group, a silicon-containing group, It is a group selected from a germanium-containing group and a tin-containing group.

  Specific examples of the divalent alkylene group having 1 to 20 carbon atoms, substituted alkylene group, and alkylidene group include alkylene groups such as methylene, ethylene, propylene, butylene, isopropylidene, diethylmethylene, dipropylmethylene, diisopropylmethylene, Dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methyl Substituted alkylene groups such as ethylene, 1,2-dimethylethylene, 1-ethyl-2-methylethylene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cycl And cycloalkylidene groups such as hexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene and dihydroindanilidene, and alkylidene groups such as ethylidene, propylidene and butylidene. .

  Divalent silicon-containing groups include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolyl. Examples include silylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and divalent germanium-containing groups. Examples of the tin-containing group include groups obtained by converting silicon into germanium or tin in the silicon-containing group.

  As the divalent halogen-containing group, a group in which one or more hydrogen atoms in the above-mentioned alkylene group, substituted alkylene group, alkylidene group or silicon-containing group are substituted with an appropriate halogen atom is selected. Fluoromethyl) methylene, 4,4,4-trifluorobutylmethylmethylene, bis (trifluoromethyl) silylene, 4,4,4-trifluorobutylmethylsilylene and the like.

Among these, preferred groups for Q ¹ include alkylene groups having 1 to 20 carbon atoms, substituted alkylene groups, alkylidene groups, halogen-containing alkylene groups, halogen-containing substituted alkylene groups, halogen-containing alkylidene groups, silicon-containing groups, and halogen-containing silicons. A group selected from the containing group, and a particularly preferred group is a silicon-containing group or a halogen-containing silicon-containing group.

X is a monovalent group, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group (for example, a halogen-containing hydrocarbon group), a silicon-containing group, an oxygen-containing group, a sulfur-containing group, or a nitrogen-containing group. A group selected from a group and a phosphorus-containing group, preferably a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, hydrocarbon group, halogen-containing group (for example, halogen-containing hydrocarbon group), silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group and phosphorus. Examples of the containing group include the same groups as those exemplified as R ¹ , R ² , R ³ and R ⁴ above.

Although the metallocene compound represented by the general formula (I) is not particularly limited, specific examples thereof include, for example, ethylene (cyclopentadienyl) (2-methylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl). ) (3-methylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2-ethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride , Ethylene (cyclopentadienyl) (2-n-propylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3- -Propylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-pentylcyclopentadienyl) zirconium Dichloride, ethylene (cyclopentadienyl) (3-n-hexylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) ) (3-n-decylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,3-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,4-dimethylcycline) Pentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,5-dimethyl-cyclopentadienyl) zirconium dichloride,
Ethylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3,4-di-n-propylcyclopentadienyl) zirconium dichloride, ethylene (cyclopenta Dienyl) (3,4-di-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,3-ethylmethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,4-Ethylmethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-methyl, 4 -N-propylcyclopen Dienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-methyl, 4-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,3,4-trimethylcyclopentadienyl) Zirconium dichloride, ethylene (cyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,5-dimethyl, 3-n-propylcyclopentadienyl) Zirconium dichloride, ethylene (cyclopentadienyl) (2,5-dimethyl, 3-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, ethylene Cyclopentadienyl) (2,5-dimethyl, 3,4-di-n-propylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,5-dimethyl, 3,4-di-n A bridged asymmetric metallocene compound having an alkylene group at the crosslinking site, such as -butylcyclopentadienyl) zirconium dichloride;
Isopropylidene (cyclopentadienyl) (2-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2 -Ethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2-n-propylcyclopentadienyl) zirconium Dichloride, isopropylidene (cyclopentadienyl) (2-n-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-propylcyclopentadienyl) Zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-pentylcyclopentadienyl) zirconium dichloride, isopropylidene ( Cyclopentadienyl) (3-n-hexylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) ( 3-n-decylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) ) (2,4-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,5-dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4- Dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-di-n-propylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-di-) n-butylcyclopentadienyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (2,3-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,4-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclo Pentadienyl) (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methyl, 4-n-propylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopenta Dienyl) (3-methyl, 4-n-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3,4-trimethylcyclopentadienyl) zirconium dichloride, isopropyl Pyridene (cyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,5-dimethyl, 3-n-propylcyclopentadienyl) zirconium dichloride Isopropylidene (cyclopentadienyl) (2,5-dimethyl, 3-n-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (Cyclopentadienyl) (2,5-dimethyl, 3,4-di-n-propylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,5-dimethyl, 3,4-di -N-Butylcyclopentadie Bridged asymmetric metallocene compounds having Le) zirconium dichloride, a substituted alkylene group such as a crosslinking site;
Dimethylsilylene (cyclopentadienyl) (2-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2 -Ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2-n-propylcyclopentadienyl) zirconium Dichloride, dimethylsilylene (cyclopentadienyl) (2-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) Zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-pentylcyclopentadienyl) zirconium dichloride, dimethylsilylene ( Cyclopentadienyl) (3-n-hexylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ( 3-n-decylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ) (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,5-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4- Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-di-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-di-) n-butylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene (cyclopentadienyl) (2,3-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,4-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclo Pentadienyl) (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl, 4-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopenta Dienyl) (3-methyl, 4-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,4-trimethylcyclopentadienyl) zirconium dichloride, dimethyl Silylene (cyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,5-dimethyl, 3-n-propylcyclopentadienyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (2,5-dimethyl, 3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (Cyclopentadienyl) (2,5-dimethyl, 3,4-di-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,5-dimethyl, 3,4-di -N-Butylcyclopentadie Le) zirconium dichloride, and a bridged asymmetric metallocene compounds having a silicon-containing group to the crosslinking sites, such as.

  Other metallocene compounds represented by the general formula (I) include bridged asymmetric metallocenes in which the isopropylidene bridging group of the substituted alkylene group is changed to di-n-butylmethylene bridging group, and dimethylsilylene bridging group of silicon-containing group Type asymmetric metallocenes in which one or more hydrogen atoms in the bridging group are changed to halogen atoms, substituents bonded to the cyclopentadienyl ring And a bridged asymmetric metallocene obtained by changing one or more hydrogen atoms to halogen atoms. Moreover, the metallocene compound etc. whose center metal of the said compound is titanium or hafnium are mentioned.

  Among these metallocene compounds represented by the general formula (I), a crosslinked asymmetric metallocene compound having a silicon-containing group such as a dimethylsilylene group at a crosslinking site is preferable. Among the bridged asymmetric metallocene compounds, dimethylsilylene (cyclopentadiene) is preferable. Enyl) (3-ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-butyl) Cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) ) Zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, trifluoro Methylbutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, trifluoro More preferred is methylbutylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride.

  In the present invention, among the compounds represented by the general formula (I), two or more kinds of metallocene compounds having different chemical structures may be used. Further, optical isomers having the same chemical structure may be used alone, or optical isomer mixtures having the same chemical structure (for example, meso isomer mixture or racemic mixture) may be used.

Such a bridged metallocene compound represented by the general formula (I) can be produced by the method disclosed in International Publication No. 01/27124.
The bridged metallocene compound of component (B) used in the present invention is a group 4 metallocene compound represented by the following general formula (II). The metallocene compound of Group 4 of the periodic table represented by the following general formula (II) will be described in detail.

一般式（II）中、Ｍは、上記一般式（I）中のＭと同様の周期表第４族遷移金属原子が挙げられ、好ましくはジルコニウムである。

In the general formula (II), M may be the same group 4 transition metal atom of the periodic table as M in the general formula (I), and is preferably zirconium.

R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ and R ¹² are monovalent groups, and the same as R ¹ , R ² , R ³ and R ^{4 in} the above general formula (I) Preferably, it is a group selected from a hydrogen atom, a hydrocarbon group and a halogen-containing group.

R ⁷ and R ¹¹ are divalent saturated hydrocarbon groups having 3 to 8 carbon atoms, and examples include trimethylene, tetramethylene, pentamethylene, hexamethylene and the like. R ⁷ and R ¹¹ may be the same or different from each other, preferably a divalent saturated hydrocarbon group having 4 to 6 carbon atoms (for example, tetramethylene, pentamethylene, hexamethylene), particularly preferably carbon A divalent saturated hydrocarbon group of number 4 (for example, tetramethylene).

n is 0 or an integer less than twice the number of carbon atoms of R ⁷ and R ¹¹ , and when n is an integer of 2 or more, the plurality of R ⁷ and R ¹¹ may be the same or different from each other.
Q ² is a divalent group, and examples thereof include those similar to Q ¹ in the general formula (I), preferably an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, an alkylidene group, a halogen-containing alkylene. Group, halogen-containing substituted alkylene group, halogen-containing alkylidene group, silicon-containing group and halogen-containing silicon-containing group, particularly preferably an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, and a silicon-containing group. Or it is a halogen containing silicon.

X is a monovalent group, and the same as X in the general formula (I) can be mentioned, and preferably a halogen atom or a hydrocarbon group.
The metallocene compound represented by the general formula (II) is not particularly limited, but specific examples thereof include, for example, methylene bis (tetrahydroindenyl) zirconium dichloride, ethylene bis (tetrahydroindenyl) zirconium dichloride, ethylene bis (tetrahydroindenyl). ) Zirconium monohydride monochloride, ethylenebis (tetrahydroindenyl) methylzirconium monochloride, ethylenebis (tetrahydroindenyl) zirconium monomethoxide monochloride, ethylenebis (tetrahydroindenyl) zirconium diethoxide, ethylenebis (tetrahydroindene) Nyl) zirconium dimethyl, ethylidenebis (tetrahydroindenyl) zirconium dichloride, ethylidenebis (tetrahydroindenyl) Zirconium dimethyl, ethylenebis (2-methyltetrahydroindenyl) zirconium dichloride, ethylenebis (2-ethyltetrahydroindenyl) zirconium dichloride, ethylenebis (2,4-dimethyltetrahydroindenyl) zirconium dichloride, ethylenebis (4-phenyl) A bridged metallocene compound having an alkylene group at the crosslinking site such as tetrahydroindenyl) zirconium dichloride;
Isopropylidenebis (tetrahydroindenyl) zirconium dichloride, isopropylidenebis [4- (2-methyltetrahydroindenyl)] zirconium dichloride, isopropylidenebis [4- (2,7-dimethyltetrahydroindenyl)] zirconium dichloride, isopropyl A bridged metallocene compound having a substituted alkylene group such as lidenebis [4- (2-phenyltetrahydroindenyl)] zirconium dichloride at the crosslinking site;
Dimethylsilylene bis (tetrahydroindenyl) zirconium dichloride, dimethylsilylene bis (tetrahydroindenyl) zirconium dimethyl, dimethylsilylene bis (2-methyltetrahydroindenyl) zirconium dichloride, dimethylsilylene bis (2,4-dimethyltetrahydroindenyl) zirconium Dichloride, dimethylsilylenebis (2-methyl-4,5-benzo-4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenyltetrahydroindenyl) zirconium dichloride, dimethyl Silylene bis (2-methyl-4,4-dimethyltetrahydro-4-silylidenyl) zirconium dichloride, dimethylsilylene bis [4- (2-phenyltetra Droindenyl)] zirconium dichloride, dimethylsilylenebis [4- (2-tert-butyltetrahydroindenyl)] zirconium dichloride, dimethylsilylenebis [4- (1-phenyl-3-methyltetrahydroindenyl)] zirconium dichloride, dimethylsilylene Bis [4- (2-phenyl-3-methyltetrahydroindenyl)] zirconium dichloride, phenylmethylsilylene bis (tetrahydroindenyl) zirconium dichloride, diphenylsilylene bis (tetrahydroindenyl) zirconium dichloride, tetramethyldisylylene bis (tetrahydro Indenyl) zirconium dichloride, dimethylsilylene bis [1,1 ′-(2- (2-furyl) tetrahydroindenyl)] zirconium dichloride , Dimethylsilylenebis [1,1 ′-(2- (2-furyl) -4-phenyltetrahydroindenyl)] zirconium dichloride, ethylenebis [1,1 ′-(2- (2-furyl) -4,5 And a bridged metallocene compound having a silicon-containing group at the crosslinking site, such as benzo-4,5,6,7-tetrahydroindenyl)] zirconium dichloride.

  Other metallocene compounds represented by the general formula (II) include cross-linked metallocenes in which the isopropylidene cross-linking group of the substituted alkylene group is changed to a di-n-butylmethylene cross-linking group, and dimethylsilylene cross-linking groups of silicon-containing groups. Examples thereof include a bridged metallocene changed to a di-n-butylsilylene bridge group and a bridged metallocene obtained by changing one or more hydrogen atoms in the bridge group to a halogen atom. Moreover, the metallocene compound etc. whose center metal of the said compound is titanium or hafnium are mentioned.

  Of these metallocene compounds represented by the general formula (II), a crosslinked metallocene compound having an alkylene group such as an ethylene group and a silicon-containing group such as a dimethylsilylene group at a crosslinking site is preferable.

  In the present invention, among the compounds represented by the general formula (I), two or more kinds of metallocene compounds having different chemical structures may be used. Further, optical isomers having the same chemical structure may be used alone, or optical isomer mixtures having the same chemical structure (for example, meso isomer mixture or racemic mixture) may be used.

Next, the component (C) will be described in detail.
In the olefin polymerization catalyst according to the present invention, the component (C) used together with the compound represented by the component (A) and the component (B),
(C-1) Organometallic compound represented by the following general formula (III, (IV) or (V): R ^a _m Al (OR ^b ) _n H _p X _q (III)
[In the general formula (III), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different, X represents a halogen atom, and m represents 0 < m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a AlR ^a ₄ (IV)
[In General Formula (IV), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
_{^{R a r M b R b s}} X t ... (V)
[In the general formula (V), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different, and M ^b is selected from Mg, Zn and Cd X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]

It is at least one compound selected from the group consisting of (c-2) an organoaluminum oxy compound and (c-3) a compound that reacts with component (A) and component (B) to form an ion pair.
Among the organometallic compounds (c-1) represented by the general formula (III), (IV) or (V), the organometallic compound represented by the general formula (III) is preferable, and the general formula (III) Specific examples of the organometallic compounds shown include, for example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, dimethylaluminum chloride, Dialkylaluminum halides such as diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride , Alkylaluminum sesquichlorides such as isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide, dimethylaluminum hydride, Diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec- Examples include alkylaluminum hydrides such as heptyl aluminum hydride and di-sec-nonylaluminum hydride, and dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide and diisobutylaluminum ethoxide.

These compounds are used alone or in combination of two or more.
Moreover, as an example of general formula (V), the dialkyl zinc compound etc. which were described in Unexamined-Japanese-Patent No. 2003-171212 etc. are mentioned, It can also use in combination with a phenol compound etc.

As the organoaluminum oxy compound (c-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and an aluminoxane prepared from trimethylaluminum or triisobutylaluminum is particularly preferable.
Such organoaluminum oxy compounds are used singly or in combination of two or more.

  As the compound (c-3) which reacts with the component (A) and the component (B) to form an ion pair, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005 Lewis acids, ionic compounds, borane compounds and carborane compounds, and heteropoly compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. Isopoly compounds and the like can be used.

  In the olefin polymerization catalyst according to the present invention, when an organoaluminum oxy compound such as methylaluminoxane is used in combination as a co-catalyst component, the olefin compound exhibits not only very high polymerization activity but also active hydrogen in the solid support. It is preferable to use the organoaluminum oxy compound (c-2) as the component (C) because a solid carrier component that reacts and contains a promoter component can be easily prepared.

Next, the solid carrier (S) will be described in detail.
The solid carrier (S) that can be used as necessary in the present invention is an inorganic or organic compound, and is a granular or particulate solid.

  Among these, examples of the inorganic compound include porous oxides, inorganic halides, clays, clay minerals, and ion-exchangeable layered compounds. Among these inorganic compounds, porous oxides are preferable.

Examples of the porous oxide include porous oxides having compositions such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , or these compositions Or a mixture of these porous oxides, specifically, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ — Examples thereof include porous oxides having compositions such as V ₂ O ₅ , SiO ₂ —Cr ₂ O _3, and SiO ₂ —TiO ₂ —MgO. Of these, porous oxides mainly composed of SiO ₂ are preferred.

The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO _{3). 2} ), Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 0.2 to 300 μm, preferably 1 to 200 μm, and a specific surface area of 50. ~1200m ² / g, preferably in the range of 100~1000m ² / g, it is desirable that the pore volume is in the range of 0.3~30cm ³ / g. Such a carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, for _{example, MgCl 2, MgBr 2, MnCl} 2, MnBr 2 and the like. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use an inorganic halide dissolved in a solvent such as alcohol and then precipitated into fine particles by a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchange layered compound is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

In addition, as clay, clay mineral, or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ionizable layered compounds include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O, and the like.

Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^{+ and} other metal hydroxide ions Etc. These compounds may be used alone or in combination of two or more. Polymerization obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.), etc., when intercalating these compounds And colloidal inorganic compounds such as SiO ₂ can coexist. Examples of the pillar include an oxide generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specific examples of the organic compound include, for example, (co) polymer or vinyl produced mainly from an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc. Examples thereof include (co) polymers and reactants produced mainly from cyclohexane, styrene and divinylbenzene, and granular or fine particle solids composed of modified products thereof.

  Further, a solid component obtained by insolubilizing the component (C) by a method described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, WO2010 / 55652A1, or the like. Can also be used as a solid support (S).

Next, a method for preparing the olefin polymerization catalyst in the present invention will be described.
The first olefin polymerization catalyst according to the present invention is prepared by adding the component (A), the component (B) and the component (C) in an inert hydrocarbon or a polymerization system using an inert hydrocarbon. it can.

The order of adding each component is arbitrary, but as a preferred order, for example,
i) Method of adding component (C), component (A), and component (B) to the polymerization system in this order
ii) A method in which component (C), component (B), and component (A) are added to the polymerization system in this order.
iii) A method in which a contact product obtained by mixing and contacting component (A) and component (C) is added to the polymerization system, and then component (B) is added to the polymerization system.
iv) A method in which a contact product obtained by mixing and contacting component (B) and component (C) is added to the polymerization system, and then component (A) is added to the polymerization system.
v) A method in which component (C) is added to the polymerization system, and then a contact product obtained by mixing and contacting components (A) and (B) is added to the polymerization system.
vi) A method in which component (C), component (A) and component (B) are added to the polymerization system in this order, and component (C) is added again to the polymerization system.
vii) A method in which component (C), component (B), and component (A) are added to the polymerization system in this order, and component (C) is added to the polymerization system again.
viii) A contact product obtained by mixing and contacting component (A) and component (C) is added to the polymerization system, and then component (B) is added to the polymerization system, and then component (C) is added again to the polymerization system. How to add
ix) A contact product obtained by mixing and contacting the component (B) and the component (C) is added to the polymerization system, and then the component (A) is added to the polymerization system, and then the component (C) is again added to the polymerization system. How to add
x) Component (C) is added to the polymerization system, and then a contact product obtained by mixing and contacting component (A) and component (B) is added to the polymerization system, and then component (C) is added again to the polymerization system. The method of adding etc. is mentioned. Among these, particularly preferable contact order includes the order of i), ii) and v).

  The second olefin polymerization catalyst according to the present invention includes a solid support (S), the solid catalyst component (K1) formed from the component (C) and the component (A), and the solid support (S). The solid catalyst component (K2) formed from the component (C) and the component (B) can be prepared by adding it into an inert hydrocarbon or a polymerization system using an inert hydrocarbon.

Although the contact order of each component is arbitrary, as a preferable method, for example,
xi) The component (C) and the component (S) are contacted, and then the solid catalyst component (K1), the component (C) and the component (S) prepared by contacting the component (A) are contacted, and then the component (B) ) Using the solid catalyst component (K2) prepared by contacting
xii) The solid catalyst component (K1), the component (B) and the component (C) prepared by bringing the component (A) and the component (C) into contact with each other and then contacting with the component (S) are brought into contact with mixing, and then the component Method using solid catalyst component (K2) prepared by contacting with (S)
xiii) The solid catalyst component (K1), the component (C), and the component (S) prepared by bringing the component (C) and the component (S) into contact with each other and then contacting the contact product of the component (A) with the component (C). Using the solid catalyst component (K2) prepared by bringing the catalyst into contact with each other and then bringing the contact product of component (B) and component (C) into contact with each other
xiv) The solid catalyst component (K1), the component (C) and the component (C) prepared by bringing the component (C) and the component (S) into contact, then contacting the component (A), and then contacting the component (C) again. Examples thereof include a method using a solid catalyst component (K2) prepared by contacting S), then contacting component (B), and again contacting component (C). Among these, particularly preferable contact order includes the order of xi) and xiii).

  The third olefin polymerization catalyst (K3) according to the present invention can be prepared by contacting the component (A), the component (B), the component (C) and the solid carrier (S) in an inert hydrocarbon. .

The order of contacting the components is arbitrary, but as a preferred order, for example,
xv) A method in which component (C) is mixed and contacted with component (S), and then component (A) is contacted and then component (B) is contacted.
xvi) A method in which the component (S) is mixed and contacted with the component (S), then the component (B) is contacted, and then the component (A) is contacted.
xvii) a method in which component (C) is mixed and contacted with component (S), and then a contact mixture of component (A) and component (B) is contacted;
xviii) a method in which component (A) and component (B) are mixed and contacted, then contacted with component (C), and subsequently contacted with component (S);
xix) Method in which component (C) is brought into contact with component (S), further contacted with component (C), and then contacted in the order of component (A) and component (B)
xx) Method in which component (C) is brought into contact with component (S), further contacted with component (C), and then contacted in the order of component (B) and component (A)
xxi) Method in which component (C) is contacted with component (S), further contacted with component (C), and then the contact mixture of component (A) and component (B) is contacted
xxii) Method in which component (C) is mixed and contacted with component (S), and then the contact mixture of component (A), component (B) and component (C) is contacted
xxiii) Method in which component (C) is mixed and contacted with component (S), then the contact mixture of component (A) and component (C) is contacted, and further component (B) is contacted
xxiv) Method in which component (C) is mixed and contacted with component (S), then the contact mixture of component (B) and component (C) is contacted, and further component (A) is contacted
xxv) After contacting component (S) with component (C) and further contacting component (C), then contact mixture of component (A) and component (C), component (B) and component (C) Method of contacting in order of contact mixture
xxvi) After contacting component (S) with component (C) and further contacting component (C), the contact mixture of component (B) and component (C), then component (A) and component (C) Method of contacting in order of contact mixture
xxvii) Method in which component (C) is contacted with component (S), and further contacted with component (C), and then the contact mixture of component (A), component (B) and component (C) is contacted
xxviii) A method in which a mixture of component (A) and component (C) and a mixture of component (B) and component (C) are mixed in advance and brought into contact with the contact product of component (S) and component (C)
xxix) A mixture of component (A) and component (C) and a mixture of component (B) and component (C) are mixed in advance, and this is brought into contact with component (S), component (C), and further component (C). The method of making it contact with the contacted thing etc. is mentioned. When a plurality of components (C) are used, the components (C) may be the same or different. Among these, particularly preferable contact order includes the order of xv), xvi), xvii), xxii), xxiii), and xxiv).

  In each method showing the contact order form, the step (P1) including the contact between the component (S) and the component (C), the step (P2) including the contact between the component (S) and the component (A), and the component (S ) And the component (B) in the step (P3) and in the step including the contact of the component (S), the component (A) and the component (B), the component (G) is (g-1) polyalkylene oxide. Block, (g-2) higher aliphatic amide, (g-3) polyalkylene oxide, (g-4) polyalkylene oxide alkyl ether, (g-5) alkyldiethanolamine, and (g-6) polyoxyalkylene alkyl At least one compound selected from amines may coexist. By allowing the component (G) to coexist, fouling during the polymerization reaction can be suppressed, and the particle properties of the resulting polymer are improved. Among the components (G), (g-1), (g-2), (g-3), and (g-4) are preferable.

  Examples of the solvent used for the preparation of the solid catalyst component of the present invention include inert hydrocarbon solvents. Specifically, aliphatic carbonization such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Examples thereof include alicyclic hydrocarbons such as hydrogen, cyclopentane, cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. It is done.

  Due to the contact between the component (C) and the component (S), the component (C) and the component (S) are chemically bonded by the reaction between the reaction site in the component (C) and the reaction site in the component (S), A contact between component (C) and component (S) is formed. The contact time between component (C) and component (S) is usually 0 to 20 hours, preferably 0 to 10 hours, and the contact temperature is usually -50 to 200 ° C, preferably -20 to 120 ° C. . When the initial contact between the component (C) and the component (S) is suddenly performed, the component (S) collapses due to the reaction heat generation or reaction energy, and the morphology of the resulting solid catalyst component deteriorates, and this is used for polymerization. In many cases, continuous operation becomes difficult due to poor polymer morphology. Therefore, the initial contact temperature between the component (C) and the component (S) can be maintained at a low temperature of −20 to 30 ° C. for the purpose of suppressing the reaction exotherm, or the initial contact temperature can be maintained by controlling the reaction exotherm. It is preferable to react at a moderate rate. The same applies to the case where the component (C) and the component (S) are contacted and the component (C) is further contacted. The molar ratio of contact between the component (C) and the component (S) (component (C) / component (S)) can be arbitrarily selected, but the higher the molar ratio, the higher the component (A) and the component (B). Can be increased, and the activity per solid catalyst component can be improved.

As a preferred range, the molar ratio of the component (C) to the component (S) [= molar amount of the component (C) / molar amount of the component (S)] is usually 0.2 to 2.0, particularly preferably 0. .4 to 2.0.
Regarding the contact between the contact product of component (C) and component (S), and component (A) and component (B), the contact time is usually 0 to 5 hours, preferably 0 to 2 hours, and the contact temperature is Usually, it is in the range of −50 to 200 ° C., preferably −50 to 100 ° C. The amount of contact of component (A) and component (B) with component (C) largely depends on the type and amount of component (C). In the case of component (c-1), component (c-1) and component (C-1) The molar ratio [(c-1) / M] to (A) and all transition metal atoms (M) in component (B) is usually 0.01 to 100,000, preferably 0.05 to 50,000. In the case of component (c-2), the molar ratio of aluminum atoms in component (c-2) to all transition metal atoms (M) in component (A) and component (B) [( c-2) / M] is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. In the case of component (c-3), the molar ratio [(c-3) / M] of component (c-3) and all transition metal atoms (M) in component (A) and component (B) is The amount is usually 1 to 10, preferably 1 to 5. The molar ratio of component (C) to all transition metal atoms (M) in component (A) and component (B) can be determined by inductively coupled plasma emission analysis (ICP analysis).

  The use ratio of the component (A) to the component (B) can be appropriately determined according to the molecular weight and molecular weight distribution of the polyolefin to be produced, but the preferred range is the ratio of the polymer produced from the component (A) and the component (B). [= Production amount of component (A) / Production amount of component (B)] is usually 40/60 to 95/5, preferably 50/50 to 95/5, particularly preferably 60/40 to 95/5. Here, the reason why a larger amount of the polymer derived from the component (A) is preferable is that a macromonomer is generated from the component (A), and a larger amount of this generation is advantageous for generating a longer chain branch. For such as. Further, the molar ratio of the component (A) and the component (B) to be used per transition metal compound should satisfy the above-mentioned polymer ratio, and the ratio is approximately the contact product of the component (S) and the component (C). And the component (A) or the component (B) can be determined by the activity ratio expressed from the solid catalyst component that is brought into contact with each other independently.

  For the (co) polymerization of olefins, the solid catalyst component as described above can be used as it is, but it can also be used after prepolymerizing the olefin with this solid catalyst component to form a prepolymerized solid catalyst component.

  The prepolymerization catalyst component can be prepared by introducing an olefin usually in an inert hydrocarbon solvent in the presence of the solid catalyst component. As the reaction system, any of batch system, semi-continuous system and continuous system can be used. The reaction can be carried out under reduced pressure, normal pressure or increased pressure. By this prepolymerization, a polymer of usually 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g is produced per 1 g of the solid catalyst component.

  The prepolymerization catalyst component prepared in the inert hydrocarbon solvent may be separated from the suspension, then suspended in the inert hydrocarbon again, and the olefin may be introduced into the resulting suspension. Further, olefin may be introduced after drying.

The prepolymerization temperature is usually -20 to 80 ° C, preferably 0 to 60 ° C. The prepolymerization time is usually 0.5 to 100 hours, preferably 1 to 50 hours.
As the form of the solid catalyst component used for the prepolymerization, those already described can be used without limitation. In addition, component (C) is used as required, and in particular, an organoaluminum compound represented by the above formula (III) in (c-1) is preferably used. When the organoaluminum compound of the formula (III) is used as the component (C), the moles of the aluminum atom (Al-C) in the component (C) and the transition metal compound as the components (A) and (B) The ratio (component (C) / transition metal compound) is usually 0.1 to 10,000, preferably 0.5 to 5,000.

  The concentration of the solid catalyst component in the prepolymerization system is usually 1 to 1000 g / liter, preferably 10 to 500 g / liter, in the ratio of solid catalyst component (X) / polymerization volume of 1 liter. At the time of preliminary polymerization, the component (G) can coexist for the purpose of suppressing fouling or improving particle properties.

  In addition, for the purpose of improving the fluidity of the prepolymerized solid catalyst component, heat spot sheeting during polymerization, and suppressing the generation of polymer lumps, the component (G) may be brought into contact with the prepolymerized solid catalyst component once produced by prepolymerization. Good. In this case, as the component (G) to be used, (g-1), (g-2), (g-3), and (g-4) are preferable.

The temperature at which the component (G) is mixed and contacted is usually −50 to 50 ° C., preferably −20 to 50 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes.
In mixing and contacting the solid catalyst component and the component (G), the component (G) is usually 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, with respect to 100 parts by weight of the solid catalyst component. More preferably, it is used in an amount of 0.4 to 5 parts by weight.

  The mixed contact between the solid catalyst component and the component (G) can be performed in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same solvents as those used for the preparation of the solid catalyst component.

  The olefin polymerization catalyst according to the present invention can be used as a dry prepolymerization catalyst by drying a prepolymerized solid catalyst component. Drying of the prepolymerized solid catalyst component is usually performed after removing the hydrocarbon as a dispersion medium from the obtained suspension of the prepolymerized catalyst by filtration or the like.

  Drying of the prepolymerized solid catalyst component is carried out by maintaining the prepolymerized solid catalyst component at a temperature in the range of 70 ° C. or lower, preferably 20 to 50 ° C. under the flow of inert gas. The amount of volatile components of the obtained dry prepolymerization catalyst is 2.0% by weight or less, preferably 1.0% by weight or less. The amount of volatile components in the dry prepolymerization catalyst is preferably as small as possible, and there is no particular lower limit, but it is practically 0.001% by weight. The drying time is usually 3 to 8 hours depending on the drying temperature. When the amount of the volatile component of the dry prepolymerization catalyst exceeds 2.0% by weight, the fluidity of the dry prepolymerization catalyst is lowered, and it may be impossible to stably supply the polymerization reactor.

Here, the amount of volatile components of the dry prepolymerization catalyst is measured by, for example, a weight loss method, a method using gas chromatography, or the like.
In the weight loss method, the weight loss when the dried prepolymerized catalyst is heated at 110 ° C. for 1 hour in an inert gas atmosphere is determined and expressed as a percentage of the dried prepolymerized catalyst before heating.

  In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dry prepolymerization catalyst, a calibration curve is prepared according to the internal standard method, and then calculated from the GC area as weight%.

  As a method for measuring the amount of volatile components in the dry prepolymerized catalyst, when the amount of volatile components in the dry prepolymerized catalyst is about 1% by weight or more, a weight reduction method is adopted, and the amount of volatile components in the dry prepolymerized catalyst is about 1 When the content is not more than% by weight, a method using gas chromatography is employed.

  Examples of the inert gas used for drying the prepolymerized solid catalyst component include nitrogen gas, argon gas, and neon gas. Such an inert gas has an oxygen concentration of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (volume basis), and a moisture content of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (weight basis). ) Is desirable. If the oxygen concentration and water content in the inert gas exceed the above ranges, the olefin polymerization activity of the dry prepolymerization catalyst may be greatly reduced.

  Since the dry prepolymerization catalyst is excellent in fluidity, it can be stably supplied to the polymerization reactor. Further, since it is not necessary to entrain the solvent used for suspension in the gas phase polymerization system, the polymerization can be stably performed.

  Next, the method for polymerizing an ethylene polymer according to the present invention will be described. Ethylene polymers are obtained by polymerizing or copolymerizing olefins in the presence of the above-mentioned catalyst for olefin polymerization. The ethylene-based polymer in the present invention refers to a polymer having an ethylene content of 10 mol% or more in the polymer.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method, but the solution polymerization method is preferred under the first olefin polymerization catalyst according to the present invention, Suspension polymerization and gas phase polymerization are preferred under the second and third olefin polymerization catalysts.

  Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methyl Examples thereof include alicyclic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. In the liquid phase polymerization method, the olefin itself can be used as a solvent.

When the olefin polymerization is performed using the above-mentioned catalyst for olefin polymerization, the component (A) and the component (B) are usually 10 ⁻¹² to 10 ⁻¹ mol, preferably 10 ⁻⁸ to It is used in such an amount that it becomes 10 ⁻² mol. Component (C) is used, and an organoaluminum compound represented by general formula (III) in (c-1) is particularly preferred and used.

Moreover, the polymerization temperature of the olefin using the above-mentioned solid catalyst component is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C., particularly preferably 60 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction is carried out in any of batch, semi-continuous and continuous methods. Can do. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting ethylene polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. At the time of polymerization, the component (G) can coexist for the purpose of suppressing fouling or improving particle properties.

  In the present invention, the olefin supplied to the polymerization reaction is usually one or more monomers selected from ethylene and an olefin having 3 to 20 carbon atoms. Of these olefins, at least one is preferably ethylene or propylene. Specific examples of the olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-decene, Α-olefins such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5 , 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like, and the like. Specific examples of the olefin include, for example, styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, and the like; methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid And polar monomers.

  In general, the reactivity of olefin polymerization catalysts to ethylene polymers increases as the molecular weight of the ethylene polymer decreases and the proportion of terminal double bonds increases, producing many long chain branches. can do. Since component (A) has a relatively low molecular weight and can produce a polymer having a number of double bonds at its terminals, it can be efficiently incorporated by component (B), and has a longer length than that of conventionally known polymers. A polymer having a chain branch can be produced. In addition, a polymer having a long chain branch can be produced with high productivity derived from the polymerization activity of the component (A).

The characteristics of the ethylene-based polymer obtained by the present invention are usually as follows.
The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is preferably 0.1 to 100 g / 10 minutes, more preferably 1.0 to 50 g / 10 minutes, and further preferably 4 to 30 g / 10 minutes. It is a range.

  When the MFR is 0.1 g / 10 min or more, the shear viscosity of the ethylene-based resin is not too high, and the moldability is excellent. For example, the appearance of a film is good. When MFR is 100 g / 10 min or less, the tensile strength and heat seal strength of the ethylene-based polymer are good.

The density (D) is preferably in the range of 875 to 970 kg / m ³ , more preferably 885 to 964 kg / m ³ , and still more preferably 905 to 960 kg / m ³ .
When the density (D) is 875 kg / m ³ or more, the heat resistance of the ethylene polymer is good, and the film surface formed from the ethylene polymer is less sticky. On the other hand, when the density (D) is 970 kg / m ³ or less, the low-temperature sealing property of the ethylene polymer is good. In general, the density depends on the α-olefin content of the ethylene-based polymer. The smaller the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density.

The ratio [MT / η * (g / P)] of the melt tension [MT (g)] at 190 ° C. to the shear viscosity [η * (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec is preferably 5. It is in the range of 0 × 10 ^{−5 to} 1.0 × 10 ⁻³ , more preferably 7.5 × 10 ^{−5 to} 6.1 × 10 ⁻⁴ .

When MT / η * is 5.0 × 10 ⁻⁵ or more, the resulting ethylene polymer has a high melt tension relative to the molecular weight, so the neck-in in T-die molding is small, and the bubble stability in inflation molding is excellent. Excellent moldability.

The intrinsic viscosity ([η] (dl / g)) of an ethylene polymer measured in decalin at 135 ° C and the weight average molecular weight Mw measured by GPC-viscosity detector method (GPC-VISCO) are preferably as follows: The relational expression (Eq-1) is satisfied.
0.90 × 10 ⁻⁴ × Mw ^0.776 ≦ [η] ≦ 2.25 × 10 ⁻⁴ × Mw ^0.776 ----- (Eq-1)
More preferably, the following relational expression (Eq-2) is satisfied.
0.95 × 10 ⁻⁴ × Mw ^0.776 ≦ [η] ≦ 2.05 × 10 ⁻⁴ × Mw ^0.776 ----- (Eq-2)
More preferably, the following relational expression (Eq-3) is satisfied.
1.00 × 10 ⁻⁴ × Mw ^0.776 ≦ [η] ≦ 1.82 × 10 ⁻⁴ × Mw ^0.776 ----- (Eq-3)

It is known that when long chain branching is introduced into an ethylene polymer, the intrinsic viscosity [η] (dl / g) is smaller for the molecular weight than a straight chain ethylene polymer without long chain branching. (For example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched Polymer II, p.137 (1999)). Therefore, even in the present ethylene polymer, when the intrinsic viscosity [η] (dl / g) is 2.25 × 10 ⁻⁴ × Mw ^0.776 or less, it has a large number of long chain branches. Excellent fluidity.

  In order to suppress variation in physical property values, the ethylene polymer particles obtained by the polymerization reaction and other components added as desired are melted by an arbitrary method, kneaded, granulated, and the like.

The ethylene polymer obtained in the present invention may be pelletized by the following method.
A method of mechanically blending an ethylene-based polymer and other components added as required using an extruder, a kneader or the like, and cutting the mixture into a predetermined size.
Dissolve the ethylene polymer and other components added as desired in a suitable good solvent (for example, hydrocarbon solvents such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then remove the solvent. A method of mechanically blending using an extruder, kneader, etc. and then cutting into a predetermined size.

  The ethylene polymer obtained in the present invention is a weather resistance stabilizer, heat resistance stabilizer, antistatic agent, anti-slip agent, anti-blocking agent, anti-fogging agent, lubricant, pigment, as long as the object of the present invention is not impaired. Additives such as dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents and antioxidants may be blended as necessary.

  The ethylene polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and additives are processed by general film molding, blow molding, injection molding and extrusion molding. Examples of film molding include extrusion lamination molding, T-die film molding, and inflation molding (air cooling, water cooling, multistage cooling, high-speed processing), and the like. Although the obtained film can be used as a single layer, various functions can be imparted by forming a multilayer. In that case, the coextrusion method in each said shaping | molding method is mentioned. On the other hand, lamination with paper and barrier films (aluminum foil, vapor-deposited film, coating film, etc.) that are difficult to co-extrusion by a lamination method such as extrusion lamination or dry lamination is mentioned. Production of high-functional products by multilayering by co-extrusion methods in blow molding, injection molding, and extrusion molding is possible in the same manner as film molding.

  As a molded product obtained by processing the ethylene-based polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and additives, a film, a blown infusion bag, a blow bottle, a gasoline tank, Examples include tubes, pipes, tear caps by extrusion molding, injection molded products such as daily goods, fibers, and large molded products by rotational molding.

  Furthermore, as a film obtained by processing the ethylene-based polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and additives, a water packaging bag, a liquid soup bag, a liquid paper container , Lami fabric, special shape liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, food packaging packaging films, protective films, infusion bags, agriculture Suitable for materials for use. It can also be used as a multilayer film by being bonded to a base material such as nylon or polyester.

A method for measuring physical properties of the ethylene polymer is shown below.
The melt flow rate (MFR) was measured under conditions of 190 ° C. and 2.16 kg load (kgf) according to ASTM D1238-89.

The density (D) was measured by the density gradient tube method after heat-treating the strand obtained at the time of MFR measurement at 100 ° C. for 1 hour and allowing it to stand at room temperature for 1 hour in accordance with JIS K7112.
The melt tension (MT) was determined by measuring the stress when stretched at a constant speed, the melt tension (MT) at 190 ° C. (unit: g). For the measurement, a capillary rheometer: Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. The conditions are a resin temperature of 190 ° C., a melting time of 6 minutes, a barrel diameter of 9.55 mmφ, an extrusion speed of 15 mm / min, a winding speed of 24 m / min (if the molten filament breaks, the winding speed is decreased by 5 m / min. The nozzle diameter was 2.095 mmφ and the nozzle length was 8 mm.

For the intrinsic viscosity (η: [dl / g]), about 20 mg of a measurement sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity η _sp was measured in the same manner. This dilution operation was further repeated twice, and the value of η _sp / C when the concentration (C) was extrapolated to 0 as shown in the following formula (Eq-4) was determined as the intrinsic viscosity [η] (unit: dl / g ).
[Η] = lim (η _sp / C) (C → 0) ------- (Eq-4)

For the shear viscosity (η *), the angular velocity [ω (rad / sec)] dispersion of the shear viscosity (η *) at a measurement temperature of 200 ° C. is measured in the range of 0.01 ≦ ω ≦ 100. For measurement, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used, a 25 mmφ parallel plate was used as a sample holder, and a sample thickness was about 2.0 mm. The number of measurement points was 5 per ω digit. The amount of strain was appropriately selected within a range of 3 to 10% so that the torque in the measurement range could be detected and torque was not exceeded. The sample used for the shear viscosity measurement was a press molding machine manufactured by Shinfuji Metal Industry, with a preheating temperature of 190 ° C, a preheating time of 5 minutes, a heating temperature of 190 ° C, a heating time of 2 minutes, a heating pressure of 100 kgf / cm ² , and a cooling temperature of 20 The measurement sample was produced by press-molding to a thickness of 2 mm under conditions of a cooling time of 5 minutes and a cooling pressure of 100 kgf / cm ² .

  The weight average molecular weight (Mw) by GPC-VISCO method was measured as follows using GPC / V2000 manufactured by Waters. The guard column uses Shodex AT-G, the analytical column uses two AT-806, the column temperature is 145 ° C., the mobile phase uses o-dichlorobenzene and BHT 0.3 wt% as an antioxidant, 1.0 ml The sample concentration was 0.1 wt%, and a differential refractometer and a three-capillary viscometer were used as detectors. Standard polystyrene used was manufactured by Tosoh Corporation. In the molecular weight calculation, the actually measured viscosity was calculated from a viscometer and a refractometer, and the weight average molecular weight (Mw) was calculated from the actually measured universal calibration.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[Example 1]
Preparation of solid support In a reactor equipped with a stirrer with an internal volume of 270 liters, silica gel (manufactured by Fuji Silysia Co., Ltd .: average particle size 70 μm, specific surface area 340 m ² / g, pore volume 1.3 cm ³ / g, (10 hours dried at 250 ° C.) 10 kg was suspended in 77 liters of toluene and then cooled to 0 to 5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mmol / mL in terms of Al atom) was added dropwise over 30 minutes. At this time, the system temperature was kept at 0 to 5 ° C. Subsequently, contact was performed at 0 to 5 ° C. for 30 minutes, and then the system temperature was raised to 95 ° C. over about 1.5 hours, followed by contact at 95 ° C. for 4 hours. Thereafter, the temperature was lowered to normal temperature, the supernatant was removed by decantation, and further washed twice with toluene, and then a total amount of 115 liters of toluene slurry was prepared. When a part of the obtained slurry component was sampled and the concentration was examined, the slurry concentration was 122.6 g / L and the Al concentration was 0.62 mol / L.

Preparation of solid catalyst component A reactor equipped with a stirrer with an internal volume of 200 ml was charged with 50 ml of toluene and 8.2 ml of the solid support slurry obtained above (5.0 mmol in terms of Al atoms) in a nitrogen atmosphere. I entered. Next, 0.015 mmol of dimethylsilylene bis (tetrahydroindenyl) zirconium dichloride (purchased from Wako Pure Chemical Industries, Ltd.) as Zr, 0.015 mmol, dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) ) After adding 0.010 mmol of a toluene solution of zirconium dichloride (synthesized based on JP 2009-143901 A) as Zr and bringing it into contact at an internal temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and further hexane After washing twice with a total amount of 50 ml, a solid catalyst component slurry was prepared.

Production of Ethylene Polymer After adding 500 ml of heptane to a SUS autoclave having an internal volume of 1 liter in a nitrogen atmosphere, ethylene was circulated to saturate the liquid phase and gas phase with ethylene. Next, 10 milliliters of 1-hexene, 0.375 mmol of triisobutylaluminum, and 10 mg of a solid catalyst component as a solid content were charged, and then the temperature was increased to 80 ° C. and 0.8 MPaG, and the polymerization reaction was performed for 90 minutes. . The obtained polymer was filtered and then vacuum-dried at 80 ° C. for 10 hours to obtain 57.1 g of an ethylene polymer.

  As a heat-resistant stabilizer, Irganox 1076 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1% by weight and Irgafos 168 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1% by weight are added to the obtained ethylene polymer powder, and Laboplast mill (stock) The product was melt kneaded for 5 minutes at a resin temperature of 180 ° C. and a rotation speed of 50 rpm. Further, this molten polymer was cooled using a press molding machine (manufactured by Shinfuji Metal Industry Co., Ltd.) under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm 2. Physical properties were measured using the sample as a measurement sample. The results are shown in Table 1.

[Example 2]
Preparation of solid catalyst component In a reactor with an internal volume of 200 ml, with a stirrer, 50 ml of toluene under a nitrogen atmosphere, and 8.2 ml of the solid support slurry obtained in Example 1 (5.0 mmol in terms of Al atom) Was loaded. Next, 0.015 mmol of toluene solution of ethylenebis (tetrahydroindenyl) zirconium dichloride (purchased from Wako Pure Chemical Industries, Ltd.) as Zr, dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) After adding 0.010 mmol of a zirconium dichloride toluene solution as Zr and contacting at a system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation and further washed twice with hexane, and then the total amount of 50 A slurry of the solid catalyst component was prepared in milliliters.

Production of Ethylene Polymer After adding 500 ml of heptane to a SUS autoclave having an internal volume of 1 liter in a nitrogen atmosphere, ethylene was circulated to saturate the liquid phase and gas phase with ethylene. Next, 10 ml of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30 mg of a solid catalyst component as a solid content were charged, and then the temperature was increased to 80 ° C. and 0.8 MPaG, and the polymerization reaction was performed for 90 minutes. . The obtained polymer was filtered and then vacuum-dried at 80 ° C. for 10 hours to obtain 75.8 g of an ethylene polymer.
The obtained ethylene-based polymer was melt kneaded and cooled in the same manner as in Example 1, and physical properties were measured using the obtained sample as a measurement sample. The results are shown in Table 1.

[Comparative Example 1]
The ethylene / 1-octene copolymer (trade name: Affinity PF1140) obtained by a solution polymerization method commercially available from Dow Chemical Company was evaluated for physical properties using a product pellet as a measurement sample. The results are shown in Table 1.

Claims (8)

An olefin polymerization catalyst comprising the following component (A), component (B) and component (C).
Component (A): A bridged metallocene compound represented by the following general formula (I).

[In the general formula (I), R ¹ , R ² , R ³ and R ⁴ are monovalent groups, a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, A group selected from a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and these groups may be the same or different from each other, but all of them are not hydrogen atoms at the same time. Of these, adjacent groups may be bonded to each other to form an aliphatic ring, Q ¹ is a divalent group, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, germanium X is a monovalent group, each independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group. Groups, nitrogen-containing groups and lithium A group selected from-containing group, M is a titanium atom, a zirconium atom or a hafnium atom. ]
Component (B): A bridged metallocene compound represented by the following general formula (II).

[In the general formula (II), R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹² are monovalent groups, a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, nitrogen Group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group and tin-containing group, each of which may be the same or different. R ⁷ and R ¹¹ may be a divalent saturated hydrocarbon group having 3 to 8 carbon atoms, and may be the same or different from each other, and n is 0 Or, when R is an integer not more than twice the carbon number of R ⁷ and R ¹¹ and n is an integer of 2 or more, the plurality of R ⁷ and R ¹¹ may be the same or different, and Q ² is divalent A hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, X is a monovalent group, each independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen A group selected from a containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group, and M is a titanium atom, a zirconium atom or a hafnium atom. ]
Component (C); (c-1) an organometallic compound represented by the following general formula (III), (IV) or (V), (c-2) an organoaluminum oxy compound, and (c-3) component ( A) at least one compound selected from the group consisting of compounds that react with component (B) to form ion pairs.
R ^a _m Al (OR ^b ) _n H _p X _q (III)
[In the general formula (III), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. ]
M ^a AlR ^a ₄ (IV) [In the general formula (IV), M ^a represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^a _r M ^b R ^b _s X _t (V) [In the general formula (V), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, and may be the same or different from each other. even better, M ^b, Mg, selected from Zn and Cd, X is a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]   From the solid carrier (S), the solid catalyst component (K1) formed from the component (C) and the component (A), the solid carrier (S), the component (C) and the component (B). The olefin polymerization catalyst according to claim 1, comprising a solid catalyst component (K2) to be formed.   The catalyst for olefin polymerization according to claim 1, comprising a solid support (S), a solid catalyst component (K3) formed from the component (A), the component (B) and the component (C). . The olefin polymerization according to any one of claims 1 to 3, wherein in the general formula (I), at least one of R ¹ , R ² , R ³ and R ⁴ is a hydrocarbon group. Catalyst. 5. The olefin polymerization catalyst according to claim 1, wherein R ⁷ and R ¹¹ have 4 carbon atoms in the general formula (II).   The olefin polymerization catalyst according to any one of claims 1 to 5, wherein the component (C) is an organoaluminum oxy compound.   The olefin polymerization catalyst according to any one of claims 1 to 6, wherein the solid support (S) is a porous oxide.   A method for producing an ethylene polymer, comprising polymerizing ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst according to any one of claims 1 to 7. .