JP5405806B2 - Olefin polymerization catalyst and method for producing ethylene polymer using the same - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst and a method for producing an ethylene polymer using the catalyst, and more specifically, an ethylene polymer having a high melt tension, excellent mechanical strength, and excellent particle properties. The present invention relates to an olefin polymerization catalyst that can be produced with polymerization activity and a method for producing an ethylene polymer 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.

  Low-density polyethylene (LDPE) produced by high-pressure radical polymerization has a complex long-chain branching structure, so it has a high melt tension and, therefore, has a good processability such as a small neck-in. It is offered to. However, the mechanical strength such as tensile strength, tear strength, and impact strength of the molded body is low, and the problem remains that it is inferior in high-speed film forming workability in T-die molding.

  On the other hand, in contrast to LDPE, ethylene polymers obtained with Ziegler catalysts and metallocene catalysts have high tensile strength, tear strength, or impact strength, and therefore require mechanical strength. However, there is a problem that the melt tension is small and the 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 [1]
In this method, a significant increase in cost is inevitable in preparing the blend. [2], [3], [4]
The ethylene polymer obtained by the method [5] has a small number of long-chain branches, and sufficient melt tension and molding processability cannot be obtained. Furthermore, in the method [6], when a large amount of diene is introduced, there is a concern that the mechanical properties inherent to the polymer are deteriorated or gel is generated.

  In recent years, examples of using two or more types of metallocene compounds and organometallic complexes have been reported for the purpose of generating more long-chain branches and improving melt tension (Patent Documents 7 and 8). The number of long-chain branches is still not sufficient, and it can be said that problems remain in terms of moldability. In fact, the catalyst activity is far from the industrial performance level.

As described above, it has been difficult to obtain a resin having a high melt tension and excellent mechanical strength at low cost and efficiently with a conventionally known catalyst system or resin blending technique. In other words, the emergence of an efficient production technique for an ethylene polymer having both high melt tension and excellent mechanical strength is important for industrial production and its value is extremely high.
WO99 / 046325 pamphlet JP-A-2-53811 JP-A-4-213306 JP-A-8-502303 Japanese National Publication No. 1-50163 JP-T-4-506372 Japanese Patent Application Laid-Open No. 7-252311 JP 2006-2057 A

  The present invention has been made in view of the above prior art, and can produce an olefin polymer having high melt tension, excellent mechanical strength, and excellent particle properties with high polymerization activity. It is an object of the present invention to provide such an 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 coexisted multiple types of bridged metallocene compounds composed of cyclopentadienyl derivative groups having different structures in the same polymerization system, and are sources of long chain branching. By simultaneously inducing the formation of macromonomer and repolymerization of the generated macromonomer, the inventors have found an olefin polymerization catalyst and a polymerization method that can efficiently produce an olefin polymer having many long-chain branches, and completed the present invention. It was. 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〜Ｒ⁴は、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、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、隣接する基が互いに結合して脂肪族環を形成していてもよい。Ｑ¹は
、炭素数１〜２０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、Ｘは、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。〕
成分（Ｂ）；下記一般式（II）で表される架橋型メタロセン化合物。

[In the general formula (I), R ^{1 to} R ⁴ are a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, They are selected from a germanium-containing group and a tin-containing group, and may be the same or different from each other, but all are not hydrogen atoms at the same time, and adjacent groups may be bonded to each other to form an aliphatic ring. Q ¹ is selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, M is a group selected from a halogen-containing group, a silicon-containing group, an oxygen-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 (B) : A bridged metallocene compound represented by the following general formula (II).

〔一般式（II）中、Ｒ⁷〜Ｒ¹⁰およびＲ¹³〜Ｒ²⁰は、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、また、隣接した置換基は互いに結合して環を形成してもよく、Ｑ²は、
炭素数１〜２０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、Ｍは、チタン原子、ジルコニウム原子およびハフニウム原子から選ばれ、Ｘは、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る。〕

[In the general formula (II), R ^{7 to} R ¹⁰ and R ^{13 to} R ²⁰ are hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing A group selected from a group, a silicon-containing group, a germanium-containing group, and a tin-containing group, which may be the same or different, and adjacent substituents may be bonded to each other to form a ring, and Q ² Is
Is selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group; M is selected from a titanium atom, a zirconium atom and a hafnium atom; and X is independently , A hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. ]

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) at least one compound selected from the group consisting of compounds that react with component (A) and 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 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 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, 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. ]

  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, and the component (C) is an organoaluminum oxy compound, It is also preferred that the solid support (S) is a porous oxide.

The method for producing an ethylene polymer according to the present invention is characterized by polymerizing ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst. In the present invention, two or more peaks are observed in gel permeation chromatography (GPC), and the maximum peak peak Log M _Max satisfies 3.8 ≦ Log M _Max ≦ 4.6, and the peak intensity of the maximum peak. It is preferable to produce an ethylene polymer in which (H _Max ) and the peak intensity (H _second ) of the next largest peak satisfy the relationship of H _Max ≧ 2 × H _second .

  According to the present invention, there are provided an ethylene polymer excellent in molding processability and having a long chain branching amount and an efficient production method thereof.

  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 metallocene compound belonging to Group 4 of the periodic table 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 general formula (I), M represents a group 4 transition metal atom in the periodic table, specifically titanium, zirconium, or hafnium, preferably zirconium.

R ^{1 to} R ⁴ are hydrogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups. They may be the same or different from each other, but not all are hydrogen atoms at the same time. Moreover, R < ¹ > -R < ⁴ > may combine the adjacent group mutually and may form the aliphatic ring.

The hydrocarbon group means an alkyl group composed of 1 to 20 carbon atoms and hydrogen, a cycloalkyl group, an alkenyl group, an aryl group, and an arylalkyl group. For example, as an alkyl group, a methyl group, an ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-octyl group, nonyl group, dodecyl group, eicosyl group Etc. Examples of the cycloalkyl group 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 include a vinyl group, a propenyl group, and a cyclohexenyl group. Examples of the aryl group include phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, Examples include anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl, and arylalkyl groups include benzyl, phenylethyl, phenylpropyl, and the like.

Examples of the halogen-containing group include a group in which one or more hydrogen atoms in the hydrocarbon group are substituted with an appropriate halogen atom, such as a trifluoromethyl group.
Examples of the oxygen-containing group include a methoxy group and an ethoxy group. Examples of the sulfur-containing group include a thiol group and a sulfonic acid group. Examples of the nitrogen-containing group include a dimethylamino group. Examples thereof include a phenylphosphine group. Examples of the boron-containing group include a boranediyl group, a boranetriyl group, and a diboranyl group.

  Silicon-containing groups include silyl, methylsilyl, dimethylsilyl, diisopropylsilyl, methyl-t-butylsilyl, dicyclohexylsilyl, methylcyclohexylsilyl, methylphenylsilyl, diphenylsilyl, methylnaphthylsilyl, dinaphthylsilyl, cyclodimethylenesilyl, cyclo Examples include trimethylene silyl, cyclotetramethylene silyl, cyclopentamethylene silyl, cyclohexamethylene silyl, cycloheptamethylene silyl, and the like. Germanium and tin-containing groups include groups obtained by converting silicon into germanium and tin in the silicon-containing groups. Etc.

Examples of the case where adjacent groups of R ^{1 to} 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, substituted cyclopenta in which R ³ and R ⁴ are cyclically bonded via a tetramethylene group and R ¹ and R ² are cyclically bonded via a tetramethylene group A dienyl group etc. are mentioned.

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 or an alkylidene group, a halogen-containing group, a silicon-containing group, germanium It is a group selected from a containing group and a tin-containing group.

  Specific examples of the alkylene group having 1 to 20 carbon atoms, the substituted alkylene group, and the alkylidene group include alkylene groups such as methylene, ethylene, propylene, and butylene, isopropylidene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, and methyl. Ethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1, Substituted alkylene groups such as 2-dimethylethylene and 1-ethyl-2-methylethylene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylide , Cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthyl dust Den, cycloalkylene groups such as dihydroindolyl mites isopropylidene, ethylidene, propylidene, and the like alkylidene group such as butylidene.

Examples of silicon-containing groups include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolylsilylene, methyl Naphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like, and germanium and tin-containing groups include the above Examples of the silicon-containing group include a group obtained by converting silicon into germanium or tin.

  As the 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. For example, bis (trifluoromethyl) Examples include 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 silicon-containing groups. And a particularly preferred group is a silicon-containing group or a halogen-containing silicon.

Q ¹ may have a structure represented by either the following general formula [1] or [2].

ここで、Ｙは炭素原子、ケイ素原子、ゲルマニウム原子およびスズ原子から選ばれる。Ｒ⁵およびＲ⁶は水素原子、炭化水素基、ケイ素含有基、ゲルマニウム含有基、スズ含有基およびハロゲン含有基から選ばれ、それぞれ同一でも異なっていてもよい。Ａは不飽和結合を含んでいてもよい炭素原子数２〜２０の二価の炭化水素基を示し、ＡはＹと共に形成する環を含めて二つ以上の環構造を含んでいてもよい。黒丸（●）は置換シクロペンタジエニル基およびシクロペンタジエニル基との結合点を表す。

Here, Y is selected from a carbon atom, a silicon atom, a germanium atom, and a tin atom. R ⁵ and R ⁶ are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, and a halogen-containing group, and may be the same or different. A represents a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, and A may contain two or more ring structures including a ring formed with Y. A black circle (●) represents a point of attachment to a substituted cyclopentadienyl group or cyclopentadienyl group.

In the general formulas [1] and [2], Y is preferably a carbon atom or a silicon atom, and particularly preferably a silicon atom.
The hydrocarbon group, silicon-containing group, germanium-containing group, tin-containing group, and halogen-containing group of R ⁵ and R ^{6 in} the general formula [1] are the same as those for R ¹ , R ² , R ³ , and R ^4. It can be mentioned as an example. Among the hydrocarbons, methyl group, chloromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, cycloheptyl It is preferably a group selected from a group, a phenyl group, an m-tolyl group and a p-tolyl group, and particularly preferably selected from a methyl group, a chloromethyl group, an n-butyl group, an n-pentyl group and a phenyl group. .

  In the general formula [2], A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, Y is bonded to this A, and a 1-silacyclopentylidene group or the like Configure. In the present specification, the 1-silacyclopentylidene group represents the following formula [3].

（上記式［３］において、黒丸（●）は、一般式［２］と同様である。）
また、ＡはＹとともに形成する環を含めて二つ以上の環構造を含んでいてもよい。

(In the above formula [3], the black circle (●) is the same as the general formula [2].)
A may include two or more ring structures including a ring formed with Y.

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 silicon-containing groups. And a particularly preferred group is a silicon-containing group or a halogen-containing silicon-containing group.

  X 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, a nitrogen-containing group, or a phosphorus-containing group. The selected group is 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 described above.

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

Specific examples of the transition metal compound of the component (A) represented by the general formula (I) are shown below.
Specific examples include 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-n-propylcyclopentadienyl) zirconium dichloride, ethylene (cycl Pentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-pentylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3-n-hexyl) Cyclopentadienyl) 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-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) ) (2,5-dimethylcyclopentadienyl) 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-propylcyclopentadienyl) 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 ( Cyclo Pentadienyl) (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-butylcyclopentadienyl) zirconium A bridged asymmetric metallocene compound having an alkylene group such as dichloride at the crosslinking site;

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 (cyclopentadienyl) (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methyl, 4-n- Propylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methyl, 4-n-butylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3,4- Trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (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- Substituted alkylene groups such as di-n-propylcyclopentadienyl) zirconium dichloride and isopropylidene (cyclopentadienyl) (2,5-dimethyl, 3,4-di-n-butylcyclopentadienyl) zirconium dichloride; A bridged asymmetric metallocene compound at the 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 (cyclopentadienyl) (2,5-ethylmethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl, 4-n- Propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl, 4-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,4- Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (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- Silicon-containing groups such as di-n-propylcyclopentadienyl) zirconium dichloride and dimethylsilylene (cyclopentadienyl) (2,5-dimethyl, 3,4-di-n-butylcyclopentadienyl) zirconium dichloride. A cross-linked asymmetric metallocene compound at a cross-linked site.

  In addition, a crosslinked asymmetric metallocene in which the isopropylidene crosslinking group of the substituted alkylene group is changed to a di-n-butylmethylene crosslinking group, and a crosslinked type in which the dimethylsilylene crosslinking group of a silicon-containing group is changed to a di-n-butylsilylene crosslinking group Asymmetric metallocenes, bridged asymmetric metallocenes in which one or more of the hydrogen atoms in the bridging group are changed to halogen atoms, bridges in which one or more hydrogen atoms of the substituents bonded to the cyclopentadienyl ring are changed to halogen atoms Type asymmetric metallocenes. Moreover, although the metallocene compound etc. whose center metal of the said compound is titanium or hafnium are mentioned, it is not limited to these.

  Among these, as a preferable compound, a crosslinked asymmetric metallocene having a silicon-containing group such as a dimethylsilylene group at a crosslinking site is selected. Among them, a particularly preferable compound is dimethylsilylene (cyclopentadienyl) (3-ethyl). Cyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium Dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, Methylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene ( Cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene ( Cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride and the like. In the present invention, two or more types of metallocene compounds represented by the general formula (I) having different structures are used, or metallocenes having the same structure and comprising an optical isomer mixture (for example, meso / racemic mixture). There is no restriction on the use of the compound.

Such a bridged metallocene compound represented by the general formula (I) can be produced by the method disclosed in WO 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、チタン、ジルコニウムおよびハフニウムから選ばれた遷移金属であり、好ましくは、ジルコニウムである。

In the general formula (II), M is a transition metal selected from titanium, zirconium and hafnium, preferably zirconium.

R ^{7 to} R ¹⁰ , R ^{13 to} R ²⁰ are hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing Selected from a group and a tin-containing group, which may be the same or different from each other, and two adjacent groups may be linked to each other to form a ring.

Q ² 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 or an alkylidene group, a halogen-containing group, a silicon-containing group, germanium It is a group selected from a containing group and a tin-containing group. Specific examples of these groups include those described for Q ¹ above.

Q ² may have a structure represented by any one of the following general formulas [4] and [5].

ここで、Ｙは炭素原子、ケイ素原子、ゲルマニウム原子およびスズ原子から選ばれる。Ｒ²¹およびＲ²²は水素原子、炭化水素基、ケイ素含有基、ゲルマニウム含有基、スズ含有基、およびハロゲン含有基から選ばれ、それぞれ同一でも異なっていてもよい。Ａ’は不飽和結合を含んでいてもよい炭素原子数２〜２０の二価の炭化水素基を示し、Ａ’はＹと共に形成する環を含めて二つ以上の環構造を含んでいてもよい。黒丸（●）は置換シクロペンタジエニル基および置換フルオレニル基との結合点を表す。

Here, Y is selected from a carbon atom, a silicon atom, a germanium atom, and a tin atom. R ²¹ and R ²² are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, and a halogen-containing group, and may be the same or different. A ′ represents a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, and A ′ may contain two or more ring structures including a ring formed with Y. Good. A black circle (●) represents a point of attachment to the substituted cyclopentadienyl group and the substituted fluorenyl group.

In the general formulas [4] and [5], Y is preferably a carbon atom or a silicon atom, particularly preferably a carbon atom.
The hydrocarbon group, silicon-containing group, germanium-containing group, tin-containing group, and halogen-containing group of R ²¹ and R ^{22 in} the general formula [4] are the same as R ^{7 to} R ¹⁰ and R ^{13 to} R ^20. It can be mentioned as an example. Among the hydrocarbon groups, methyl group, chloromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, cyclohexane It is preferably a group selected from a heptyl group, a phenyl group, an m-tolyl group, and a p-tolyl group, and particularly preferably selected from a methyl group, a chloromethyl group, an n-butyl group, an n-pentyl group, and a phenyl group. preferable.

  In the general formula [5], A ′ is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond, Y binds to this A ′, and 1-silacyclopentylidene Configure the group. In the present specification, the 1-silacyclopentylidene group represents the following formula [6].

（上記式［６］において、黒丸（●）は、一般式［５］と同様である。）
また、Ａ’はＹとともに形成する環を含めて二つ以上の環構造を含んでいてもよい。

(In the above formula [6], the black circle (●) is the same as the general formula [5].)
A ′ may include two or more ring structures including a ring formed with Y.

Among these, Q ² is preferably an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, an alkylidene group, a halogen-containing alkylene group, a halogen-containing substituted alkylene group, a halogen-containing alkylidene group, a silicon-containing group or a halogen-containing silicon-containing group. A particularly preferred group is an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, an alkylidene group, or a silicon-containing group.

  X 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, a nitrogen-containing group, or a phosphorus-containing group. The selected group is 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 described above.

Hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing R ^{7 to} R ¹⁰ and R ^{13 to} R ²⁰ As for the group or tin-containing group, those specifically described in R ^{1 to} R ⁴ in the general formula (I) can be used without limitation, and X is also described for X in the general formula (I). Can be used without limitation. Also, R ^{7 to} R ¹⁰ on the cyclopentadienyl ring are bonded to each other to form a ring, for example, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group. R ^{13 to} R ²⁰ on the fluorene ring may be bonded to each other to form a ring, for example, a benzofluorenyl group or a dibenzofluorenyl group. An octahydrodibenzofluorenyl group, an octamethyloctahydrodibenzofluorenyl group, or the like may be formed.

As the above preferred group form, R ^{7 to} R ¹⁰ are hydrogen atoms, and R ^{13 to} R ²⁰ are
A hydrogen atom or a hydrocarbon group is selected, and an octahydrodibenzofluorenyl group or an octamethyloctahydrodibenzofluorenyl group in which at least one of adjacent hydrocarbon groups is bonded to each other to form a ring Selected as a preferred group. For Q ² , the general formula [4
], A group represented by the general formula [5] is selected, Y is a carbon atom, and R ²¹ and R ²² are preferably a hydrocarbon group. When these substituents and crosslinking groups are used, the improvement in molecular weight is relatively suppressed, and the amount of macromonomer generated from component (A) increases due to the reduction in the amount of hydrogen necessary to adjust the molecular weight. Is expected to increase the number of long chain branches.

Specific examples of such metallocene compounds belonging to Group 4 of the periodic table represented by the general formula (II) are shown below, but the present invention is not limited thereto.
Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3 6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, Dibutylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) Luconium dichloride, dibutylmethylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2 , 7-di-tert-
Butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorene) Nyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
Cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium Dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) ( 2,7-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (cyclope Tadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (2,7-di-tert-butylfluorene) Nyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium Dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfullyl) Reniru)
Zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (octamethylocta Hydridodibenzfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (2,7-di-tert) -Butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclo Ntajieniru) (octamethyl octa hydride blunder benz fluorenyl) zirconium dichloride,

Cyclohexylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, Cyclohexylidene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride , Cyclohexylidene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butylcyclopentadienyl) (octamethylocta Hydridodibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (2,7-di -tert- Tylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (Octamethyloctahydridodibenzfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-
tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, diphenylmethylene (3-tert -Butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride,
Diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) ) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohex Silidene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert- Butylfluorenyl) zirconium dichloride, cyclohexylide (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butyl-5-methylcyclopentadienyl) (Octamethyloctahydrido-dibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5) -Methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert -Butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, and dibromide compounds, dialkyl compounds, diaralkyl compounds, disilyl compounds, dialkoxy compounds of the above metallocene compounds, Examples thereof include a dithiol compound, a disulfonic acid compound, a diamino compound, a diphosphine compound, or a metallocene compound in which the central metal of the above compound is titanium or hafnium.

Among these, preferred metallocene compounds include isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene ( Cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadi) Enyl) (fluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) ) Zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di-tert-butylfull) Olenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride Dimethylsilyl (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, And dimethylsilyl (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride.

Further, as specific examples of preferred metallocene compounds having adjacent groups of R ^{7 to} R ¹⁰ on the cyclopentadienyl ring to form a ring and having an indenyl ring and a substituted indenyl ring, isopropylidene (indenyl) (Fluorenyl) zirconium dichloride, isopropylidene (indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (indenyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, Isopropylidene (indenyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (fluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (2,7-di-tert-butylfluorenyl) Zirconium dichloride, cyclohexylidene (
Indenyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (indenyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilyl (indenyl) (fluorenyl) zirconium dichloride, Dimethylsilyl (indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (indenyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilyl (indenyl) ( And octamethyloctahydridodibenzfluorenyl) zirconium dichloride. In the present invention, the use of two or more kinds of metallocene compounds represented by the general formula (II) having different structures is not limited.

Such a bridged metallocene compound represented by the general formula (II) is disclosed in WO 01/27124.
Next, the component (C) will be specifically described.

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) an 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 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 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 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, 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. ]

(C-2) an organoaluminum oxy compound, and (c-3) a compound that reacts with component (A) and component (B) to form an ion pair,
At least one compound selected from the group consisting of
As compound (c-1), Japanese Patent Application Laid-Open No. 11-315109 and EP087 by the present applicant.
The compound disclosed in 4005A can be used without limitation.

(C-1) Among the organometallic compounds represented by the general formula (III), (IV) or (V), those represented by the general formula (III) are preferable, specifically, trimethylaluminum, triethyl Trialkylaluminum such as aluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide Dialkylaluminum halide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum Alkyl aluminum sesquihalides such as cyclochloride and ethylaluminum sesquibromide, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, alkylaluminum dihalides such as ethylaluminum dibromide, dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropyl Aluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, di-sec-nonylaluminumhigh Examples thereof include alkyl aluminum hydrides such as dride, dialkyl aluminum alkoxides such as dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum methoxide and diisobutyl aluminum ethoxide.

These are used singly or in combination of two or more.
(C-2) The organoaluminum oxy compound is preferably an aluminoxane prepared from trialkylaluminum or tricycloalkylaluminum, and particularly preferably an organoaluminum oxy compound prepared from trimethylaluminum or triisobutylaluminum. Such organoaluminum oxy compounds are used singly or in combination of two or more.

(C-3) As compounds that react with component (A) and component (B) to form ion pairs, JP-A-1-501950, JP-A-1-503636, 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 can be used without limitation.

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. Since a solid carrier component that reacts and contains a cocatalyst component can be easily prepared, it is preferable to use (c-2) an organoaluminum oxy compound as the component (C).

Next, the solid carrier (S) will be described in detail. The solid carrier (S) may be simply expressed as “component (S)”.
The solid carrier (S) that may be used in the present invention is an inorganic or organic compound and is a granular or fine particle solid, and the above-described components are converted into the following solid carrier. It is supported.

  Among these, examples of the inorganic compound include inorganic oxides such as porous oxides and inorganic chlorides, clays, clay minerals, and ion-exchangeable layered compounds. Preferably, the porous oxides and inorganic chlorides described below are used. Inorganic halides such as can be used.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or a composite or mixture containing these is used. For example, natural or synthetic zeolite, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, etc. Can be used. Of these, those containing SiO ₂ as the main component are preferred.

Note that the inorganic oxide contains 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.

Although such porous oxides have different properties depending on the type and production method, 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 to 1200 m. ² / g, preferably in the range of 100 to 1000 m ² / g, and the pore volume is in the range of 0.3 to ³⁰ cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. 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.

Also, clay, clay minerals or ion-exchangeable layered compounds include clays, clay minerals, ionic crystalline compounds 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 and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of 20 cc or more and a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, as measured by a mercury intrusion method. Here, the pore volume is measured for a pore radius of 20 to 3 × 10 ⁴ Å by a mercury intrusion method using a mercury porosimeter.

When a pore volume with a radius of 20 mm or more and a pore volume 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 that removes impurities adhering to the surface, a treatment that affects 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), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Is mentioned. These compounds are used alone or in combination of two or more. In addition, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO _2, etc. can also 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. Specifically, a (co) polymer produced mainly from an olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or vinylcyclohexane, styrene, divinyl. Examples thereof include (co) polymers and reactants produced with benzene as a main component, and modified products thereof.

It describes about the preparation method of the catalyst for olefin polymerization in this invention.
The first olefin polymerization catalyst according to the present invention is prepared by adding component (A), component (B) and component (C) to 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) Component (C) is added to the polymerization system. And then adding a contact product obtained by mixing and contacting the component (A) and the component (B) into 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 again to the polymerization system.
viii) A contact product obtained by mixing and contacting component (A) and component (C) is added to the polymerization system, then component (B) is added to the polymerization system, and component (C) is added again to the polymerization system. how to
ix) A contact product obtained by mixing and contacting component (B) and component (C) is added to the polymerization system, then component (A) is added to the polymerization system, and component (C) is added again to the polymerization system. Method 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 again added to the polymerization system. The method of adding in is mentioned. Among these, particularly preferable contact orders include i), ii), and v).

  The second olefin polymerization catalyst according to the present invention comprises 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) prepared by contacting the component (A), the component (C) and the component (S) 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). And then using the solid catalyst component (K2) prepared by contacting the contact product of component (B) and component (C) xiv) contacting component (C) and component (S), A) is contacted, and the solid catalyst component (K1), component (C), and component (S) prepared by contacting component (C) again is contacted, then component (B) is contacted, and component (B) is contacted again. Examples thereof include a method using a solid catalyst component (K2) prepared by contacting (C). Among these, particularly preferable contact order includes 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 contact order of each component is arbitrary, but as a preferable order, for example,
xv) A method in which component (S) is mixed and contacted with component (S), then contacted with component (A), and then contacted with component (B)
xvi) A method in which component (S) is mixed and contacted with component (S), then contacted with component (B), and then contacted with component (A)
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) A method of contacting the component (S) with the component (C), further contacting the component (C), and then contacting the component (A) and then the component (B) in this order,
xx) A method of contacting the component (S) with the component (C), further contacting the component (C), and then contacting the component (B) and then the component (A) in this order,
xxi) A method in which the component (S) is contacted with the component (C), the component (C) is further contacted, and then the contact mixture of the component (A) and the component (B) is contacted.
xxii) a method in which component (C) is mixed and contacted with component (S), and then a contact mixture of component (A), component (B) and component (C) is contacted;
xxiii) A method in which the component (S) is mixed and contacted with the component (S), then the contact mixture of the component (A) and the component (C) is contacted, and the component (B) is further contacted.
xxiv) A method in which component (C) is mixed and contacted with component (S), then a 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) A method of contacting in the order of the 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) A method of contacting in the order of the contact mixture,
xxvii) a method of contacting the component (S) with the component (C), further contacting the component (C), and then contacting the contact mixture of the component (A), the component (B) and the component (C);
xxviii) a method in which a mixture of component (A) and component (C) and a mixture of component (B) and component (C) are premixed and contacted 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 orders include xv), xvi), xvii), xxii), xxiii), and xxiv), and more preferably xvii) and xxii).

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 component (B)
In step (P3) including contact of component (S), component (S), component (A) and component (B), component (G) (g-1) polyalkylene oxide block, (g-2) At least one selected from higher aliphatic amides, (g-3) polyalkylene oxides, (g-4) polyalkylene oxide alkyl ethers, (g-5) alkyldiethanolamines and (g-6) polyoxyalkylene alkylamines. A compound may coexist. By allowing the component (G) to coexist, fouling during the polymerization reaction is suppressed, and the particle properties of the produced polymer are improved. Among the components (G), (g-1), (g-2), (g-3) and (g-4) are preferable, and (g-1) and (g-2) are particularly preferable.

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

  The contact between the component (C) and the component (S) is chemically combined by the reaction between the reaction site in the component (C) and the reaction site in the component (S), and the contact between the component (C) and the component (S) A contact 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. Is called. 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 carried out within a range of -50 to 200 ° C, preferably -50 to 100 ° C. The contact amount of component (A) and component (B) largely depends on the type and amount of component (C). In the case of component (c-1), all transitions in component (A) and component (B) Molar ratio of metal atom (M) to component (c-1) [(c-1)
/ M] is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000, and the component (c-2) is composed of the aluminum atom in the component (c-2) and the component (A ) And the molar ratio [(c-2) / M] to all transition metal atoms (M) in component (B) is usually 10 to 500,000.
The amount is preferably 20 to 100,000. Component (c-3) is a molar ratio [(c-3) / M] of component (c-3) and all transition metal atoms (M) in component (A) and component (B).
Is usually used in an amount of 1 to 10, preferably 1 to 5. The 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 arbitrarily determined from the molecular weight and molecular weight distribution of the polyolefin to be produced. As a preferred range, the ratio of the polymer produced from the component (A) and the component (B) [= Component (A) produced polymer amount / component (B) produced polymer amount] is usually 40/60 to 95/5, preferably 50/50 to 95/5, particularly preferably 60/40 to 95 /. 5. Here, it is preferable that the amount of the polymer derived from the component (A) is large because the macromonomer is generated from the component (A), and the amount of the generated amount is more advantageous for generating a long chain branch. is there. In addition, 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 between the component (S) and the component (C). It can be arbitrarily selected depending on the activity ratio expressed from the solid catalyst component in which the component (A) or the component (B) is contacted independently. In addition, the ratio of the polymer produced | generated from a component (A) and a component (B) can be calculated | required from the below-mentioned peak separation.

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 prepolymerized solid catalyst component can be prepared by prepolymerizing an olefin in the presence of the solid catalyst component, usually in an inert hydrocarbon solvent, and can be prepared by any of batch, semi-continuous and continuous methods. Can also be carried out under reduced pressure, normal pressure or increased pressure. Further, it is desirable that the prepolymerized solid catalyst component is produced by prepolymerization in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g, per 1 g of the solid catalyst component.

  After separating the prepolymerized solid catalyst component produced in the inert hydrocarbon solvent from the suspension, it may be suspended again in the inert hydrocarbon, and the olefin may be introduced into the resulting suspension. Further, olefin may be introduced after drying.

In the prepolymerization, the prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours. In the prepolymerization, an olefin similar to the olefin used in the polymerization described later is used, but an olefin mainly composed of ethylene is preferable.

  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 necessary, and an organoaluminum compound represented by general formula (III) in (c-1) is particularly preferred and used. When the component (C) is used, the molar ratio of the aluminum atom (Al-C) and the transition metal compound in the component (C) (component (C) / transition metal compound) is 0.1 to 10,000, Preferably it is used in an amount of 0.5 to 5000.

  The concentration of the solid catalyst component in the prepolymerization system is preferably 1 to 1000 g / liter, more preferably 10 to 500 g / liter, in a ratio of solid catalyst component / polymerization volume of 1 liter. At the time of prepolymerization, the component (G) can be present together 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) is brought into contact with the prepolymerized solid catalyst component once produced by prepolymerization. Also good. In this case, as the component (G) to be used, (g-1), (g-2), (g-3), (g-4) are preferable, and (g-1), (g-2) are particularly preferable. 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 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the solid catalyst component. Preferably, it is used in an amount of 0.4 to 5 parts by weight.

The mixed contact of the solid catalyst component and the component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same as described above.
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 a 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. The angle of repose of the dry prepolymerized catalyst is 50 ° or less, preferably 5 to 47 °, more preferably 10 to 45 °. When the angle of repose of the dry prepolymerized catalyst exceeds 50 °, the fluidity of the dry prepolymerized catalyst is lowered, and it may not be possible 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 used under the first catalyst for olefin polymerization according to the present invention. In the presence of the solid catalyst component according to the second and third inventions, it is preferable to use a suspension polymerization method or a gas phase polymerization method.

  Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and the like aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof. The olefin itself is used as a solvent. You can also

When the olefin polymerization is performed using the above-mentioned olefin polymerization catalyst, 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. In addition, 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 atmospheric pressure to 100 kg / cm ^2, preferably under conditions of normal pressure to 50 kg / cm ^2,
The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out 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.

  Moreover, the olefin supplied to the polymerization reaction in the present invention is one or more monomers selected from ethylene and olefins having 3 to 20 carbon atoms. Of these, at least one of the monomers 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-dodecene, Α-olefins such as 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1, 4, 5, Mention may be made of cyclic olefins such as 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc .; polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid, etc. can also be used. .

  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. I can do it. 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).

  Next, the ethylene polymer polymerized using the olefin polymerization catalyst of the present invention will be described. The ethylene polymer obtained by polymerizing ethylene or ethylene and an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst of the present invention has the following two characteristics.

Feature 1
Two or more peaks are observed by gel permeation chromatography (GPC), and the peak peak Log (M _Max ) of the maximum peak is
3.8 ≦ Log (M _Max ) ≦ 4.6, preferably 4.0 ≦ Log (M _Max ) ≦ 4.4
The peak intensity (H _Max ) of the largest peak is the peak intensity (H _second ) of the next largest peak.
H _Max ≧ 2 × H _second
Have the relationship.

The gel permeation chromatography (GPC) was calculated from a molecular weight distribution curve obtained by a water permeation chromatograph (High Temperature Size Exclusion Chromatograph) of a Waters model “Alliance GPC 2000”. As follows:

[Devices and conditions]
Measuring device: Gel permeation chromatograph allianceGPC2000 (Waters)
Analysis software: Chromatographic data system Empower (Waters)
Column: TSKgel GMH ₆ -HT x 2 + TSKgel GMH _6- HTL x 2
(Inner diameter 7.5mm x length 30cm, Tosoh Corporation)
Mobile phase: o-dichlorobenzene [= ODCB] (Wako Pure Chemical)
Detector: Differential refractometer (built-in device)
Column temperature; 140 ° C
Flow rate: 1.0mL / min
Injection volume: 500 μL
Sampling time interval: 1 second Sample concentration: 0.15% (w / v)
Molecular weight calibration monodisperse polystyrene (Tosoh Corp.) / molecular weight molecular weight 495 20600000 molecular weight distribution and various average molecular weight, Z. Crubisic, P. Rempp, H. Benoit, J. Polym. Sci., To B5, 753 (1967) Calculated as polyethylene molecular weight equivalent according to the general calibration procedure described.

In the present invention, the maximum peak obtained by GPC is defined as (i) the point having the maximum value in the GPC curve, or (ii) the point giving the maximum value or the minimum value in the second derivative of the GPC curve. When peaks overlap and are observed as a single peak or shoulder, it is effective to determine the peak based on the maximum and minimum values in the second derivative.

The peak intensity of the peak as determined by the above method represents a H, most peaks strong peak peak intensity of the H _Max, the peak intensity of the next largest peak when the H _Second, the relationship of H _Max ≧ 2 × H _second Meet.

In the ethylene-based polymer obtained in the present invention, the peak top Log of the normal maximum peak is usually used.
The peak giving (M _Max ) and H _Max is a peak due to the component (A), and the peak giving H _second is often the peak due to the component (B) or the third peak described later. .

  The polymer derived from the component (A) has a relatively small molecular weight on the GPC chart and has a double bond at the terminal, and thus contributes as one of the monomers (macromonomer) during polymerization, and thus long chain branching. Can be a chain. That is, the higher the proportion of the polymer due to the component (A) in the present polymer, the more advantageous for long-chain branch formation.

  Further, the molecular weight of the polymer due to the component (A) is advantageous in that the smaller one is advantageous for long-chain branching, but if it is too small, the mechanical strength of the molded body such as a film is lowered and the wall adhesion occurs during polymerization. On the contrary, if the molecular weight is large, it will not be incorporated as a macromonomer and it will be difficult to produce long chain branching, so an appropriate molecular weight is desirable.

The polymer is substantially composed of three peaks, and the first peak is a peak derived from the component (A) (sometimes referred to as “component (A) peak”). The peak of is a peak due to the component (B) (may be described as “component (B) peak”), and the third peak is when both the component (A) and the component (B) are used. Is the first peak generated (sometimes referred to as “third peak”). The abundance ratio of each peak can be clearly confirmed by separation according to the peak separation method described below.

  In addition, regarding the determination of the generation ratio when each peak is overlapped and observed as a single peak or a shoulder, if the separation is performed by the method described later, the peak is caused by the component (A) and the component (B). The presence of the peak as well as the third peak can be clearly confirmed.

The peak separation of the molecular weight curve (G1) of the ethylene polymer produced by the polymerization method according to the present invention is the component (A), component (C), component polymerized under the same polymerization conditions as the ethylene polymer. Molecular weight curve (G2) of ethylene polymer [may be described as a polymer containing only component (A)] obtained using a particulate catalyst comprising (S), component (B), component (C) , Component (S)
Using a molecular weight curve (G3) of an ethylene polymer [sometimes referred to as a polymer containing only component (B)] obtained using a particulate catalyst comprising: In addition, the molecular weight curve used what was obtained by GPC measurement mentioned above, and the calculation of peak separation used Excel (trademark) 97 by Microsoft Corporation.

[1] In the numerical data of (G1), (G2), (G3), log (molecular weight) is divided into 0.02 intervals, and the strength [dwt / d (log molecular weight) is set so that the area of the molecular weight curve becomes 1. ] Is standardized.
[2] A composite curve (G4) of (G2) and (G3) is created.
[3] The intensity at each molecular weight of (G2) and (G3) is arbitrarily set at a fixed ratio so that the absolute value of the difference between the intensity of (G1) and the intensity of (G4) at each molecular weight is 0.0004 or less. change. Note that, on the high molecular weight side, the absolute value of the difference between the intensity of (G1) and the intensity of (G4) becomes larger than 0.0004 due to the influence of the generated third peak. The strengths of (G2) and (G3) are changed so that the absolute value of the difference between the strength and the strength of (G4) is 0.0004 or less.
[4] The portion (G5) [(G1)-(G4)] where (G1) and (G4) do not overlap with each other on the high molecular weight side from the peak top is defined as the third peak. The polymer polymerization ratio Wa caused by the component (A), the polymer weight ratio Wb caused by the component (B), and the third peak weight ratio W ₃ are calculated as follows.
Wa = S (G2) / S (G4)
Wb = S (G3) / S (G4)
W ₃ = S (G5) / S (G4)
Here, S (G2) and S (G3) are the peak areas of (G2) and (G3) after the intensity is changed, and S (G4) and S (G5) are those of (G4) and (G5). It is the peak area.

Wa, Wb, and W ₃ can be arbitrarily determined from the molecular weight and molecular weight distribution of the polyolefin to be produced. Preferred ranges are 40% <Wa ≦ 95%, 5% <Wb ≦ 60%, 2% ≦ W ₃ ≦ 30. The particularly preferable range is 60% <Wa ≦ 95%, 5% <Wb.
≦ 40%, 2% ≦ W ₃ ≦ 20%. Here, the reason why the amount of the polymer derived from the component (A) is larger is preferable, as described above, but the larger amount of the macromonomer derived from the component (A) is more advantageous for generating a long chain branch. .

The second feature of this polymer is described below.
Feature 2
The following requirements [1] to [5] are satisfied at the same time.
[1] The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 100 g / 10.
[2] The density (d) is in the range of 875 to 970 kg / m ³ .
[3] Ratio [MT / η ^* (g / P)] of melt tension [MT (g)] at 190 ° C. and shear viscosity [η ^* (P)] at an angular velocity of 1.0 rad / sec at 200 ° C. Is in the range of 1.50 × 10 ^{−4 to} 9.00 × 10 ⁻⁴ .
[4] Zero shear viscosity [η ₀ (P)] at 200 ° C. and GPC-viscosity detector method (GPC-V
The weight average molecular weight (Mw) measured by ISCO) satisfies the following relational expression (Eq-1).
0.01 × 10 ⁻¹³ × Mw ^3.4 ≦ η ₀ ≦ 4.5 × 10 ⁻¹³ × Mw ^3.4・ ・ (Eq-1)
In addition, the ethylene polymer obtained in the present invention exhibits the effects described later in most plastic industrial applications as long as the above requirements [1] to [4] are satisfied. From the viewpoint that certain problems can be reliably prevented, the above requirement [1]
It is preferable that the following requirement [5] is simultaneously satisfied in addition to [4].
[5] Intrinsic viscosity ([η] (dl / g)) measured in 135 ° C. decalin and weight measured by GPC-viscosity detector method (GPC-VISCO) of the ethylene polymer obtained in the present invention The average molecular weight (Mw) satisfies the following relational expression (Eq-2).
0.80 × 10 ⁻⁴ × Mw ^0.776 ≦ [η] ≦ 1.65 × 10 ⁻⁴ × Mw ^0.776・ ・ (Eq-2)
The significance, measurement method, and preferred range of each of the above requirements [1] to [5] are fully explained by the description in WO 2006/080578 by the present applicant.

The ethylene polymer obtained in the present invention may be pelletized by the following method. (1) A method of mechanically blending an ethylene-based polymer and other components added as required using an extruder, a kneader, etc., and cutting the mixture into a predetermined size.
(2) Ethylene-based polymer and other components added as required are suitable good solvents (for example,
In hydrocarbon solvents such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene, and then the solvent is removed, and then mechanically blended using an extruder, kneader, etc., to a predetermined size. How to cut.

  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, the resin composition containing the thermoplastic resin [R] 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.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
The compounds described in the synthesis examples are 270 MHz ¹ H-NMR (JEOL GSH-270), FD-mass spectrometry (FD-MS) (JEOL SX-102A), gas chromatograph-mass spectrometry (GC-MS). (Shimadzu GCMS-QP5050A) and the like. The physical properties of the polymers obtained by the production methods described in the examples and comparative examples were measured by adding Irganox 1076 (Ciba Specialty Chemicals) 0.1% by weight and Irgafos168 (Ciba Specialty Chemicals) 0.1% by weight as heat stabilizers. Using a Labo plast mill manufactured by Toyo Seiki Seisakusho, melt-kneaded for 5 minutes at a resin temperature of 180 ° C. and a rotation speed of 50 rpm. What was cooled for 5 minutes under the conditions of a cooling pressure of 100 kg / cm ² was used. The physical properties of the polymer were determined by the equipment and methods described in the above specification.

[Intrinsic viscosity ([η])]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of granulated pellets are dissolved in 15 ml of decalin, and the specific viscosity η _sp is 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 is measured in the same manner. This dilution operation is further repeated twice, and the value of η _sp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity.
[Η] = lim (η _sp / C) (C → 0)

[Synthesis Example 1]
[Preparation of dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (A1)]
<Step.1> Synthesis of (3-n-butylcyclopentadienyl) chlorodimethylsilane
50 ml of THF was added to 30.1 g (61.5 mmol) of 25 wt% -butylcyclopentadiene / THF solution. The solution was cooled to 0 ° C., and 38.4 ml (58.4 mol) of a 1.52 M-n-butyllithium / hexane solution was added dropwise.
The mixture was stirred at room temperature for 2 hours and added dropwise to 14.3 g (110 mmol) of dimethylsilyl dichloride and 50 ml of THF at −78 ° C. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, the filtrate was distilled under reduced pressure. Distillation under reduced pressure was performed to obtain 8.09 g (yield 64%) of (3-n-butylcyclopentadienyl) chlorodimethylsilane. The target product was identified by GC-MS. GC-MS; 214 (MS)

<Step.2> Dimethylsilyl (3-n-butylcyclopentadienyl) (cyclopentadiene)
Nyl) synthesis
50 ml of THF was added to 8.8 ml (16.6 mmol) of 2M-sodium cyclopentadienide in THF and cooled to -78 ° C. 1.89 g (8.8 mmol) of (3-n-butylcyclopentadienyl) chlorodimethylsilane was dissolved in 20 ml of THF and added dropwise to the reactor. After stirring at room temperature for 2 hours, the mixture was stirred at 50 ° C. for 2 hours. The completion of the reaction was confirmed by TLC, and the reaction was stopped by adding water at 0 ° C. Extraction was performed with hexane, and the organic layer was washed with saturated brine. After drying with magnesium sulfate, the solution obtained after filtration was concentrated under reduced pressure. Distillation under reduced pressure was performed to obtain 1.07 g (yield 50%) of dimethylsilyl (3-n-butylcyclopentadienyl) (cyclopentadienyl). ^The target product was identified by ¹ H-NMR and GC-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.0-6.0 (br, 7H), 3.2 (d, 1H), 2.9 (d, 1H), 2.3 (t, 2H), 1.4 (m, 4H) 0.9 ( t, 3H), 0.1 (t, 3H), -0.2ppm (s, 3H); GC-MS; 244 (MS)

<Step.3> Synthesis of dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (A1) Dimethylsilyl (3-n-butylcyclopentadienyl) (cyclopentadienyl) 0.58 g (2.38 mmol) was dissolved in 30 ml of diethyl ether. After cooling to −78 ° C., 3.16 ml (4.99 mmol) of 1.57M-nBuLi was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 6 ml of hexane. The obtained white solid was suspended in 60 ml of hexane, -78 ° C
Below, 500 mg (2.15 mmol) of zirconium tetrachloride was added. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure to obtain 510 mg of a crude product. The solid obtained after washing with diethyl ether and pentane was dried under reduced pressure to obtain 190 mg (yield 20%) of dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (A1). It was. ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 6.9 (d, 2H), 6.6 (s, 1H), 5.9 (t, 3H), 5.5 (s, 1H), 2.6 (m, 2H), 1.4 (m , 2H), 1.3 (m, 2H), 0.9 (t, 3H), 0.8 ppm (m, 3H); FD-MS; 404 (MS)

〔合成例２〕
［ジメチルシリレン（3−n−プロピルシクロペンタジエニル）（シクロペンタジエニル）ジルコニウムジクロリド（Ａ２）の調製］

[Synthesis Example 2]
[Preparation of dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A2)]

<Step.1> Synthesis of chloro (cyclopentadienyl) dimethylsilane 100 ml of THF was added to 14.3 g (110 mmol) of dimethylsilyl dichloride and cooled to -78 ° C. 38.7 ml (77.4 mmol) of 2M-sodium cyclopentadiene in THF was added dropwise over 30 minutes, the temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration under reduced pressure was performed, and sodium chloride was removed by filtration. After washing with hexane, hexane in the filtrate was distilled under reduced pressure, and the resulting chloro (cyclopentadienyl) dimethylsilane was used in the next step.

<Step.2> Dimethylsilyl (3-n-propylcyclopentadienyl) (cyclopentadienyl)
Synthesis)
100 ml of THF was added to 2.16 g (20 mmol) of n-propylcyclopentadiene and cooled to -78 ° C. 13.3 ml (22 mmol) of 1.57M-n-butyllithium / hexane solution was slowly added dropwise and stirred at room temperature for 3 hours. The reactor was cooled again to −78 ° C., and 3.97 g (25 mmol) of chloro (cyclopentadienyl) dimethylsilane was dissolved in 20 ml of THF and added dropwise to the reactor. After stirring for 18 hours at room temperature, the completion of the reaction was confirmed by TLC. The reaction was stopped by adding water at 0 ° C. Extraction was performed with hexane, and the organic layer was washed with saturated brine. After drying with magnesium sulfate, the solution obtained after filtration was concentrated under reduced pressure. Purification by silica gel column chromatography (solvent; hexane: triethylamine = 98: 2 v / v) and vacuum distillation, 1.73 g (yield) of dimethylsilyl (3-n-propylcyclopentadienyl) (cyclopentadienyl) 38%). ^The target product was identified by ¹ H-NMR and GC-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.0-6.0 (br, 7H), 3.0 (s, 1H), 2.9 (s, 1H), 2.3 (m, 2H), 1.6 (m, 2
H) 0.9 (t, 3H), 0.1 (t, 3H), -0.2ppm (s, 3H); GC-MS; 230 (MS)

<Step.3> Dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopenta
Synthesis of dienyl) zirconium dichloride (A2) 0.90 g (3.9 mmol) of dimethylsilyl (3-n-propylcyclopentadienyl) (cyclopentadienyl) was dissolved in 40 ml of diethyl ether. After cooling to −78 ° C., 5.09 ml (8.0 mmol) of 1.57 M-n-butyllithium / hexane solution was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 13 ml of hexane. The obtained white solid was suspended in 50 ml of hexane, and 820 mg (3.5 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure and washed with pentane. The obtained solid was dried under reduced pressure to obtain 210 mg (yield 14%) of dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A2). ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 7.1-6.9 (m, 2H), 6.6 (s, 1H), 6.0-5.8 (m, 3H), 5.5 (s, 1H), 2.6 (m, 2H) , 1.5 (m, 2H), 0.9 (t, 3H), 0.8-0.7ppm (d, 6H); FD-MS; 388 (MS)

〔合成例３〕
［ジメチルシリレン(シクロペンタジエニル)(3−n−オクチルシクロペンタジエニル)ジルコニウムジクロリド（Ａ３）の調製］

[Synthesis Example 3]
[Preparation of dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride (A3)]

<Step.1> Synthesis of n-octylcyclopentadienide
100 ml of THF was added to 50 ml (100 mmol) of a THF solution of 2M-sodium cyclopentadienide. The solution was cooled to −78 ° C., and a THF solution of 19.3 g (100 mmol) of 1-bromooctane was added dropwise. Further, 11.4 g (100 mol) of 1,3-dimethyl-2-imidazolidinone was added dropwise and stirred at −78 ° C. The mixture was stirred at room temperature for 24 hours and then cooled to 0 ° C. The reaction was terminated with 1N hydrochloric acid, hexane was added, and the mixture was washed successively with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting solution was purified by distillation under reduced pressure to obtain 6.7 g (37.5 mmol) of n-octylcyclopentadiene as a target product. The target product was identified by GC-MS. GC-MS; 178 (MS)

<Step.2> Synthesis of dimethylsilyl (cyclopentadienyl) (3-n-octylcyclopentadienyl)
100 ml of THF was added to 5.34 g (30 mmol) of n-octylcyclopentadiene. The mixture was cooled to −78 ° C., and 18.9 ml (30 mmol) of a 1.58 M-n-butyllithium / hexane solution was added dropwise. The mixture was stirred at room temperature for 2 hours, and dropwise added to 14.3 g (110 mmol) of dimethylsilyl dichloride and 50 ml of THF at −78 ° C. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, hexane in the filtrate was distilled under reduced pressure to obtain chlorodimethyl (3-n-octylcyclopentadienyl) silane. After identifying the target product by GC-MS, 100 ml of THF was added to the reactor and cooled to -78 ° C. 15 ml (30 mmol) of 2M-sodium cyclopentadienide / THF solution was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. After confirming the progress of the reaction, water was added at 0 ° C. to stop the reaction. Extraction was performed with hexane, and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. The organic layer was dried over magnesium sulfate and filtered, and the resulting solution was concentrated under reduced pressure. Purification by silica gel column chromatography (solvent; hexane: triethylamine = 98: 2 v / v) and 3.5 g of the target product, dimethylsilyl (cyclopentadienyl) (3-n-octylcyclopentadienyl) 39%). The target product was identified by GC-MS. GC-MS; 300 (MS)

<Step.3> Synthesis of dimethylsilylene (cyclopentadienyl) (3-n- octylcyclopentadienyl) zirconium dichloride (A3) Dimethylsilyl (cyclopentadienyl) (3-n-octylcyclopentadienyl) 3.1 g (10 mmol) was dissolved in 80 ml of diethyl ether. After cooling to −78 ° C., 13.1 ml (20.5 mmol) of a 1.57 M-n-butyllithium hexane solution was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. Concentrated under reduced pressure and washed with hexane. The obtained solid was suspended in 80 ml of hexane, and 1.96 g (8.4 mmol) of zirconium tetrachloride was added at −78 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. The filtrate was concentrated under reduced pressure, washed with a mixed solvent of diethyl ether and pentane, the obtained solid was dried under reduced pressure, and dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride (A3 240 mg (yield 5%) was obtained. ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard): 7.0 (s, 1H), 6.9 (s, 1H), 6.5 (s, 1H), 5.9-5.8 (m, 3H), 5.5 (s, 1H), 2.7 (m, 2H), 1.5 (m, 2H), 1.2 (m, 10H), 0.8 (t, 3H), 0.7ppm (m, 6H); FD-MS; 458 (MS)

〔合成例４〕
［ジメチルシリレン（3−ブチル−2,4,5−トリメチルシクロペンタジエニル）（シクロペンタジエニル）ジルコニウムジクロリド（Ａ４）の調製］

[Synthesis Example 4]
[Preparation of dimethylsilylene (3-butyl-2,4,5-trimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A4)]

<Step.1> Synthesis of 2-butyl-1,3,4-trimethylcyclopentadiene 259 g of polyphosphoric acid was added, and 50.7 g of sec-butyl methacrylate was added dropwise with stirring at 40 ° C. The mixture was stirred for 1 hour, and the temperature was raised to 80 ° C. After stirring for 1 minute, cooling was performed, and an aqueous sodium hydroxide solution was added to make the solution slowly alkaline. Extraction was performed with hexane and diethyl ether, and the organic layer was dried over sodium sulfate. The solution was concentrated under reduced pressure and purified by distillation under reduced pressure. To 6.8 g of the obtained 2,3,5-trimethylcyclopent-2-enone, 75 ml of diethyl ether was added. Cool to -78 degrees, and add 0.5 ml of 0.84M-n-butylmagnesium chloride / THF solution
It was added dropwise over a period of minutes. The temperature was gradually raised to room temperature, the mixture was stirred for 24 hours, and saturated aqueous ammonium chloride solution was added dropwise at -10 ° C. The mixture was stirred for 10 minutes, 20% aqueous sulfuric acid solution was added, and the organic layer was extracted with diethyl ether. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and concentrated under reduced pressure. Purification by vacuum distillation and silica gel chromatography (solvent: hexane)
5.2 g of butyl-1,3,4-trimethylcyclopentadiene was obtained. The target product was identified by GC-MS. GC-MS; 164 (MS)

<Step.2> Synthesis of (2-Butyl-1,3,4-trimethylcyclopentadienyl) (cyclopentadienyl) chlorodimethylsilane
100 ml of THF was added to 1.6 g (12.9 mmol) of 2-butyl-1,3,4-trimethylcyclopentadiene. After cooling to 0 ° C., 8.6 ml (13.5 mmol) of a hexane solution of 1.57M-n-butyllithium was added dropwise. The mixture was stirred at room temperature for 2 hours, and 2.0 g (15.5 mmol) of dimethylsilyl dichloride and 50 ml of THF were added to -78.
It was dripped at ° C. The temperature was gradually raised, and the mixture was stirred at room temperature for 8 hours to obtain a transparent solution. Concentration was performed under reduced pressure, and insoluble materials were removed by filtration. After washing with hexane, hexane in the filtrate was distilled under reduced pressure. Distillation under reduced pressure was performed to remove dimethylsilyl dichloride. 100 ml of THF was added and cooled to -78 ° C. 4.7 ml (9.4 mmol) of 2M-sodium cyclopentadienide / THF solution
) Was gradually added dropwise and stirred at room temperature for 24 hours. The reaction was stopped by adding water at 0 ° C., and the organic layer was extracted with hexane. The extract was washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and filtered. The solution was concentrated under reduced pressure and purified by silica gel column chromatography (solvent: hexane: triethylamine = 98: 2 v / v). The target product (3-butyl-2,4,5-
4.6 g (16.1 mmol) of trimethylcyclopentadienyl) (cyclopentadienyl) chlorodimethylsilane was obtained. The target product was identified by GC-MS. GC-MS; 286 (MS)

<Step.2> Dimethylsilylene (3-butyl-2,4,5-trimethylcyclopentadienyl)
Synthesis of ( cyclopentadienyl) zirconium dichloride (A4) (3-butyl-2,4,5-trimethylcyclopentadienyl) (cyclopentadienyl) chlorodimethylsilane 0.53 g (1.9 mmol) in 50 ml of diethyl ether Dissolved. The mixture was cooled to −78 ° C., and 0.76 ml (1.7 mmol) of a hexane solution of 1.57M-n-butyllithium was added dropwise. The temperature was gradually raised, and the mixture was stirred at room temperature for 24 hours. The solution was concentrated under reduced pressure and washed 3 times with 6 ml of hexane. The obtained solid was suspended in hexane 50 ml, and zirconium tetrachloride 400 mg (1.7 mmol) at −78 ° C.
Was added. The temperature was gradually raised and the mixture was stirred at room temperature for 24 hours. Filter and wash with hexane to remove salts. It was dissolved in diethyl ether, and pentane was added while stirring to precipitate gradually. 30 mg of dimethylsilylene (3-butyl-2,4,5-trimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A4) was washed with pentane and the resulting solid was dried by concentration under reduced pressure. Obtained. ^The target product was identified by ¹ H-NMR and FD-MS.
¹ H-NMR (CDCl ₃ , TMS standard); 6.9 (s, 2H), 5.6 (s, 2H), 5.6 (2H), 2.4-2.2 (m, 2H), 2.0-1.8 (m, 9H), 1.5 -1.2 (m, 4H), 0.9-0.7 (m, 9H); FD-MS; 444 (MS)

〔合成例１１〕
下記構造式で表される（Ｂ１）は、特開平４−６９３９４号公報に記載の方法に基づいて合成した。

[Synthesis Example 11]
(B1) represented by the following structural formula was synthesized based on the method described in JP-A-4-69394.

〔合成例１２〕
下記構造式で表される（Ｂ２）は、ＥＰ３５１３９２パンフレットに記載の方法に基づいて合成した。

[Synthesis Example 12]
(B2) represented by the following structural formula was synthesized based on the method described in the pamphlet of EP351392.

〔合成例１３〕
下記構造式で表される（Ｂ３）は、特開２０００−２１２１９４号公報に記載の方法に基づいて合成した。

[Synthesis Example 13]
(B3) represented by the following structural formula was synthesized based on the method described in JP-A No. 2000-212194.

〔合成例１４〕
下記構造式で表される（Ｂ４）は、ＥＰ９５５３０５パンフレットに記載の方法に基づいて合成した。

[Synthesis Example 14]
(B4) represented by the following structural formula was synthesized based on the method described in the EP955305 pamphlet.

〔合成例１５〕
下記構造式で表される（Ｂ５）は、特開２００５−２００４５１号公報に記載の方法に基づいて合成した。

[Synthesis Example 15]
(B5) represented by the following structural formula was synthesized based on the method described in JP-A-2005-200451.

〔合成例１６〕
下記構造式で表される（Ｂ６）は、特開２００４−１６８７４４号公報に記載の方法に基づいて合成した。

[Synthesis Example 16]
(B6) represented by the following structural formula was synthesized based on the method described in JP-A No. 2004-168744.

［実施例１］
〔固体成分（Ｓ）の調製〕
内容積２６０Ｌの攪拌機付き反応器に、窒素雰囲気下、２５０℃で１０時間乾燥したシリカ（ＳｉＯ₂：平均粒子径６０μｍ）１０ｋｇを９０．５Ｌのトルエンに懸濁した後、
０〜５℃まで冷却した。この懸濁液にメチルアルモキサンのトルエン溶液（Ａｌ原子換算で３．０ｍｍｏｌ／ｍＬ）４５．５Ｌを３０分間かけて滴下した。この際、系内の温度を０〜５℃に保った。引き続き０〜５℃で３０分間反応させた後、約１．５時間かけて９５〜１００℃まで昇温して、引き続き９５〜１００℃で４時間反応させた。その後常温まで降温して、上澄み液をデカンテーションにより除去した。このようにして得られた固体成分をトルエンで２回洗浄した後、トルエンを加えて全量１２９Ｌとし、固体成分（Ｓ）のトルエンスラリーを調製した。得られた固体成分の一部を採取し、濃度を調べたところ、スラリー濃度：９６．５ｇ／Ｌ、Ａｌ濃度：０．４８９ｍｏｌ／Ｌであった。

[Example 1]
[Preparation of solid component (S)]
After suspending 10 kg of silica (SiO ₂ : average particle size 60 μm) dried at 250 ° C. for 10 hours under a nitrogen atmosphere in 90.5 L of toluene in a reactor with an internal volume of 260 L,
Cooled to 0-5 ° C. To this suspension, 45.5 L of a toluene solution of methylalumoxane (3.0 mmol / mL in terms of Al atom) was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 to 5 ° C. Subsequently, the mixture was reacted at 0 to 5 ° C. for 30 minutes, then heated to 95 to 100 ° C. over about 1.5 hours, and then reacted at 95 to 100 ° C. for 4 hours. Thereafter, the temperature was lowered to room temperature, and the supernatant was removed by decantation. The solid component thus obtained was washed twice with toluene, and then toluene was added to make a total amount of 129 L to prepare a toluene slurry of the solid component (S). A part of the obtained solid component was collected and examined for concentration. As a result, the slurry concentration was 96.5 g / L and the Al concentration was 0.489 mol / L.

[Preparation of solid catalyst component (Y-1)]
50 mL of toluene was placed in a 200 mL glass flask purged with nitrogen, and the toluene slurry of the solid component (S) prepared above (1.0 g in terms of solid part) was charged. Next, 7.6 mL of a metallocene compound (dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A2)) in toluene (0.002 mmol / mL in terms of Zr atom) and metallocene 5.1 mL of a toluene solution (0.002 mmol / mL in terms of Zr atom) of the compound (B1) was mixed and dropped (molar ratio (A2) / (B1) = 60/40), and the mixture was reacted at room temperature for 1 hour. Zr was not detected in the supernatant toluene after the reaction for 1 hour. Next, the supernatant was removed by decantation and washed twice with heptane to obtain a 50 ml heptane slurry (solid catalyst component Y-1). A part of the resulting heptane slurry of the solid catalyst component (Y-1) was collected to examine the concentration. As a result, the Zr concentration was 0.046 mg / mL, and the Al concentration was 2.6 mg / mL.

Polymerization Purified heptane (500 mL) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, and ethylene was circulated to saturate the liquid phase and gas phase with ethylene. Next, 10 mL of 1-hexene and 0.375 mmol of triisobutylaluminum were added, and further 20 mg of solid catalyst component (Y-1) was charged in terms of solid component, and the temperature was raised to 80 ° C., and 0.78 MPa · Polymerization was conducted at G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 76.25 g of an ethylene / 1-hexene copolymer. The GPC analysis results and various physical properties of the obtained polymer are shown in Table 1, and the GPC chart is shown in FIG.

[Example 2]
Polymerization The polymerization in Example 1 was carried out in the same manner as in Example 1 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.1 vol%) was used instead of ethylene gas. The obtained polymer was vacuum-dried for 10 hours to obtain 75.45 g of an ethylene / 1-hexene copolymer. Table 1 shows the GPC analysis results and various physical properties of the polymer obtained.

[Example 3]
Polymerization A nitrogen-substituted SUS autoclave with an internal volume of 2 liters was charged with 250 g of NaCl, and the contents were vacuum-dried at 100 ° C. for 90 minutes. Next, the inside of the autoclave was returned to normal pressure with 1-butene / ethylene mixed gas (1-butene concentration: 4 vol%), the internal temperature was set to 75 ° C., and 0.75 mmol of triisobutylaluminum was added under the mixed gas flow, Further, 34.4 mg of the solid catalyst component (Y-1) was charged in terms of solid component, and polymerization was performed at 0.78 MPa · G and 80 ° C. for 90 minutes. The obtained contents were washed with sufficient water to completely remove NaCl, and then the polymer was vacuum-dried for 10 hours to obtain 68.86 g of an ethylene / 1-butene copolymer. Table 1 shows the GPC analysis results and various physical properties of the polymer obtained.

[Example 4]
[Preparation of solid catalyst component (Y-2)]
50 mL of toluene was put into a 200 mL glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S) prepared in Example 1 was charged. Next, 7.6 mL of a metallocene compound (dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride (A1)) in toluene (0.002 mmol / mL in terms of Zr atom) and metallocene 5.1 mL of a toluene solution of compound (B1) (0.002 mmol / mL in terms of Zr atom) was mixed and added dropwise (molar ratio of (A1) / (B1) = 60/40), and reacted at room temperature for 1 hour. Zr was not detected in the supernatant toluene after the reaction for 1 hour. Next, the supernatant was removed by decantation and washed twice with heptane to obtain a 50 ml heptane slurry (solid catalyst component Y-2). A part of the resulting heptane slurry of the solid catalyst component (Y-2) was collected to examine the concentration. As a result, the Zr concentration was 0.034 mg / mL and the Al concentration was 2.1 mg / mL.

Polymerization The polymerization was conducted in the same manner as in Example 1, except that 15 mg of the solid catalyst component (Y-2) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 60.22 g of an ethylene / 1-hexene copolymer. The GPC analysis results and various physical properties of the obtained polymer are shown in Table 1, and the GPC chart is shown in FIG.

[Example 5]
Polymerization Polymerization in Example 4 was performed in the same manner as in Example 4 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.05 vol%) was used instead of ethylene gas. The obtained polymer was vacuum-dried for 10 hours to obtain 55.09 g of an ethylene / 1-hexene copolymer. The GPC analysis results and various physical properties of the obtained polymer are shown in Table 1, and the GPC chart is shown in FIG.

[Example 6]
Polymerization Polymerization in Example 3 was performed in the same manner as in Example 3, except that 34.4 mg of solid catalyst component (Y-2) was used instead of solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 41.59 g of an ethylene / 1-butene copolymer. The GPC analysis results and various physical properties of the obtained polymer are shown in Table 1, and the GPC chart is shown in FIG.

[Example 7]
[Preparation of solid catalyst component (Y-3)]
In the preparation of the solid catalyst component (Y-1) of Example 1, the metallocene compound (A3) was used instead of the metallocene compound (A2), and the reaction molar ratio of the metallocene compound (A3) and the metallocene compound (B1) was ( A solid catalyst component (Y-3) was synthesized in the same manner as the solid catalyst component (Y-1) except that A3) / (B1) = 80/20 (molar ratio). Zr was not detected in the supernatant toluene after the reaction for 1 hour. Further, when a portion of the resulting heptane slurry of the solid catalyst component (Y-3) was collected to examine the concentration, the Zr concentration was 0.049 mg / mL, and the Al concentration was 3.2 mg / mL.

Polymerization The polymerization was conducted in the same manner as in Example 1 except that 30 mg of the solid catalyst component (Y-3) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 80.02 g of an ethylene / 1-hexene copolymer. The GPC analysis results and various physical properties of the obtained polymer are shown in Table 1, and the GPC chart is shown in FIG.

[Example 8]
Polymerization Polymerization in Example 7 was performed in the same manner as in Example 7, except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.1 vol%) was used instead of ethylene gas. The obtained polymer was vacuum-dried for 10 hours to obtain 84.69 g of an ethylene / 1-hexene copolymer. Table 2 shows the results of GPC analysis and various physical properties of the polymer obtained.

[Example 9]
[Preparation of solid catalyst component (Y-4)]
In the preparation of the solid catalyst component (Y-1) of Example 1, the metallocene compound (A4) was used instead of the metallocene compound (A2), and the reaction molar ratio of the metallocene compound (A4) and the metallocene compound (B1) was (A4). ) / (B1) = 70/30 (molar ratio) A solid catalyst component (Y-4) was synthesized in the same manner as the solid catalyst component (Y-1). Zr was not detected in the supernatant toluene after the reaction for 1 hour. A part of the resulting heptane slurry of the solid catalyst component (Y-4) was collected to examine the concentration. As a result, the Zr concentration was 0.038 mg / mL and the Al concentration was 2.1 mg / mL.

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1, except that the solid catalyst component (Y-4) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 76.04 g of an ethylene / 1-hexene copolymer. The GPC analysis results and various physical properties of the obtained polymer are shown in Table 2, and the GPC chart is shown in FIG.

[Example 10]
Polymerization Polymerization in Example 9 was performed in the same manner as in Example 9 except that a hydrogen-ethylene mixed gas (hydrogen concentration: 0.1 vol%) was used instead of ethylene gas. The obtained polymer was vacuum-dried for 10 hours to obtain 80.33 g of an ethylene / 1-hexene copolymer. Table 2 shows the results of GPC analysis and various physical properties of the polymer obtained.

[Example 11]
Polymerization Polymerization in Example 3 was performed in the same manner as in Example 3, except that the solid catalyst component (Y-4) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 51.57 g of an ethylene / 1-butene copolymer. Table 2 shows the results of GPC analysis and various physical properties of the polymer obtained.

[Example 12]
[Preparation of solid catalyst component (Y-5)]
In the preparation of the solid catalyst component (Y-1) of Example 1, the reaction molar ratio of the metallocene compound (A2) and the metallocene compound (B1) was changed to (A2) / (B1) = 60/40 (molar ratio). The solid catalyst component (Y-5) was synthesized in the same manner as the solid catalyst component (Y-1) except that (A2) / (B1) = 45/55 (molar ratio). Zr was not detected in the supernatant toluene after the reaction for 1 hour. Further, when a portion of the obtained heptane slurry of the solid catalyst component (Y-5) was collected to examine the concentration, the Zr concentration was 0.038 mg / mL and the Al concentration was 2.1 mg / mL.

Polymerization In the polymerization of Example 3, the solid catalyst component (Y-5) was used instead of the solid catalyst component (Y-1), and instead of the 1-butene / ethylene mixed gas (1-butene concentration: 4 vol%). The same procedure as in Example 3 was performed except that 1-butene / ethylene mixed gas (1-butene concentration: 7 vol%) was used. The obtained polymer was vacuum-dried for 10 hours to obtain 46.65 g of an ethylene / 1-butene copolymer. Table 2 shows the results of GPC analysis and various physical properties of the polymer obtained.

[Example 13]
Polymerization In the polymerization of Example 6, except that 1-butene / ethylene mixed gas (1-butene concentration: 7 vol%) was used instead of 1-butene / ethylene mixed gas (1-butene concentration: 4 vol%), The same method as in Example 6 was used. The obtained polymer was vacuum-dried for 10 hours to obtain 51.85 g of an ethylene / 1-butene copolymer. Table 2 shows the results of GPC analysis and various physical properties of the polymer obtained.

[Example 14]
[Preparation of solid catalyst component (Y-6)]
In the preparation of the solid catalyst component (Y-2) of Example 4, the metallocene compound (B2) was used instead of the metallocene compound (B1), and the reaction molar ratio of the metallocene compound (A1) to the metallocene compound (B2) was (A1). ) / (B2) = 30/70 (molar ratio) A solid catalyst component (Y-6) was synthesized in the same manner as the solid catalyst component (Y-2). Zr was not detected in the supernatant toluene after the reaction for 1 hour. The obtained solid catalyst component (Y
When a part of the heptane slurry of −6) was collected to examine the concentration, the Zr concentration was 0.036 mg / mL and the Al concentration was 2.3 mg / mL.

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1, except that the solid catalyst component (Y-6) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 74.38 g of an ethylene / 1-hexene copolymer. Table 2 shows the results of GPC analysis and various physical properties of the polymer obtained.

[Example 15]
[Preparation of solid catalyst component (Y-7)]
In the preparation of the solid catalyst component (Y-2) of Example 4, the metallocene compound (B3) was used instead of the metallocene compound (B1), and the reaction molar ratio of the metallocene compound (A1) to the metallocene compound (B3) was (A1). ) / (B3) = 70/30 (molar ratio) The solid catalyst component (Y-7) was synthesized in the same manner as the solid catalyst component (Y-2). Zr was not detected in the supernatant toluene after the reaction for 1 hour. Further, when a portion of the resulting heptane slurry of the solid catalyst component (Y-7) was collected to examine the concentration, the Zr concentration was 0.035 mg / mL and the Al concentration was 2.2 mg / mL.

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1, except that the solid catalyst component (Y-7) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 121.34 g of an ethylene / 1-hexene copolymer. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 16]
[Preparation of solid catalyst component (Y-8)]
In the preparation of the solid catalyst component (Y-2) of Example 4, a solid was prepared in the same manner as the solid catalyst component (Y-2) except that the metallocene compound (B4) was used instead of the metallocene compound (B1). A catalyst component (Y-8) was synthesized. Zr was not detected in the supernatant toluene after the reaction for 1 hour. A part of the obtained heptane slurry of the solid catalyst component (Y-8) was sampled to examine the concentration. As a result, the Zr concentration was 0.034 mg / mL and the Al concentration was 2.3 mg / mL.

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1, except that the solid catalyst component (Y-8) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 75.51 g of an ethylene / 1-hexene copolymer. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 17]
[Preparation of solid catalyst component (Y-9)]
In the preparation of the solid catalyst component (Y-2) of Example 4, the metallocene compound (B5) was used instead of the metallocene compound (B1), and the reaction molar ratio of the metallocene compound (A1) to the metallocene compound (B5) was (A1). ) / (B5) = 55/45 (molar ratio) The solid catalyst component (Y-9) was synthesized in the same manner as the solid catalyst component (Y-2). Zr was not detected in the supernatant toluene after the reaction for 1 hour. Further, when a portion of the obtained heptane slurry of the solid catalyst component (Y-9) was collected to examine the concentration, the Zr concentration was 0.034 mg / mL and the Al concentration was 2.3 mg / mL.

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1, except that the solid catalyst component (Y-9) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 113.72 g of an ethylene / 1-hexene copolymer. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 18]
[Preparation of solid catalyst component (Y-10)]
In the preparation of the solid catalyst component (Y-2) of Example 4, the metallocene compound (B6) was used instead of the metallocene compound (B1), and the reaction molar ratio of the metallocene compound (A1) and the metallocene compound (B6) was (A1). ) / (B6) = 55/45 (molar ratio) The solid catalyst component (Y-10) was synthesized in the same manner as the solid catalyst component (Y-2). Zr was not detected in the supernatant toluene after the reaction for 1 hour. Further, when a portion of the resulting heptane slurry of the solid catalyst component (Y-10) was collected to examine the concentration, the Zr concentration was 0.036 mg / mL, and the Al concentration was 2.3 mg / mL.

Polymerization In the polymerization of Example 1, the solid catalyst component (Y-10) was used instead of the solid catalyst component (Y-1), and the polymerization temperature and the amount of 1-hexene added were 80 ° C., 10 ml to 70 ° C., 30 ml. The procedure was the same as in Example 1 except that the change was made. The obtained polymer was vacuum-dried for 10 hours to obtain 116.03 g of an ethylene / 1-hexene copolymer. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 19]
[Preparation of solid catalyst component (X-11)]
50 mL of toluene was put into a 200 mL glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S) prepared in Example 1 was charged. Next, 12.7 mL of a toluene solution (0.002 mmol / mL in terms of Zr atom) of the metallocene compound (B1) was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with heptane to obtain a 100 ml heptane slurry (solid catalyst component X-11). A part of the resulting heptane slurry of the solid catalyst component (X-11) was collected to examine the concentration. As a result, the Zr concentration was 0.023 mg / mL and the Al concentration was 1.3 mg / mL.

[Preparation of solid catalyst component (X-2)]
50 mL of toluene was put into a 200 mL glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S) prepared in Example 1 was charged. Next, 12.7 mL of a toluene solution (0.002 mmol / mL in terms of Zr atom) of the metallocene compound (A2) was added dropwise and reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation and washed twice with heptane to obtain a 100 ml heptane slurry (solid catalyst component X-2). A part of the resulting heptane slurry of the solid catalyst component (X-2) was collected to examine the concentration. As a result, the Zr concentration was 0.023 mg / mL and the Al concentration was 1.3 mg / mL.

Polymerization Purified heptane (500 mL) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, and ethylene was circulated to saturate the liquid phase and gas phase with ethylene. Next, 10 mL of 1-hexene and 0.375 mmol of triisobutylaluminum were added, and 8 mg of the solid catalyst component (X-2) in terms of solid component and 12 mg of solid catalyst component (X-11) in terms of solid component were charged. (Molar ratio of (A2) / (B1) = 40/60), the temperature was raised to 80 ° C., and polymerization was carried out at 0.78 MPa · G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 79.67 g of an ethylene / 1-hexene copolymer. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 20]
[Preparation of solid catalyst component (X-3)]
The solid catalyst component (X-2) of Example 19 was prepared in the same manner as the solid catalyst component (X-2) except that the metallocene compound (A1) was used instead of the metallocene compound (A2). Thus, a solid catalyst component (X-3) was obtained.

Polymerization Purified heptane (500 mL) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, and ethylene was circulated to saturate the liquid phase and gas phase with ethylene. Next, 10 mL of 1-hexene and 0.375 mmol of triisobutylaluminum were added, and further 5 mg of the solid catalyst component (X-3) in terms of solid components and 15 mg of the solid catalyst component (X-11) in terms of solid components were charged. (Molar ratio (A1) / (B1) = 25/75), the temperature was raised to 80 ° C., and polymerization was carried out at 0.78 MPa · G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 48.65 g of an ethylene / 1-hexene copolymer. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 21]
[Preparation of solid catalyst component (Y-11)]
50 mL of toluene was put into a 200 mL glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S) prepared in Example 1 was charged. Next, 5.6 mL of a metallocene compound (dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A2)) in toluene (0.002 mmol / mL in terms of Zr atom) and metallocene 7.1 mL of a toluene solution of compound (B1) (0.002 mmol / mL in terms of Zr atom) was mixed and added dropwise (molar ratio of (A2) / (B1) = 44/56), and reacted at room temperature for 1 hour. Zr was not detected in the supernatant toluene after the reaction for 1 hour. Next, the supernatant was removed by decantation and washed twice with heptane to give a 50 ml heptane slurry (solid catalyst component Y-11).

[Preparation of prepolymerization catalyst component (YP-11)]
Subsequently, after the heptane slurry of the solid catalyst component (Y-11) obtained above was cooled to 10 ° C., 2.0 mmol of diisobutylaluminum hydride (DiBAl—H) and 0.13 mL of 1-hexene were added under nitrogen flow. Was added. After the addition of 1-hexene, the ethylene flow was started, and polymerization of ethylene for 3 times in terms of weight with respect to the solid catalyst component was carried out at a system temperature of 35 ° C. (preliminary polymerization). Thereafter, the supernatant liquid was removed by decantation, and the solid catalyst component was washed three times with heptane to obtain 50 ml heptane slurry.

  Next, 10 mg of Chemiststat 2500 (manufactured by Sanyo Kasei Co., Ltd.) was added to the slurry, and the temperature inside the system was kept at 34 to 36 ° C. for 1 hour to react Chemistat 2500 with the prepolymerized catalyst. Thereafter, the supernatant was removed by decantation, and the resulting prepolymerized catalyst was washed with hexane three times.

Next, the hexane slurry was transferred to a glass Schlenk tube having an internal volume of 100 mL, and hexane was distilled off under reduced pressure at 25 ° C. under reduced pressure, whereby a prepolymerized catalyst component (3 g of polymer was polymerized per 1 g of the solid catalyst component ( 4.0 g of YP-11) was obtained.
When the composition of the obtained prepolymerized catalyst (YP-11) was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

Polymerization The polymerization in Example 1 was carried out in the same manner as in Example 1, except that the prepolymerization catalyst component (YP-11) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 64.33 g of an ethylene / 1-hexene copolymer. Table 3 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 22]
[Preparation of solid catalyst component (Y-12)]
In the preparation of the solid catalyst component (Y-11) of Example 21, the reaction molar ratio of the metallocene compound (A2) and the metallocene compound (B1) was changed to (A2) / (B1) = 44/56 (molar ratio). The solid catalyst component (Y-12) was synthesized in the same manner as the solid catalyst component (Y-11) except that (A2) / (B1) = 47/53 (molar ratio). Zr was not detected in the supernatant toluene after the reaction for 1 hour.

[Preparation of prepolymerization catalyst component (YP-12)]
In the preparation of the prepolymerization catalyst component (YP-11) of Example 21, the prepolymerization catalyst component (YP-11) was used except that the solid catalyst component (Y-12) was used instead of the solid catalyst component (Y-11). ) To obtain a solid catalyst component (YP-12). When the composition of the obtained prepolymerized catalyst (YP-12) was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1, except that the solid catalyst component (YP-12) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 81.86 g of an ethylene / 1-hexene copolymer. Table 4 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 23]
[Preparation of solid catalyst component (Y-13)]
In the preparation of the solid catalyst component (Y-11) of Example 21, the metallocene compound (A1) was used instead of the metallocene compound (A2), and the reaction molar ratio of the metallocene compound (A1) to the metallocene compound (B1) was (A1). ) / (B1) = 37/63 (molar ratio) The solid catalyst component (Y-13) was synthesized in the same manner as the solid catalyst component (Y-11). Zr was not detected in the supernatant toluene after the reaction for 1 hour.

[Preparation of prepolymerization catalyst component (YP-13)]
In the preparation of the prepolymerization catalyst component (YP-11) of Example 21, the prepolymerization catalyst component (YP-11) was used except that the solid catalyst component (Y-13) was used instead of the solid catalyst component (Y-11). ) To obtain a solid catalyst component (YP-13). When the composition of the obtained prepolymerized catalyst (YP-13) was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

Polymerization Polymerization in Example 1 was performed in the same manner as in Example 1 except that the solid catalyst component (YP-13) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 59.57 g of an ethylene / 1-hexene copolymer. Table 4 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 24]
[Preparation of solid catalyst component (Y-14)]
In the preparation of the solid catalyst component (Y-13) of Example 23, the reaction molar ratio of the metallocene compound (A1) and the metallocene compound (B1) was changed to (A1) / (B1) = 37/63 (molar ratio). In the same manner as the solid catalyst component (Y-13), except that the reaction molar ratio of the metallocene compound (A1) to the metallocene compound (B1) was changed to (A1) / (B1) = 45/55 (molar ratio). A solid catalyst component (Y-14) was synthesized. Zr was not detected in the supernatant toluene after the reaction for 1 hour.

[Preparation of prepolymerization catalyst component (YP-14)]
In the preparation of the prepolymerization catalyst component (YP-11) of Example 21, the prepolymerization catalyst component (YP-11) was used except that the solid catalyst component (Y-14) was used instead of the solid catalyst component (Y-11). ) To obtain a solid catalyst component (YP-14). When the composition of the obtained prepolymerized catalyst (YP-14) was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1, except that the solid catalyst component (YP-14) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 80.28 g of an ethylene / 1-hexene copolymer. Table 4 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 25]
[Preparation of solid catalyst component (Y-15)]
In the preparation of the solid catalyst component (Y-13) of Example 23, the reaction molar ratio of the metallocene compound (A1) and the metallocene compound (B1) was changed to (A1) / (B1) = 37/63 (molar ratio). In the same manner as the solid catalyst component (Y-13), except that the reaction molar ratio of the metallocene compound (A1) to the metallocene compound (B1) was changed to (A1) / (B1) = 49/51 (molar ratio). A solid catalyst component (Y-15) was synthesized. Zr was not detected in the supernatant toluene after the reaction for 1 hour.

[Preparation of prepolymerization catalyst component (YP-15)]
In the preparation of the prepolymerized catalyst component (YP-11) of Example 21, the prepolymerized catalyst component (YP-11) was used except that the solid catalyst component (Y-15) was used instead of the solid catalyst component (Y-11). ) To obtain a solid catalyst component (YP-15). When the composition of the obtained prepolymerized catalyst (YP-15) was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1 except that the solid catalyst component (YP-15) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 94.11 g of an ethylene / 1-hexene copolymer. Table 4 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 26]
[Preparation of solid catalyst component (Y-16)]
In the preparation of the solid catalyst component (Y-13) of Example 23, the reaction molar ratio of the metallocene compound (A1) and the metallocene compound (B1) was changed to (A1) / (B1) = 37/63 (molar ratio). In the same manner as the solid catalyst component (Y-13), except that the reaction molar ratio of the metallocene compound (A1) to the metallocene compound (B1) was changed to (A1) / (B1) = 55/45 (molar ratio). A solid catalyst component (Y-16) was synthesized. Zr was not detected in the supernatant toluene after the reaction for 1 hour.

[Preparation of prepolymerization catalyst component (YP-16)]
In the preparation of the prepolymerization catalyst component (YP-11) of Example 21, the prepolymerization catalyst component (YP-11) was used except that the solid catalyst component (Y-16) was used instead of the solid catalyst component (Y-11). ) To obtain a solid catalyst component (YP-16). When the composition of the obtained prepolymerized catalyst (YP-16) was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

Polymerization The polymerization of Example 1 was carried out in the same manner as in Example 1 except that the prepolymerized catalyst component (YP-16) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 63.63 g of an ethylene / 1-hexene copolymer. Table 4 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 27]
[Preparation of prepolymerization catalyst component (YP-17)]
In the preparation of the prepolymerization catalyst component (YP-11) of Example 21, the prepolymerization catalyst component (YP-11) was used except that the reaction amount of Chemist 2500 was increased to 40 mg instead of 10 mg. A prepolymerized catalyst component (YP-17) was prepared in the same manner as described above. When the composition of the obtained prepolymerization catalyst component (YP-17) was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

Polymerization Polymerization was carried out in the same manner as in Example 1, except that the prepolymerized catalyst component (YP-17) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 59.62 g of an ethylene / 1-hexene copolymer. Table 5 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 28]
[Preparation of solid catalyst component (Y-18)]
50 mL of toluene was put into a 200 mL glass flask purged with nitrogen, and the toluene slurry (1.0 g in terms of solid part) of the solid component (S) prepared in Example 1 was charged. Next, a toluene solution (0.002 mmol / mL in terms of Zr atom) of a metallocene compound (dimethylsilylene (3-n-propylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (A2)) at room temperature. 3 mL and 7.4 mL of a toluene solution of metallocene compound (B1) (0.002 mmol / mL in terms of Zr atom) were mixed and added dropwise (molar ratio of (A2) / (B1) = 42/58), and 75 ° C. after completion of the addition. The temperature was raised to. After reacting at 75 ° C. for 2 hours, it was washed twice with heptane to give a 50 ml heptane slurry (solid catalyst component Y-18). Zr was not detected in the supernatant toluene after the reaction for 2 hours.

[Preparation of prepolymerization catalyst component (YP-18)]
Subsequently, after the heptane slurry of the solid catalyst component (Y-18) obtained above was cooled to 10 ° C., 10 mg of Chemistat 2500 was added and reacted for 5 minutes under nitrogen flow, and then diisobutylaluminum hydride (DiBAl). -H) 2.0 mmol and 1-hexene 0.13 mL were charged in this order. After the addition of 1-hexene, the ethylene flow was started, and polymerization of ethylene for 3 times in terms of weight with respect to the solid catalyst component was carried out at a system temperature of 35 ° C. (preliminary polymerization). Thereafter, the supernatant liquid was removed by decantation, and the solid catalyst component was washed three times with heptane to obtain 50 ml heptane slurry.

Next, 40 mg of Chemistat 2500 was added to the slurry, and the system temperature was adjusted to 34 to
The temperature was kept at 36 ° C. for 1 hour, and Chemistat 2500 was reacted with the prepolymerized catalyst. Thereafter, the supernatant was removed by decantation, and the resulting prepolymerized catalyst was washed with hexane three times.

Next, the hexane slurry was transferred to a glass Schlenk tube having an internal volume of 100 mL, and hexane was distilled off under reduced pressure at 25 ° C. under reduced pressure, whereby a prepolymerized catalyst component (3 g of polymer was polymerized per 1 g of the solid catalyst component ( 4.0 g of YP-18) was obtained.
When the composition of the obtained prepolymerized catalyst (YP-18) was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

Polymerization The polymerization of Example 1 was carried out in the same manner as in Example 1 except that the prepolymerized catalyst component (YP-18) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 102.2 g of an ethylene / 1-hexene copolymer. Table 5 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 29]
[Preparation of solid catalyst component (Y-19)]
In the preparation of the solid catalyst component (Y-18) of Example 28, the reaction molar ratio of the metallocene compound (A2) and the metallocene compound (B1) was changed to (A2) / (B1) = 42/58 (molar ratio). In the same manner as the solid catalyst component (Y-18), except that the reaction molar ratio of the metallocene compound (A2) and the metallocene compound (B1) was changed to (A2) / (B1) = 24/76 (molar ratio). A solid catalyst component (Y-19) was synthesized. Zr was not detected in the supernatant toluene after the reaction for 1 hour.

[Preparation of prepolymerization catalyst component (YP-19)]
In the preparation of the prepolymerized catalyst component (YP-11) of Example 21, the prepolymerized catalyst component (YP-11) was used except that the solid catalyst component (Y-19) was used instead of the solid catalyst component (Y-11). ) To obtain a solid catalyst component (YP-19). When the composition of the obtained prepolymerization catalyst component (YP-19) was examined, 0.50 mg of Zr atom was contained per 1 g of the solid catalyst component.

Polymerization The polymerization of Example 1 was carried out in the same manner as in Example 1 except that the solid catalyst component (YP-19) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 75.86 g of an ethylene / 1-hexene copolymer. Table 5 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 30]
Polymerization In Example 1, the prepolymerization catalyst component (YP-11) was used instead of the solid catalyst component (Y-1), and the polymerization temperature was changed from 80 ° C to 70 ° C. The same method was used. The obtained polymer was vacuum-dried for 10 hours to obtain 59.09 g of an ethylene / 1-hexene copolymer. Table 5 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 31]
Polymerization Purified heptane (500 mL) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, and 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 a prepolymerization catalyst component (YP-19) were charged in the order of 35 mg in terms of a solid catalyst component, and then 1.7 mg of Chemistat 2500 was added and heated to 80 ° C. The temperature was raised and polymerization was carried out at 0.78 MPa · G for 90 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 49.31 g of an ethylene / 1-hexene copolymer. Table 5 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Example 32]
Polymerization The polymerization was conducted in the same manner as in Example 31 except that 3.3 mg of Pluronic L71 (manufactured by Adeka) was used instead of 1.7 mg of Chemistat 2500 in the polymerization of Example 31. The obtained polymer was vacuum-dried for 10 hours to obtain 52.64 g of an ethylene / 1-hexene copolymer. Table 5 shows the results of GPC analysis and various physical properties of the obtained polymer.

[Comparative Example 1]
[Preparation of solid catalyst component (EY-1)]
In the preparation of the solid catalyst component (Y-2) of Example 4, a metallocene compound (E1) represented by the following structural formula was used instead of the metallocene compound (A1), and a metallocene compound (B1) was used instead of the metallocene compound (B1). B2) and the solid catalyst component (Y-2) and the metallocene compound (E1) and the metallocene compound (B2) except that the reaction molar ratio was (E1) / (B2) = 80/20 (molar ratio) A solid catalyst component (EY-1) was synthesized by the same method. Zr was not detected in the supernatant toluene after the reaction for 1 hour. Further, when a portion of the resulting heptane slurry of the solid catalyst component (EY-1) was collected to examine the concentration, the Zr concentration was 0.037 mg / mL, and the Al concentration was 2.3 mg / mL.
E1: Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride

重 合
実施例１の重合において、固体触媒成分（Ｙ−１）の代わりに固体触媒成分（ＥＹ−１）を用い、エチレンガスの代わりに水素−エチレン混合ガス（水素濃度：０．４５ｖｏｌ％）を用いた以外は、実施例１と同様の方法で行った。得られたポリマーを１０時間真空乾燥し、エチレン・１−ヘキセン共重合体８７．４４ｇを得た。得られた重合体のＧＰＣ解析結果並びに諸物性を表６に記す。

Polymerization In the polymerization of Example 1, the solid catalyst component (EY-1) was used instead of the solid catalyst component (Y-1), and a hydrogen-ethylene mixed gas (hydrogen concentration: 0.45 vol%) was used instead of ethylene gas. The procedure was the same as in Example 1 except that was used. The obtained polymer was vacuum-dried for 10 hours to obtain 87.44 g of an ethylene / 1-hexene copolymer. Table 6 shows the results of GPC analysis and various physical properties of the polymer obtained.

  Comparing Comparative Example 1 and this example, it can be seen that the olefin polymerization catalyst according to the present invention can produce an ethylene polymer with high productivity. This is because the metallocene compound (component A) used in the present invention was able to produce a polymer having a low molecular weight and a large amount of terminal vinyl with high catalytic activity.

[Comparative Example 2]
[Preparation of solid catalyst component (EY-2)]
In the preparation of the solid catalyst component (Y-2) of Example 4, a metallocene compound (E3) represented by the following structural formula was used instead of the metallocene compound (A1), and a metallocene compound (B1) was used instead of the metallocene compound (B1). B2) and the solid catalyst component (Y-2) and the metallocene compound (E3) and the metallocene compound (B2) except that the reaction molar ratio is (E3) / (B2) = 35/65 (molar ratio). A solid catalyst component (EY-2) was synthesized by the same method. Zr was not detected in the supernatant toluene after the reaction for 1 hour. Further, when a portion of the resulting heptane slurry of the solid catalyst component (EY-2) was collected to examine the concentration, the Zr concentration was 0.033 mg / mL, and the Al concentration was 2.1 mg / mL.
E3: Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride

重 合
実施例１の重合において、固体触媒成分（Ｙ−１）の代わりに固体触媒成分（ＥＹ−２）を用い、エチレンガスの代わりに水素−エチレン混合ガス（水素濃度：０．６５ｖｏｌ％）を用いた以外は、実施例１と同様の方法で行った。得られたポリマーを１０時間真空乾燥し、エチレン・１−ヘキセン共重合体４７．９ｇを得た。得られた重合体のＧＰＣ解析結果並びに諸物性を表６に記す。

Polymerization In the polymerization of Example 1, a solid catalyst component (EY-2) was used instead of the solid catalyst component (Y-1), and a hydrogen-ethylene mixed gas (hydrogen concentration: 0.65 vol%) was used instead of ethylene gas. The procedure was the same as in Example 1 except that was used. The obtained polymer was vacuum-dried for 10 hours to obtain 47.9 g of an ethylene / 1-hexene copolymer. Table 6 shows the results of GPC analysis and various physical properties of the polymer obtained.

  Comparative Example 2 has almost no long chain branching and does not satisfy the preferable requirements for the ethylene polymer obtained by the production method of the present invention. This is because the polymer produced from the metallocene compounds having substituents on both cyclopentadienyl rings as used in Comparative Example 2 has a large molecular weight and a small amount of terminal vinyl.

[Comparative Example 3]
[Preparation of solid catalyst component (EY-3)]
In the preparation of the solid catalyst component (Y-2) of Example 4, a metallocene compound (E2) represented by the following structural formula was used instead of the metallocene compound (A1), and a metallocene compound (B1) was used instead of the metallocene compound (B1). The solid catalyst component (Y-2) was used except that the reaction molar ratio of the metallocene compound (E2) and the metallocene compound (B2) was (E2) / (B2) = 10/90 (molar ratio). A solid catalyst component (EY-3) was synthesized in the same manner. Zr was not detected in the supernatant toluene after the reaction for 1 hour. Further, when a portion of the resulting heptane slurry of the solid catalyst component (EY-2) was collected to examine the concentration, the Zr concentration was 0.030 mg / mL and the Al concentration was 2.4 mg / mL.
E2: Dimethylsilylenebis (3-n-butylcyclopentadienyl) zirconium dichloride

重 合
実施例１の重合において、固体触媒成分（Ｙ−１）の代わりに固体触媒成分（ＥＹ−３）を用いた以外は、実施例１と同様の方法で行った。得られたポリマーを１０時間真空乾燥し、エチレン・１−ヘキセン共重合体７７．８１ｇを得た。得られた重合体のＧＰＣ解析結果並びに諸物性を表６に記す。

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1 except that the solid catalyst component (EY-3) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 77.81 g of an ethylene / 1-hexene copolymer. Table 6 shows the results of GPC analysis and various physical properties of the polymer obtained.

[Comparative Example 4]
[Preparation of solid catalyst component (EY-4)]
In the preparation of the solid catalyst component (Y-1) of Example 1, the metallocene compound (E2) was used instead of the metallocene compound (A2), and the reaction molar ratio between the metallocene compound (E2) and the metallocene compound (B1) was (E2). ) / (B1) = 30/70 (molar ratio) The solid catalyst component (EY-4) was synthesized in the same manner as the solid catalyst component (Y-1) except that the molar ratio was changed. Zr was not detected in the supernatant toluene after the reaction for 1 hour. Further, when a portion of the resulting heptane slurry of the solid catalyst component (EY-4) was collected to examine the concentration, the Zr concentration was 0.035 mg / mL and the Al concentration was 2.0 mg / mL.

Polymerization Polymerization in Example 1 was carried out in the same manner as in Example 1, except that the solid catalyst component (EY-4) was used instead of the solid catalyst component (Y-1). The obtained polymer was vacuum-dried for 10 hours to obtain 91.57 g of an ethylene / 1-hexene copolymer. Table 6 shows the results of GPC analysis and various physical properties of the polymer obtained.

  Comparing Comparative Examples 3 and 4 with Examples, the olefin polymerization catalyst according to the present invention is more preferable than the catalysts used in Comparative Examples 3 and 4 (for example, the above characteristics). 1 and 2) can be produced. This is because the metallocene compound (component A) used in the present invention has a lower molecular weight than the metallocene compound (E2) having substituents on both cyclopentadienyl rings as used in Comparative Example 3 and Comparative Example 4. This is because a polymer having a large amount of terminal vinyl can be produced with high catalytic activity.

  ADVANTAGE OF THE INVENTION According to this invention, the ethylene-type polymer with many long chain branching amounts excellent in molding processability, and this efficient manufacturing method are provided. For example, this ethylene polymer exhibits its performance in the extrusion laminate field.

1 is a GPC chart of the polymer obtained in Example 1. FIG. FIG. 2 is a GPC chart of the polymer obtained in Example 4. FIG. 3 is a GPC chart of the polymer obtained in Example 5. FIG. 4 is a GPC chart of the polymer obtained in Example 6. FIG. 5 is a GPC chart of the polymer obtained in Example 7. 6 is a GPC chart of the polymer obtained in Example 9. FIG.

Claims (7)

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 to} R ⁴ are a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, They are selected from a germanium-containing group and a tin-containing group, and may be the same or different from each other, but all are not hydrogen atoms at the same time, and adjacent groups may be bonded to each other to form an aliphatic ring. Q ¹ is selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, M is a group selected from a halogen-containing group, a silicon-containing group, an oxygen-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 (B) : A bridged metallocene compound represented by the following general formula (II).

[In the general formula (II), R ^{7 to} R ¹⁰ and R ^{13 to} R ²⁰ are hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing A group selected from a group, a silicon-containing group, a germanium-containing group, and a tin-containing group, which may be the same or different, and adjacent substituents may be bonded to each other to form a ring, and Q ² Is
Is selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group; M is selected from a titanium atom, a zirconium atom and a hafnium atom; and X is independently , A hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. ]
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) at least one compound selected from the group consisting of compounds that react with component (A) and 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 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 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, 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. ]   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 catalyst for 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. .   The catalyst for olefin polymerization according to claim 2 or 3, wherein the component (C) is an organoaluminum oxy compound and the solid carrier (S) is a porous oxide.   6. A method for producing an ethylene polymer, wherein ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms is polymerized in the presence of the olefin polymerization catalyst according to claim 1. In gel permeation chromatography (GPC), two or more peaks are observed, and the maximum peak peak Log M _Max satisfies 3.8 ≦ Log M _Max ≦ 4.6, and the maximum peak intensity (H _Max ) And the peak intensity (H _second ) of the next largest peak is H _Max ≧ 2.
The method for producing an ethylene polymer according to claim 6, wherein an ethylene polymer satisfying the relationship of × H _second is produced.

Images