JP2009079180A - Catalyst component for olefin polymerization, catalyst for olefin polymerization, and manufacturing method for olefinic polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst component for olefin polymerization capable of reducing content of a different shape powder contained in a polymerization powder, a catalyst and a manufacturing method for an olefinic polymer. <P>SOLUTION: In the catalyst component for the olefin polymerization obtained by contacting a compound (a) represented by M<SP>1</SP>L<SP>1</SP><SB>m</SB>, a compound (b) represented by the formula, a compound (c) represented by R<SP>3</SP><SB>t-2</SB>TH<SB>2</SB>, and a particle (d), y and z satisfy the following formulae (1), (2) and (3) when a molar ratio of an amount used of the compound (a), (b), (c) used for the contact is made to (a):(b):(c)=1:y:z. The content of the particle (d) contained in the catalyst component for the olefin polymerization is 57-80 wt.%. ¾m-y-2z¾≤1 (1), z≥-2.5y+2.48 (2), y<0.5m (3). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer. More specifically, the present invention relates to an olefin polymerization catalyst component, an olefin polymerization catalyst, and a method for producing an olefin polymer that can reduce the content of the irregular shaped powder contained in the polymerization powder.

In recent years, a catalyst in which a transition metal component such as a metallocene complex or a nonmetallocene complex is combined with an organic metal component such as an aluminoxane has been used in the production of an olefin polymer.
For example, Japanese Patent Application Laid-Open No. 2003-171413 (Patent Document 1) is useful for preparing a highly active catalyst used for polymerization (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.) involving the formation of addition polymer particles. Particles, carriers and addition polymerization catalyst components, highly active addition polymerization catalysts, and methods for producing addition polymers are described.

JP 2003-171413 A

  However, even when the olefin polymerization catalyst component or the olefin polymerization catalyst described in the above-mentioned patent publications is used, irregular powder may be contained in the polymerization powder, and the irregular powder may cause agglomerates in the polymerization reactor. May occur or the piping may be blocked.

  Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention is to provide an olefin polymerization catalyst component, an olefin polymerization catalyst, and an olefin polymerization catalyst capable of reducing the content of the irregular powder contained in the polymerization powder It is providing the manufacturing method of an olefin polymer.

［２］
（ｃ）下式［３］で表される化合物
Ｒ³ _t-2ＴＨ₂ ［３］
（ｄ）粒子
（ただし、上式［１］〜［３］において、Ｍ¹は元素の周期表第１族、第２族、第１２族の典型金属原子、ゲルマニウム原子、スズ原子、鉛原子、アンチモン原子、ビスマス原子を表し、ｍはＭ¹の原子価に相当する数を表す。Ｌ¹は水素原子、ハロゲン原子または炭化水素基を表し、Ｌ¹が複数存在する場合、複数のＬ¹は互いに同じであっても異なっていてもよい。Ｒ¹は電子吸引性基または電子吸引性基を含有する基を表し、３つのＲ¹は互いに同じであっても異なっていてもよく、隣接する炭素原子にそれぞれ結合する２つのＲ¹は、互いに連結してベンゼン環に隣接した縮合環構造を形成していてもよい。Ｒ²は水素原子または炭化水素基を表す。Ｒ³は炭化水素基またはハロゲン化炭化水素基を表す。Ｔはそれぞれ独立に、窒素原子、リン原子、酸素原子、硫黄原子を表し、ｔはそれぞれの化合物のＴの原子価に相当する数を表す。）
｜ｍ−ｙ−２ｚ｜≦１ （１）
ｚ≧−２．５ｙ＋２．４８ （２）
ｙ＜０．５ｍ （３）
（ただし、上記式（１）〜（３）において、ｙおよびｚは０よりも大きな数を表す。） That is, the present invention is obtained by contacting the following compounds (a), (b), (c) and component (d), and the amount of the compounds (a), (b), (c) used for the contact is adjusted. When the molar ratio is (a) :( b) :( c) = 1: y: z, y and z satisfy the following formulas (1), (2) and (3) (A) The content of the component (d) contained in the olefin polymerization catalyst component (A) is 57 to 80% by weight (provided that the total weight of the olefin polymerization catalyst (A) component is 100% by weight) And a solid catalyst component for olefin polymerization.
(A) Compound M ¹ L ¹ _m [1] represented by the following formula [1]
(B) Compound represented by the following formula [2]

[2]
(C) Compound R ³ _t-2 TH ₂ [3] represented by the following formula [3]
(D) Particles (wherein, in the above formulas [1] to [3], M ¹ is a typical metal atom of Group 1, 2 and 12 of the periodic table of elements, germanium atom, tin atom, lead atom, antimony atom, a bismuth atom, .L ¹ m is representative of a number corresponding to the valence of M ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ is R ¹ may be the same as or different from each other, R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and three R ¹ may be the same or different from each other and are adjacent to each other. Two R ¹ bonded to each carbon atom may be connected to each other to form a condensed ring structure adjacent to the benzene ring, R ² represents a hydrogen atom or a hydrocarbon group, and R ³ represents a hydrocarbon group. Or a halogenated hydrocarbon group, wherein T is independently Atom, phosphorus atom, an oxygen atom, a sulfur atom, t represents a number corresponding to the valence of T of each compound.)
| M−y−2z | ≦ 1 (1)
z ≧ −2.5y + 2.48 (2)
y <0.5m (3)
(However, in the above formulas (1) to (3), y and z represent a number larger than 0.)

  By using the olefin polymerization catalyst component and the olefin polymerization catalyst of the present invention, it is possible to obtain a polymerization powder in which the content of the irregularly shaped powder contained in the polymerization powder is reduced.

  In the present invention, the term “polymerization” includes not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers.

  As the fluidized bed reactor used in the present invention, a known gas phase fluidized bed reactor can be used. For example, the gas phase flow described in JP-A-58-201802, JP-A-59-126406, JP-A-2-233708, JP-A-4-234409, JP-A-7-62009, and the like. There may be mentioned a bed reactor.

  In the present invention, olefin is continuously supplied to a fluidized bed reactor, an olefin polymerization catalyst is supplied into the fluidized bed, a fluidized bed of solid particles containing the olefin polymerization catalyst is formed, and the olefin is polymerized. .

  In the polymerization of olefins using the fluidized bed reactor of the present invention, the flow rate of the olefin gas that has passed through the fluidized bed is usually reduced in the deceleration region provided in the upper part of the fluidized bed type reaction vessel. Then, it is discharged out of the fluidized bed type reaction vessel through a gas outlet provided in the upper part of the fluidized bed type reaction vessel. Then, the gas discharged from the fluidized bed type reaction vessel is blown again into a position below the gas dispersion plate of the fluidized bed type reaction vessel by the compressor through the circulation gas line. Also, since the olefin gas usually needs to remove the heat of polymerization reaction of the gas before it is blown again below the gas dispersion plate of the fluidized bed reactor, heat exchange is performed on the circulating gas line. An oven is provided and the gas is cooled by this heat exchanger. The circulating gas line is provided with an olefin introduction pipe and a hydrogen introduction pipe, and olefin and hydrogen are supplied from the olefin introduction pipe and the hydrogen introduction pipe.

  In the present invention, olefin polymerization is carried out under known polymerization conditions. The internal pressure of the reactor may be within a range in which the entire olefin or at least a part thereof can exist as a gas phase, and is usually 0.1 to 5.0 MPa, preferably 1.5 to 3.0 MPa. The temperature in the reactor is appropriately selected depending on the catalyst used, the pressure in the reactor, the type of olefin to be polymerized, and the like, but is generally 30 to 110 ° C. The circulating gas flow rate in the reactor is usually 10 to 100 cm / second, preferably 20 to 70 cm / second. In general, hydrogen may coexist with the circulating gas, or an inert gas may coexist.

［２］
（ｃ）下記式［３］で表される化合物
Ｒ³ _t-2ＴＨ₂ ［３］
（ｄ）粒子。
（ただし、上式［１］〜［３］において、Ｍ¹は元素の周期表第１族、第２族、第１２族の典型金属原子、ゲルマニウム原子、スズ原子、鉛原子、アンチモン原子、ビスマス原子を表し、ｍはＭ¹の原子価に相当する数を表す。Ｌ¹は水素原子、ハロゲン原子または炭化水素基を表し、Ｌ¹が複数存在する場合、複数のＬ¹は互いに同じであっても異なっていてもよい。Ｒ¹は電子吸引性基または電子吸引性基を含有する基を表し、３つのＲ¹は互いに同じであっても異なっていてもよく、隣接する炭素原子にそれぞれ結合する２つのＲ¹は、互いに連結してベンゼン環に隣接した縮合環構造を形成していてもよい。Ｒ²は水素原子またはハイドロカルビル基を表す。Ｒ³は炭化水素基またはハロゲン化ハイドロカルビル基を表す。Ｔはそれぞれ独立に、窒素原子、リン原子、酸素原子、硫黄原子を表し、ｔはそれぞれの化合物のＴの原子価に相当する数を表す。）
｜ｍ−ｙ−２ｚ｜≦１ （１）
ｚ≧−２．５ｙ＋２．４８ （２）
ｙ＜０．５ｍ （３）
（ただし、上記式（１）〜（３）において、ｙおよびｚは０よりも大きな数を表す。） The olefin polymerization catalyst component (A) in the present invention is an olefin polymerization catalyst component obtained by contacting the following compounds (a), (b), (c) and particles (d).
(A) Compound M ¹ L ¹ _m [1] represented by the following formula [1]
(B) Compound represented by the following formula [2]

[2]
(C) Compound R ³ _t-2 TH ₂ [3] represented by the following formula [3]
(D) Particles.
(However, in the above formulas [1] to [3], M ¹ is a typical metal atom of Group 1, 2 and 12 of the periodic table, germanium atom, tin atom, lead atom, antimony atom, bismuth) represents an atom, m is .L ¹ representing the number corresponding to the valence of M ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ may be the same as each other R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and three R ^{1 s} may be the same as or different from each other, two R ¹ bound to the, .R ³ is or a halogenated hydrocarbon group optionally .R ² may form a fused ring structure adjacent to the benzene ring represents a hydrogen atom or a hydrocarbyl group linked to each other Represents a hydrocarbyl group, each T is German A nitrogen atom, phosphorus atom, an oxygen atom, a sulfur atom, t represents a number corresponding to the valence of T of each compound.)
| M−y−2z | ≦ 1 (1)
z ≧ −2.5y + 2.48 (2)
y <0.5m (3)
(However, in the above formulas (1) to (3), y and z represent a number larger than 0.)

The compound (a) used for the olefin polymerization catalyst component (A) of the present invention is a compound represented by the following formula [1].
M ¹ L ¹ _m [1]
In the above formula [1], M ¹ is a typical metal atom of Group 1, Group 2, Group 12, Group 14 or Group 15 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989) . Examples of M ¹ include lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, cadmium atom, germanium atom, tin atom, lead An atom, an antimony atom, and a bismuth atom are mentioned. Preferred is a magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom or bismuth atom, particularly preferred is a magnesium atom, zinc atom, tin atom or bismuth atom, and most preferred is zinc. Is an atom. Moreover, m in Formula [1] is a number corresponding to the valence of M ^1, for example, when M ¹ is a zinc atom, m is two.

In the above formula [1], L ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom for L ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group for L ¹ is preferably an alkyl group, an aryl group, or an aralkyl group.

The alkyl group of the hydrocarbon group of L ¹ is preferably an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group. , Tert-butyl, isobutyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, and n- An eicosyl group can be mentioned, and a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group is more preferable.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, and a tetrafluoroethyl group. , Pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, 1H, 1H-perfluoropropyl group, 1H, 1H-perfluorobutyl group, 1H, 1H-perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl 1H, 1H-par Le Oro pentadecyl group, IH, 1H-perfluoro eicosyl group, and "chloro" to "fluoro" in these alkyl group include an alkyl group is replaced with "bromo" or "iodo".
Any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The aryl group of the hydrocarbon group of L ¹ is preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl. Group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3 , 5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group sec-butylphenyl group, tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group , N-tetradecylphenyl group, naphthyl group, and anthracenyl group, more preferably a phenyl group.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl) Phenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl) Phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) Nyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl Group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (isobutylphenyl) methyl Group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, And anthracenylmethyl group. Among them, a benzyl group is more preferable.
These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

L ^{1 in the} formula [1] is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group.

［２］
また、本発明のオレフィン重合用触媒成分（Ａ）に用いられる化合物（ｃ）は、下記式［３］で表される化合物である。
Ｒ³ _t-2ＴＨ₂ ［３］
上記式［２］または［３］において、Ｔはそれぞれ独立に元素の周期律表（ＩＵＰＡＣ無機化学命名法改訂版１９８９）第１５族または第１６族の非金属原子である。第１５族の非金属原子としては、例えば、窒素原子、リン原子等が挙げられ、第１６族の非金属原子としては、例えば、酸素原子、硫黄原子等が挙げられる。Ｔとして好ましくは、窒素原子または酸素原子であり、特に好ましくは酸素原子である。
上記式［２］または［３］において、ｔはそれぞれの化合物のＴの原子価に相当する数である。Ｔが第１５族の非金属原子の場合、ｔは３であり、Ｔが第１６族の非金属原子の場合、ｔは２である。 The compound (b) used for the olefin polymerization catalyst component (A) of the present invention is a compound represented by the following formula [2].

[2]
Moreover, the compound (c) used for the catalyst component (A) for olefin polymerization of the present invention is a compound represented by the following formula [3].
R ³ _t-2 TH ₂ [3]
In the above formula [2] or [3], T is each independently a nonmetal atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Examples of the Group 15 nonmetallic atom include a nitrogen atom and a phosphorus atom. Examples of the Group 16 nonmetallic atom include an oxygen atom and a sulfur atom. T is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.
In the above formula [2] or [3], t is a number corresponding to the valence of T of each compound. T is 3 when T is a Group 15 non-metallic atom, and t is 2 when T is a Group 16 non-metallic atom.

In the formula [2], R ¹ is an electron-withdrawing group or a group containing an electron-withdrawing group, and three R ¹ may be the same or different from each other, and three R ¹ are the same as each other. The two R ¹ bonded to adjacent carbon atoms may be connected to each other to form a condensed ring structure adjacent to the benzene ring. Examples of the electron withdrawing index include a Hammett's rule substituent constant σ and the like, and a functional group having a positive substituent constant σ can be cited as an electron withdrawing group.

In the formula [2], examples of the electron-withdrawing group represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group. In the formula [2], examples of the group containing an electron-withdrawing group represented by R ¹ include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, Examples include ester groups (alkoxycarbonyl groups, aralkyloxycarbonyl groups and aryloxycarbonyl groups), acyl groups, and acyl halide groups.

In the formula [2], examples of the halogenated alkyl group for R ¹ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, 2,2,3,3, and the like. 3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 1H, 1H- Perfluorobutyl group, 1H, 1H-perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl group, 1H, 1H-perfluoropentadecyl group 1H, 1H-perfluoroeicosyl group, and “fluoro” of these halogenated alkyl groups is “chloro”, “bromo” or Include alkyl groups is replaced with iodine. "

In the formula [2], examples of the halogenated aryl group for R ¹ include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, and 2,6-difluorophenyl. Group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluoro Phenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1 A naphthyl group, a perfluoro-2-naphthyl group, 4,5,6,7,8-pentafluoro-2-naphthyl group, and halogens thereof "Chloro" to "fluoro" aryl group, a halogenated aryl group is replaced with "bromo" or "iodo".

In the formula [2], examples of the (halogenated alkyl) aryl group for R ¹ include a 2- (trifluoromethyl) phenyl group, a 3- (trifluoromethyl) phenyl group, and a 4- (trifluoromethyl) phenyl group. 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, and 2,4,6-tris (trifluoromethyl) phenyl group, and their (halogenated) (Halogenated alkyl) aryl groups in which “fluoro” in the alkyl) aryl group is replaced with “chloro”, “bromo” or “iodo”.

In the formula [2], examples of the cyanated aryl group for R ¹ include a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group.

In the formula [2], examples of the nitrated aryl group for R ¹ include a 2-nitrophenyl group, a 3-nitrophenyl group, and a 4-nitrophenyl group.

In the formula [2], examples of the ester group for R ¹ include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, phenoxycarbonyl group, trifluoromethoxycarbonyl group, and pentafluorophenoxycarbonyl. Groups.

In the formula [2], examples of the acyl group and acyl halide group represented by R ¹ include a formyl group, an ethanoyl group, a propanoyl group, a butanoyl group, a trifluoroethanoyl group, a benzoyl group, a pentafluorobenzoyl group, and a perfluoroethano group. Yl group, perfluoropropanoyl group, perfluorobutanoyl group, perfluoropentanoyl group, perfluorohexanoyl group, perfluoroheptanoyl group, perfluorooctanoyl group, perfluorononanoyl group, perfluorodecanoyl group , Perfluoroundecanoyl group, and perfluorododecanoyl group.

In the formula [2], R ¹ is preferably a halogen atom, a halogenated alkyl group, a halogenated aryl group, a cyano group, a cyanated alkyl group, a cyanated aryl group, a nitro group, a nitrated alkyl group, or a nitrated aryl group. Or it is an ester group, More preferably, they are a halogen atom, a halogenated alkyl group, or a halogenated aryl group. More preferably, fluorine atom, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2, 2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluoro Phenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4, 5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4- Trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, chloromethyl group, dichloromethyl group, trichloro Methyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2-trichloro-1-trichloromethylethyl group, 1,1-bis (trichloro Methyl) -2,2,2-trichloroethyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3.5-dichlorophenyl group, 2,4,6-trichlorophenyl group, or pentachlorophenyl group, especially Preferred is a fluorine atom, a fluoroalkyl group or a fluoroaryl group, and most preferred is a fluorine atom .

In the formula [2], R ² is a hydrogen atom or a hydrocarbon group. The hydrocarbon group of R ^{2 in} the formula [2] is preferably an alkyl group, an aryl group or an aralkyl group, and the substituents exemplified as L ^{1 in the} formula [1] are each an alkyl group, an aryl group or an aralkyl group. Can be mentioned. R ² is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

In the formula [3], R ³ is a hydrocarbon group or a halogenated hydrocarbon group. The hydrocarbon group represented by R ^{3 in} the formula [3] is preferably an alkyl group, an aryl group or an aralkyl group, and the substituents exemplified as L ^{1 in the} formula [1] are each represented as an alkyl group, an aryl group or an aralkyl group. Can be mentioned. Examples of the halogenated hydrocarbon group for R ³ include halogenated alkyl groups, halogenated aryl groups, and (halogenated alkyl) aryl groups. Halogenated alkyl groups, halogenated aryl groups, and (halogenated alkyl) ) As the aryl group, a halogenated alkyl group, a halogenated aryl group and a (halogenated alkyl) aryl group exemplified as the electron-withdrawing group for R ^{1 in} the formula [2] can be mentioned.

In the formula [3], R ³ is preferably a halogenated hydrocarbon group, more preferably a fluorinated hydrocarbon group.

As the compound (a) used in the olefin polymerization catalyst component (A) of the present invention, when M ¹ is a zinc atom, for example, dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, Dialkyl zinc such as di-n-hexyl zinc, diphenyl zinc, dinaphthyl zinc, and diaryl zinc such as bis (pentafluorophenyl) zinc, dialkenyl zinc such as diallyl zinc, bis (cyclopentadienyl) zinc, methyl zinc chloride, Ethyl zinc chloride, propyl zinc chloride, n-butyl zinc chloride, isobutyl zinc chloride, n-hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide , N-hexyl zinc bromide, methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide, iodine Of n- butyl zinc, isobutyl iodide, zinc, and halogenated alkyl zinc iodide and like n- hexyl zinc, zinc fluoride, zinc chloride, zinc bromide, and halogenated zinc such as zinc iodide.

  The compound (a) is preferably dialkyl zinc, more preferably dimethyl zinc, diethyl zinc, dipropyl zinc, di n-butyl zinc, diisobutyl zinc or di n-hexyl zinc, particularly preferably dimethyl zinc or diethyl. Zinc.

  Examples of the compound (b) used in the olefin polymerization catalyst component (A) of the present invention include phenol, thiophenol, naphthol, naphthylthiol, amine and phosphine compounds. Examples of the phenol, naphthol, thiophenol, and naphthylthiol compound of the compound (b) include 3,4,5-trifluorophenol, 3,4,5-tris (trifluoromethyl) phenol, 3,4,5. -Tris (pentafluorophenyl) phenol, 3,5-difluoro-4-pentafluorophenylphenol, 4,5,6,7,8-pentafluoro-2-naphthol, 3,5-difluoro-4-nitrophenol, 3,5-difluoro-4-cyanophenol, and phenols in which the fluoro of these phenols is replaced with chloro, bromo or iodo. Moreover, the thiophenol compound which replaced the oxygen atom of the said phenol compound with the sulfur atom can be mentioned similarly. These thiophenol compounds are compounds represented by replacing “phenol” in the above phenol compounds with “thiophenol” (in the case of naphthol, compounds represented by replacing “naphthol” with “naphthylthiol”), etc. It is. In addition, a hydrogen atom at the 2-6 position of the phenol compound (a hydrogen atom at the 1st, 3rd position in the case of naphthol or naphthylthiol) is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, A phenol compound substituted with an isobutyl group, a tert-butyl group, or a phenyl group, or a thiophenol compound is also exemplified.

  Examples of the amine and phosphine compound of the compound (b) include bis (3,4,5-trifluorophenyl) amine, bis (3,4,5-tris (trifluoromethyl) phenyl) amine, bis (3, 4,5-tris (pentafluorophenyl) phenyl) amine, bis (3,5-difluoro-4-pentafluorophenylphenyl) amine, bis (4,5,6,7,8-pentafluoro-2-naphthyl) Mention may be made of amines and amines in which “fluoro” in these amines is replaced by “chloro”, “bromo” or “iodo”. Moreover, the phosphine compound which substituted the nitrogen atom of the said amine compound with the phosphorus atom can be mentioned similarly. These phosphine compounds are compounds represented by substituting “amine” of “amine compound” with “phosphine”. In the above-mentioned specific examples, the hydrogen atom at the 2-6 position (in the case of naphthylamine or naphthylphosphine, the hydrogen atom at the 1-3 position) is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group. An amine compound substituted with an isobutyl group, a tert-butyl group, or a phenyl group, or a phosphine compound is also exemplified.

  Preferably as the compound (b), as the phenol, 3,4,5-trifluorophenol, 3,4,5-tris (trifluoromethyl) phenol, 3,4,5-tris (pentafluorophenyl) phenol, 3,5-difluoro-4-pentafluorophenylphenol or 4,5,6,7,8-pentafluoro-2-naphthol, and amines include bis (3,4,5-trifluorophenyl) amine, bis (3,4,5-tris (trifluoromethyl) phenyl) amine, bis (3,4,5-tris (pentafluorophenyl) phenyl) amine, bis (3,4-difluoro-4-pentafluorophenylphenyl) An amine or bis (4,5,6,7,8-pentafluoro-2-naphthyl) amine.

  More preferably, the compound (b) is 3,4,5-trifluorophenol, 4,5,6,7,8-pentafluoro-2-naphthol, bis (3,4,5-trifluorophenyl) amine, Alternatively, bis (4,5,6,7,8-pentafluoro-2-naphthyl) amine is preferable, and 3,4,5-trifluorophenol is particularly preferable.

  Examples of the compound (c) include water, hydrogen sulfide, amine, and aniline compounds. Examples of the amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, and n-hexyl. Alkylamines such as amine, n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, and n-eicosylamine, aralkylamines such as allylamine, cyclopentadienylamine, and benzylamine, fluoro Methylamine, difluoromethylamine, trifluoromethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,2-trifluoro-1-trifluoro Methylethylamine, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluoro Dodecylamine, perfluoropentadecylamine, perfluoroeicosylamine, and halogenated alkylamines in which “fluoro” of these amines is replaced with “chloro”, “bromo”, or “iodo”.

  Examples of the aniline compound of the compound (c) include aniline, naphthylamine, anthracenylamine, 2-tolylamine, 3-tolylamine, 4-tolylamine, 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4,6 -Trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline, penta Methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2,3-diethylaline Phosphorus, 2,4-diethylaniline, 2,5-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline, 3,5-diethylaniline, 2,3,4-triethylaniline, 2,3, 5-triethylaniline, 2,3,6-triethylaniline, 2,4,6-triethylaniline, 3,4,5-triethylaniline, 2,3,4,5-tetraethylaniline, 2,3,4,6 -Tetraethylaniline, 2,3,5,6-tetraethylaniline, pentaethylaniline, and their "ethyl" are "n-propyl", "isopropyl", "n-butyl", "sec-butyl", " tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, Alkylaniline substituted with “n-tetradecyl”, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, Halogenated anilines such as 3,4,5-trifluoroaniline and pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6 -Di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) aniline, 2,4,6-tri (trifluoromethyl) aniline, and their “fluoro” are “chloro”, “bromo” Or (halogenated alkyl) aniline substituted with “iodo”.

  The compound (c) is preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2, 6-xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, Perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoro Oroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3 -(Trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline or 2,4,6-tris (tri Fluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2, 6-difluoroaniline, 3,5-difluoroa Phosphorus, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) ) Aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, or 2,4,6-tris (trifluoromethyl) aniline, most preferably water or penta Fluoroaniline.

The particles (d) used for the catalyst component for olefin polymerization of the present invention are not particularly limited as long as they are a solvent used for the production of the catalyst component for olefin polymerization or a solid substance insoluble in the polymerization solvent. A porous substance having a uniform particle size used as a carrier, more preferably an inorganic substance or an organic polymer, and still more preferably an inorganic substance.
As the particle size distribution of the particles (d), from the viewpoint of the particle size distribution of the resulting addition polymer, the volume standard geometric standard deviation of the particle size of the particles (d) is preferably 2.5 or less. Preferably it is 2.0 or less, More preferably, it is 1.7 or less.

Examples of the inorganic substance of the particles (d) include inorganic oxides, clays, and clay minerals. You may mix and use these some inorganic substance.
Examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , and mixtures thereof, 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, and SiO ₂ -TiO ₂ -MgO and the like. These inorganic oxides are preferably SiO ₂ and / or Al ₂ O ₃ , and particularly preferably SiO ₂ (ie, silica). The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , Carbonic acid salts such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

Examples of the clay or clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, vylophilite, talc, ummo group, smectite, montmorillonite group, hectorite, laponite, saponite, vermiculite, ryokdeite stone. Group, palygorskite, kaolinite, nacrite, dickite, halloysite.
Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.

The inorganic substance is preferably an inorganic oxide.
The inorganic material is preferably dried and substantially free of moisture, and the drying method is preferably heat drying. The drying temperature is usually 100 to 1500 ° C., preferably 100 to 1000 ° C., more preferably 200 to 800 ° C. for inorganic substances whose moisture cannot be visually confirmed. The drying time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method of drying by circulating an inert gas (for example, nitrogen or argon) dried during heating at a constant flow rate, or a method of heat drying under reduced pressure. .

  Inorganic oxides usually have hydroxyl groups formed on the surface, but modified inorganic oxides in which active hydrogen of the surface hydroxyl groups are substituted with various substituents may be used as inorganic oxides. Examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diaryldichlorosilanes such as diphenyldichlorosilane. Alkyltrichlorosilanes such as methyltrichlorosilane, aryltrichlorosilanes such as phenyltrichlorosilane, trialkylalkoxysilanes such as trimethylmethoxysilane, triarylalkoxysilanes such as triphenylmethoxysilane, and dialkyldialkoxysilanes such as dimethyldimethoxysilane , Diaryldialkoxysilanes such as diphenyldimethoxysilane, and alkyltols such as methyltrimethoxysilane Alkoxysilane, aryltrialkoxysilane such as phenyltrimethoxysilane, tetraalkoxysilane such as tetramethoxysilane, alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, methanol and Examples include inorganic oxides obtained by contact treatment with alcohols such as ethanol, dialkylmagnesium such as phenol, dibutylmagnesium, butylethylmagnesium and butyloctylmagnesium, and alkyllithiums such as butyllithium.

  Furthermore, after contact with trialkylaluminum, there can be mentioned dialkylamines such as diethylamine and diphenylamine, alcohols such as methanol and ethanol, and inorganic oxides contacted with phenol.

  Inorganic oxides may have increased strength due to hydrogen bonding between hydroxyl groups. In that case, if all the active hydrogens of the surface hydroxyl group are substituted with various substituents, the particle strength may be lowered. Therefore, it is not always necessary to substitute all the active hydrogens on the surface hydroxyl groups of the inorganic oxide, and the substitution rate of the surface hydroxyl groups may be determined as appropriate. The method for changing the substitution rate of the surface hydroxyl group is not particularly limited. As this method, the method of changing the usage-amount of the compound used for a contact process is mentioned, for example.

The average particle diameter of the inorganic substance is not particularly limited, but is usually 1 to 5000 μm, preferably 5 to 1000 μm, more preferably 10 to 500 μm, and further preferably 10 to 100 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. Preferably by the specific surface area and a 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  Any organic polymer may be used as the organic polymer of the particles (d), and a mixture of plural kinds of organic polymers may be used. The organic polymer is preferably a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group.

  The functional group having active hydrogen is not particularly limited as long as it has active hydrogen. Examples of the functional group include primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, Examples thereof include a sulfinic acid group, a sulfenic acid group, a thiol group, a thioformyl group, a pyrrolyl group, an imidazolyl group, a piperidyl group, an indazolyl group, and a carbazolyl group. Preferred are primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group or thiol group, and particularly preferred are primary amino group, 2 A primary amino group, an amide group or a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  The non-proton-donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base portion having no active hydrogen atom. Examples of the functional group include a pyridyl group, an N-substituted imidazolyl group, an N-substituted indazolyl group, a nitrile group, an azide group, an N-substituted imino group, an N, N-substituted amino group, and an N, N-substituted aminooxy group. Group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N, N-substituted carbamoyl group, thioalkoxy group , Substituted sulfinyl group, substituted sulfonyl group, and substituted sulfonic acid group. A heterocyclic group is preferable, and an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring is more preferable. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  The content of the functional group having active hydrogen or the non-proton donating Lewis basic functional group in the organic polymer is not particularly limited. The content is preferably 0.01 to 50 mmol / g, more preferably 0.1 to 20 mmol / g, as the molar amount of the functional group per unit gram of the polymer.

  Examples of the method for producing an organic polymer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group include a functional group having active hydrogen or a non-proton donating Lewis basic functional group and one or more. And a method of homopolymerizing a monomer having a polymerizable unsaturated group, or a method of copolymerizing the monomer and another monomer having a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.

Examples of the polymerizable unsaturated group include alkenyl groups such as vinyl group and allyl group, and alkynyl groups such as ethyne group.
Examples of the monomer having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, and vinyl group-containing hydroxy compounds. Is mentioned. Examples of the monomer include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methylamine. 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol Is mentioned.
Examples of monomers having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups include vinyl pyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole. Is mentioned.

Examples of the other monomer having a polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compound and cyclic olefin compound. Examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, norbornene, and dicyclopentadiene. Preferred is ethylene or styrene. Two or more of these monomers may be used.
Examples of the cross-linkable polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

Although the average particle diameter of an organic polymer is not specifically limited, Usually, it is 1-5000 micrometers, Preferably it is 5-1000 micrometers, More preferably, it is 10-500 micrometers. Although it does not specifically limit as pore volume, Preferably it is 0.1 ml / g or more, More preferably, it is 0.3-10 ml / g. Although it does not specifically limit as a specific surface area, Preferably it is 10-1000 m < ² > / g, More preferably, it is 50-500 m < ² > / g.

  These organic polymers are preferably dried and substantially free of moisture, and those dried by heat drying are preferred. The drying temperature is usually 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, and more preferably 1 hour to 30 hours. Examples of the heat drying method include a method of drying by circulating an inert gas (for example, nitrogen or argon) dried during heating at a constant flow rate, or a method of heat drying under reduced pressure. .

In order to obtain the catalyst component (A) for olefin polymerization of the present invention, the order in which the components (a), (b), (c) and (d) are brought into contact with each other is not particularly limited. The following order can be given.
<1> A contact object obtained by contacting (a) and (b) with (c) and a contact object obtained by bringing (c) into contact with each other.
<2> A contact object obtained by bringing (a) and (b) into contact with each other and a contact object obtained by bringing (d) into contact with each other.
<3> A contact object obtained by bringing (a) and (c) a contact object into contact with (b) is brought into contact with (d).
<4> A contact object obtained by bringing (a) and (c) into contact with each other and (d) in contact with (b).
<5> A contact product obtained by contacting (b) with a contact product between (a) and (d) and (c) are brought into contact with each other.
<6> A contact object obtained by bringing (a) and (d) into contact with each other and (c) with the contact object obtained in contact with (b).
<7> A contact product obtained by contacting (b) with the contact product between (b) and (c) is brought into contact with (d).
<8> A contact product obtained by contacting (b) with the contact product between (b) and (c) and (a) are brought into contact with each other.
<9> A contact product obtained by contacting (b) with the contact product between (b) and (d) and (c) are brought into contact with each other.
<10> The contact product obtained by bringing (b) and (d) into contact with each other and (c) with the contact product are brought into contact with each other.
<11> A contact object obtained by contacting (a) with a contact object between (c) and (d) and (b) are brought into contact with each other.
<12> A contact product obtained by contacting (b) with a contact product between (c) and (d) and (a) are contacted.
The contact order is preferably <1>, <2>, <3>, <5>, <11> or <12>. Particularly preferred is <2> or <5>.

  Such contact treatment is preferably performed in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Such treatment may use a solvent, or may directly contact these compounds without using a solvent.

  As the solvent, a solvent inert to the above compounds (a), (b), (c), (d), and their contacts is used. However, as described above, when each compound is brought into contact in stages, even if the solvent reacts with a compound at a certain stage, as long as the solvent does not react with each compound at another stage, The solvent can be used in other stages. That is, the solvents in each stage are the same or different from each other. Examples of the solvent include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, and nitrile solvents. Examples include solvents, nitro compounds, amine solvents, and polar solvents such as sulfur compounds. For example, aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, dichloromethane, difluoromethane, chloroform, Halide solvents such as 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene, dimethyl ether, Diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl-ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran, tetra Ether solvents such as dropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, ethylene Glycols, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, alcohol solvents such as glycerin, phenol solvents such as phenol, p-cresol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, Carbonyl solvents such as ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethyl Phosphoric acid derivatives such as triphosphate, triethyl phosphate, nitrile solvents such as acetonitrile, propionitrile, succinonitrile, benzonitrile, nitro compounds such as nitromethane, nitrobenzene, amine solvents such as pyridine, piperidine, morpholine, And sulfur compounds such as dimethyl sulfoxide and sulfolane.

  When the contact product (e) obtained by bringing the compounds (a), (b) and (c) into contact with the particles (d), that is, the above <1>, <3>, <7> In each of the methods, the solvent (s1) for producing the contact product (e) is preferably the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

A polar solvent is preferable as the solvent (s2) when the contact product (e) and the particles (d) are brought into contact with each other. As an index representing the polarity of the solvent, E _T ^N value (C.Reichardt, "Solvents and Solvents Effects in Organic Chemistry", 2nd ed., VCH Verlag (1988).) And the like are known, 0.8 ≧ A solvent satisfying the range of E _T ^N ≧ 0.1 is particularly preferable. Examples of the polar solvent include dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, Bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol Cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, Mention may be made of ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide and sulfolane. More preferably, the solvent (s2) is dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl). ) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol or triethylene glycol, particularly preferably di-n-butyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol or cyclohexanol Most preferably, it is tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.

Moreover, as said solvent (s2), the mixed solvent of these polar solvents and hydrocarbon solvents can also be used. As the hydrocarbon solvent, the aliphatic hydrocarbon solvent and aromatic hydrocarbon solvent exemplified above are used. Examples of the mixed solvent of the polar solvent and the hydrocarbon solvent include hexane / methanol mixed solvent, hexane / ethanol mixed solvent, hexane / 1-propanol mixed solvent, hexane / 2-propanol mixed solvent, heptane / methanol mixed solvent, heptane. / Ethanol mixed solvent, heptane / 1-propanol mixed solvent, heptane / 2-propanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, toluene / 1-propanol mixed solvent, toluene / 2-propanol mixed solvent, xylene And xylene / ethanol mixed solvent, xylene / 1-propanol mixed solvent, and xylene / 2-propanol mixed solvent. Preferably in hexane / methanol mixed solvent, hexane / ethanol mixed solvent, heptane / methanol mixed solvent, heptane / ethanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, xylene / methanol mixed solvent, xylene / ethanol mixed solvent is there. More preferred are a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a toluene / methanol mixed solvent or a toluene / ethanol mixed solvent. Most preferred is a toluene / ethanol mixed solvent.
The preferable range of the ethanol fraction in the toluene / ethanol mixed solvent is 10 to 50% by volume, more preferably 15 to 30% by volume.

  A method of contacting the contact product (e) obtained by contacting the compounds (a), (b) and (c) with (d), that is, the above-mentioned <1>, <3>, <7> In each method, a hydrocarbon solvent can be used as both the solvent (s1) and the solvent (s2). In this case, after the compounds (a), (b) and (c) are brought into contact with each other, it is preferable that the time until the obtained contact product (e) and the particles (d) are brought into contact with each other is short. The time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. Further, the temperature when the contact product (e) and the particles (d) are contacted is usually −100 ° C. to 40 ° C., preferably −20 ° C. to 20 ° C., most preferably −10 ° C. to 10 ° C.

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12> above, any of the above nonpolar solvents and polar solvents may be used. it can. Preferably, it is a nonpolar solvent. This is because the contact product of (a) and (c) and the contact product of (a) and (b) and the contact product of (c) are generally dissolved in a nonpolar solvent. This is because it is considered that the contact product produced is deposited on the surface of (d) and is more easily immobilized when (d) is present in the reaction system when these contact products are formed. is there.

As the usage-amount of the said compound (a), (b) and (c), the molar ratio of the usage-amount of the compound (a), (b), (c) used for a contact is (a) :( b) :( c) = 1: When y: z, y and z are used so as to satisfy the following formulas (1), (2) and (3).
| M−y−2z | ≦ 1 (1)
z ≧ −2.5y + 2.48 (2)
y <0.5m (3)
(In the above formulas (1) to (3), m represents a number corresponding to the valence of M ¹ of the compound (a), and y and z represent a number greater than 0.)
The molar ratio y of the usage amount of the compound (b) to the usage amount of the compound (a) and the molar ratio z of the usage amount of the compound (c) to the usage amount of the compound (a) are the above formulas (1) and (2). As long as the conditions (3) and (3) are satisfied, there is no particular limitation. When the value of z is smaller than the value on the right side of the formula (2), a higher molecular weight addition polymer that is the object of the present invention may not be obtained. When the value of y is larger than the value on the right side of the formula (3), the polymerization activity may decrease. Specifically, when m is 2, y usually takes a value of 0.5 to 0.99, more preferably 0.55 to 0.95, and even more preferably 0.6 to 0.9. Yes, most preferably 0.7 to 0.8. In this case, the normal ratio, more preferable ratio, further preferable ratio, and most preferable ratio of z are the valence of M ¹ , the molar ratio of the amount of the compound (b) used, and the above formulas (1), (2) and It is calculated by (3), respectively.

  The compound (a) is used in an amount of 0.001 when the typical metal atoms derived from the compound (a) contained in the olefin polymerization catalyst component (A) are converted to the number of moles of typical metal atoms contained in 1 g of the obtained particles. The amount is preferably at least 05 mmol, more preferably from 0.1 to 20 mmol.

  The amount of the compound (d) used is such that the content of the component (d) contained in the olefin polymerization catalyst component is 57 to 80% by weight (provided that the entire olefin polymerization catalyst component is 100% by weight). It is preferable.

  In order to make the reaction proceed faster, it is preferable to add a heating step at a higher temperature after the contact treatment as described above. In the heating step, it is preferable to use a solvent having a high boiling point in order to obtain a higher temperature. In performing the heating step, the solvent used in the contact step may be replaced with another solvent having a higher boiling point.

  In the olefin polymerization catalyst component (A) of the present invention, as a result of such contact treatment, the starting compounds (a), (b), (c) and / or (d) remain as unreacted substances. May be. However, it is preferable to perform a washing process for removing unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  Further, after such contact treatment or washing treatment, it is preferable to distill off the solvent from the product, and then to dry under reduced pressure for 1 to 24 hours at a temperature of 0 ° C. or higher. More preferably, it is 1 hour to 24 hours at a temperature of 0 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 10 ° C. to 200 ° C., particularly preferably 2 at a temperature of 10 ° C. to 160 ° C. Time to 18 hours, most preferably 4 to 18 hours at a temperature of 15 ° C to 160 ° C.

Specific examples of the method for producing the catalyst composition for olefin polymerization (A) of the present invention are as follows: M ¹ is a zinc atom, compound (b) is 3,4,5-trifluorophenol, and compound (c) is water. The case where the particle (d) is silica is shown in more detail below. Tetrahydrofuran is used as a solvent, and a hexane solution of diethylzinc is added thereto, followed by cooling to 3 ° C., and an equimolar amount of 3,4,5-trifluorophenol is added dropwise thereto relative to diethylzinc for 10 minutes at room temperature. After stirring for 24 hours, 0.5 times molar amount of water is further added dropwise to diethyl zinc, and the mixture is stirred at room temperature for 10 minutes to 24 hours. Thereafter, the solvent is distilled off, followed by drying at 120 ° C. under reduced pressure for 8 hours. Tetrahydrofuran and silica are added to the solid component obtained by the above operation, and the mixture is stirred at 40 ° C. for 2 hours. The solid component is washed with tetrahydrofuran and then dried at 120 ° C. under reduced pressure for 8 hours. Thus, the modified particles of the present invention can be produced.

  The transition metal compound (B) used in the addition polymerization catalyst of the present invention is added by using together with the olefin polymerization catalyst component (A) described below (or further together with the organoaluminum compound (C)). Although it will not specifically limit if it is a transition metal compound which shows polymerization activity, Usually, the transition metal compound which forms a single site catalyst is used. The single-site catalyst in the present invention is a catalyst that is distinguished from conventional solid catalysts, and includes not only a single-site catalyst in a narrow sense that can produce an addition polymer with a narrow molecular weight distribution and high homogeneity, but also a single site in a narrow sense. It also means a catalyst which can be produced by a production method similar to the catalyst and which can produce an addition polymer having a broad molecular weight distribution and low homogeneity.

As the transition metal compound (B), a transition metal compound of Group 3 to Group 11 of the periodic table of elements or a lanthanoid series transition metal compound is usually used, and a transition metal compound represented by the following formula [4] or its μ-oxo Dimers of type transition metal compounds are preferred.
L ² _a M ² X ¹ _b [4]
(In the formula, M ² represents a transition metal atom of Group 3 to Group 11 of the periodic table of elements or a lanthanoid series. L ² represents a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, L ^{2 in the above} may be directly connected to each other, or may be connected via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and X ¹ is a halogen atom. Represents a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbon oxy group, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8. Represents.)

As M ^{2 in the} formula [4], for example, scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom Nickel atom, palladium atom, samarium atom, ytterbium atom and the like. Among them, preferred is a titanium atom, zirconium atom, hafnium atom, vanadium atom, chromium atom, iron atom, cobalt atom or nickel atom, more preferred is a titanium atom, zirconium atom or hafnium atom, and particularly preferred is a zirconium atom. It is.

Examples of the group having a cyclopentadiene-type anion skeleton of L ^{2 in} the formula [4] include (substituted) cyclopentadienyl group, (substituted) indenyl group, and (substituted) fluorenyl group. Specifically, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, tert-butylcyclopentadienyl group, 1,2-dimethylcyclopenta Dienyl group, 1,3-dimethylcyclopentadienyl group, 1-methyl-2-ethylcyclopentadienyl group, 1-methyl-3-ethylcyclopentadienyl group, 1-tert-butyl-2-methyl Cyclopentadienyl group, 1-tert-butyl-3-methylcyclopentadienyl group, 1-methyl-2-isopropylcyclopentadienyl group, 1-methyl-3-isopropylcyclopentadienyl group, 1-methyl -2-n-butylcyclopentadienyl group, 1-methyl -3-n-butylcyclopentadienyl group, eta ⁵ -1 2,3-trimethyl cyclopentadienyl group, eta ^{5-1,2,4-trimethyl} cyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, 4,5, 6,7-tetrahydroindenyl group, 2-methylindenyl group, 3-methylindenyl group, 4-methylindenyl group, 5-methylindenyl group, 6-methylindenyl group, 7-methylindenyl group 2-tert-butylindenyl group, 3-tert-butylindenyl group, 4-tert-butylindenyl group, 5-tert-butylindenyl group, 6-tert-butylindenyl group, 7-tert- Butyl indenyl group, 2,3-dimethyl indenyl group, 4,7-dimethyl indenyl group, 2,4,7-trimethyl indenyl group, -Methyl-4-isopropylindenyl group, 4,5-benzindenyl group, 2-methyl-4,5-benzindenyl group, 4-phenylindenyl group, 2-methyl-5-phenylindenyl group, 2-methyl- Examples thereof include 4-phenylindenyl group, 2-methyl-4-naphthylindenyl group, fluorenyl group, 2,7-dimethylfluorenyl group and 2,7-di-tert-butylfluorenyl group. .

The polydentate η of the group having a cyclopentadiene type anion skeleton used for L ² in the formula [4] is not particularly limited and may be any value that can be taken by the group having a cyclopentadiene type anion skeleton. For example, 5 seats, 4 seats, 3 seats, 2 seats and single seats are mentioned, preferably 5 seats, 3 seats or single seats, more preferably 5 seats or 3 seats.

Examples of the hetero atom in the group containing the L ² hetero atom in the formula [4] include an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom. Examples of such a group include an alkoxy group and an aryloxy group. , A thioalkoxy group, a thioaryloxy group, an alkylamino group, an arylamino group, an alkylphosphino group, an arylphosphino group, a chelating ligand, or a ring of oxygen, sulfur, nitrogen and / or phosphorus atoms An aromatic heterocyclic group or an aliphatic heterocyclic group is preferable.

Examples of the group containing a hetero atom of L ² in the formula [4] include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a 2-methylphenoxy group, a 2,6-dimethylphenoxy group, 2, 4,6-trimethylphenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group Group, 2,6-di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxyphenoxy group Group, 3,5-dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group 4-nitrophenoxy group, 2-aminophenoxy group, 3-aminophenoxy group, 4-aminothiophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,6-trifluorophenoxy group, thiomethoxy group, Dimethylamino group, diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, catechol, Resorcinol, 4-isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-biphenyldiol group, 1,1′-bi-2-naphthol group, 2,2′-dihydroxy-6,6′-dimethylbiphenyl group, 4,4 ′, 6 6'-tetra -tert- butyl 2,2 'methylenedianiline phenoxy group, and 4,4', mention may be made of 6,6'-tetramethyl-2,2'-isobutenyl dust Denji phenoxy group.

Moreover, as group containing the said hetero atom, group represented by following formula [5] can also be mentioned, for example.
R ⁹ ₃ P = N- [5]
(In the formula, each R ⁹ independently represents a hydrogen atom, a halogen atom or a hydrocarbon group, and the plurality of R ⁹ may be the same or different from each other, and any two of the plurality of R ⁹ may be selected. The above may be bonded to each other and may form a ring structure.)

Specific examples of R ⁹ in the formula [5] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert- Examples thereof include a butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group.

（式中、Ｒ⁴はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭化水素オキシ基、シリル基またはアミノ基を表し、複数のＲ⁴は互いに同じであっても異なっていてもよく、複数のＲ⁴のうち、任意の２つ以上が互いに結合していてもよく、環構造を形成していてもよい。） Further, examples of the group containing a heteroatom include a group represented by the following formula [6].

(In the formula, each R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group or an amino group, and the plurality of R ⁴ are the same as each other. And any two or more of R ⁴ may be bonded to each other and may form a ring structure.)

Specific examples of R ⁴ in the above formula [6] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl group, 2,6- Dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl group, triethyl Examples thereof include silyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group, and pentafluorophenyl group.

The chelating ligand of L ² in the formula [4] refers to a ligand having a plurality of coordination sites. Examples of the ligand include acetylacetonate, diimine, oxazoline, bisoxazoline, Mention may be made of terpyridine, acyl hydrazones, diethylenetriamine, triethylenetetramine, porphyrin, crown ether, and cryptate.

Examples of the heterocyclic group represented by L ² in the formula [4] include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and among them, a pyridyl group is preferable.

In the formula [4], when a plurality of L ² are linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom (that is, a cyclopentadiene anion When a group having a skeleton is linked through the residue, a group containing a hetero atom is linked through the residue, or a group having a cyclopentadiene anion skeleton and a hetero atom If the group containing is connected through the said residues), as preferably the residues, two L ² and the atoms connecting the carbon atom, silicon atom, nitrogen atom, oxygen, sulfur or It is a phosphorus atom and is a divalent residue having a minimum atomic number of 3 or less for bonding two L ² . Examples of the residue include alkylene groups such as methylene group, ethylene group and propylene group; substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group; silylene group, dimethylsilylene group, diethylsilylene group and diphenylsilylene group. And substituted silylene groups such as tetramethyldisilylene group and dimethoxysilylene group; and heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom. Among these, a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a diphenylmethylene group, a dimethylsilylene group, a diethylsilylene group, a diphenylsilylene group, or a dimethoxysilylene group is particularly preferable.

Examples of the halogen atom represented by X ¹ in the formula [4] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group for X ¹ include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Among them, an alkyl group having 1 to 20 carbon atoms, preferably 7 to 7 carbon atoms is preferable. A aralkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkenyl group having 3 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, and n-pentyl group. , Neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-eicosyl group, and more preferably methyl. Group, ethyl group, isopropyl group, tert-butyl group, isobutyl group or amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorobutyl group. Mention may be made of fluorohexyl, perfluorooctyl, perchloropropyl, perchlorobutyl and perbromopropyl groups.
These alkyl groups may be substituted with an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethyl). (Phenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, 3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, 3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3, , 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group , (N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, and anthracenylmethyl group More preferably, it is a benzyl group.
These aralkyl groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group, etc. May be substituted.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5- Xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6- Trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butyl Enyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, and anthracenyl Group, and more preferably a phenyl group.
These aryl groups are fluorine atoms, chlorine atoms, bromine atoms, halogen atoms such as iodine atoms, alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. May be substituted.

  Examples of the alkenyl group having 3 to 20 carbon atoms include an allyl group, a methallyl group, a crotyl group, and a 1,3-diphenyl-2-propenyl group, and more preferably an allyl group or a methallyl group. It is.

Examples of the hydrocarbon oxy group represented by X ¹ in the general formula [4] include an alkoxy group, an aralkyloxy group, and an aryloxy group. Among these, an alkoxy group having 1 to 20 carbon atoms is preferable, An aralkyloxy group having 7 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.

Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, and neopentoxy. Group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, and n-icosoxy group, and among them, preferably methoxy group, ethoxy group, isopropoxy group, or tert. -Butoxy group.
These alkoxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. May be substituted.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3 -Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group , (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group , (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) Ruphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) Methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy Group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, and anthracenylmethoxy group Among them, a benzyloxy group is more preferable.
These aralkyloxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. May be substituted.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 2,4-dimethylphenoxy group. Group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert- Butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy Group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethyl Ruphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6- Di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group Group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl- 3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group Group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group , Isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group And anthracenoxy group.
These aryloxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. May be substituted.

X ¹ in the formula [4] is more preferably a chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n -Butoxy group, trifluoromethoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6 -Tetrafluoro-4-pentafluorophenylphenoxy group or benzyl group.

In Formula [4], a is a number satisfying 0 <a ≦ 8, b is a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M ² . When M ² is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

  Examples of the compound represented by the formula [4] in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, Bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2-dimethylcyclopentadienyl) titanium Dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) titanium dichloride , Screw (1 Methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclopentadienyl) titanium dichloride Bis (1-methyl-3-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-3-methylcyclopenta) Dienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium Dichloride, bis (pentameth Lucyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenylindenyl) titanium dichloride ,

Bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) Indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride , Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride , Pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindene) Nil) titanium dichloride,

Dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-n- Butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-ethylmethylcyclo) Pentadienyl) titanium dichloride, dimethylsilylene bis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2, 3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride,

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylindenyl) titanium Dichloride, dimethylsilylene bis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylene bis (4,5-benzindenyl) titanium dichloride, dimethyl Silylene bis (2-methyl-4,5-benzindenyl) titanium dichloride, dimethylsilylene bis (2-phenylindenyl) titanium dichloride, dimethylsilylene bis (4-phenyl) Indenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-5-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-naphthyl) Indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilyl (Indenyl) (fluorenyl) titanium dichloride, dimethylsilylenebis (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) ) Titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl (dimethylamido) titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2,6-dimethylphenyl) ) Titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethyl) Phenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) thi Njikuroraido, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl -2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2) -Phenoxy Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-) 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride Id, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) 5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl Down (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (n- Tilcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) ( 3,5-diamil- -Phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium Dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5) -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (tert-butylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Len (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadieni) ) (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1- Naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (trimethylsilylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadi) Enyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl) Rudimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamil-2-phenoxy) titanium dichloride Dimethylsilylene (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) ( -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamil-2-phenoxy) ) Titanium dichloride, dimethylsilylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (1-naphthoxy-2-yl) titanium dichloride,

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyl titanium dichloride,
(Tert-Butylamide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (tert- Butylamido) indenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyltitanium dichloride, (tert- Butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium dichloride (Tert- butylamido) fluorenyl dimethylsilane titanium dichloride,

(Dimethylaminomethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyl titanium (III) dichloride (N-pyrrolidinylethyl) tetramethylcyclopentadienyl titanium dichloride, (B-dimethylaminoborabenzene) cyclopentadienyl titanium dichloride, cyclopentadienyl (9-mesitylboraanthracenyl) titanium dichloride,

2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride, 2,2′-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2′- Thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2'-thiobis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy) ) Titanium dichloride, 2,2'-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2, 2 ′-(4,4 ′, 6,6′-tetra-tert-butyl-1,1 ′ biphenol Shi) titanium dichloride, (di -tert- butyl-1,3-propane diamide) titanium dichloride, (dicyclohexyl-1,3-propane diamide) titanium dichloride,

[Bis (trimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1,3 -Propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide] Titanium dichloride, [bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride, [hydrotris (3,5 Dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride, [tris (3 5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, and [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, and these A compound in which “titanium” is replaced with “zirconium” or “hafnium”, “(2-phenoxy)” is “(3-phenyl-2-phenoxy)”, “(3-trimethylsilyl-2-phenoxy)” Or “(3-tert-butyldi Compound substituted with “methylsilyl-2-phenoxy)”, “dimethylsilylene” with “methylene”, “ethylene”, “dimethylmethylene (isopropylidene)”, “diphenylmethylene”, “diethylsilylene”, “diphenylsilylene”, or "Dimethoxysilylene" compound, "Dichloride" replaced with "Difluoride", "Dibromide", "Diiodide", "Dimethyl," Diethyl "," Diisopropyl "," Diphenyl "," Dibenzyl "," Dimethoxide "," “Diethoxide”, “di (n-propoxide)”, “di (isopropoxide)”, “diphenoxide”, or “di (pentafluorophenoxide)” as well as “trichloride” as “trifluoride” ”,“ Tribromide ”,“ Tria ” Iodide, Trimethyl, Triethyl, Triisopropyl, Triphenyl, Tribenzyl, Trimethoxide, Triethoxide, Tri (n-propoxide), Tri (Isopropoxide) , “Triphenoxide”, or “tri (pentafluorophenoxide)”.

  Examples of the compound represented by the formula [4] in which the transition metal atom is a nickel atom include 2,2′-methylenebis [(4R) -4-phenyl-5,5′-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-di-n -Propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diisopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl- 5,5′-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′- Methoxyoxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethoxyoxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl- 5,5′-diphenyloxazoline] nickel dibromide,

2,2′-methylenebis [(4R) -4-methyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5, 5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2 , 2′-methylenebis [(4R) -4-methyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5,5 -Di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-methyl-5,5-di- (4-methoxyphenyl) Xazoline] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4 -Methyloxazoline-5,1'-cyclopentane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclohexane}] nickel dibromide, 2,2 '-Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di-n-propyloxazoline], 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5- Diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4- Sopropyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) o Oxazoline] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2 '-Methylenebis [(4R) -4-isobutyl-5,5-diethyloxazoline] Ckell dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl- 5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- 4-isobutyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2, 2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methylphenyl) oxa Phosphorus] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) — 4-isobutyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methoxyphenyl) oxazoline ] Nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isobutyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-diethyloxazo ] Nickel dibromide, 2,2'-methylenebis [(4R) -4--4-tert-butyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-diphenyloxazoline] nickel dibromide, 2, 2'-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- ( 2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl -5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methylphenyl) oxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (4 -Methoxyphenyl) oxazoline] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyl Oxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2 '-Methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-phenyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-fur Nyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Ido,

2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-phenyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-benzyl-5,5-dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzene Dil-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Ido,

2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-benzyloxazoline-5,1′-cycloheptane}] nickel dibromide, and the enantiomers of the above compounds, the asymmetric carbon configuration of one oxazoline ring of the bisoxazoline type compound is reversed. As well as “dibromide”, “difluoride”, “dichloride”, “diaiod” Id "," dimethyl "," diethyl "," diisopropyl "," diphenyl "," dibenzyl "," dimethoxide "," diethoxide "," di-n-propoxide "," diisopropoxide "," diphenoxide " Or a compound substituted with “di (pentafluorophenoxide)”.

（式中、Ｒ⁵とＲ⁶はいずれも２，６−ジイソプロピルフェニル基を表し、Ｒ⁷およびＲ⁸はそれぞれ独立に水素原子またはメチル基あるいはＲ⁷とＲ⁸とが互いに結合したアセナフテン基を表し、Ｘ²はそれぞれ独立に、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、フェニル基、ベンジル基、メトキシ基、エトキシ基、またはフェノキシ基を表す。）
また、上記のニッケル化合物において、「ニッケル」を「パラジウム」、「コバルト」、「ロジウム」、または「ルテニウム」に置き換えた化合物も同様に例示することができる。 Examples of the compound represented by the formula [4] in which the transition metal atom is a nickel atom include compounds represented by the following structural formula.

(In the formula, R ⁵ and R ⁶ are both 2,6-diisopropylphenyl groups, and R ⁷ and R ⁸ are each independently a hydrogen atom or a methyl group or an acenaphthene group in which R ⁷ and R ⁸ are bonded to each other. X ² represents each independently a fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methoxy group, ethoxy Represents a group or a phenoxy group.)
In addition, in the above nickel compound, compounds in which “nickel” is replaced with “palladium”, “cobalt”, “rhodium”, or “ruthenium” can be exemplified as well.

  Examples of the compound represented by the formula [4] whose transition metal atom is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine iron dichloride, 2,6- Bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride and 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron dichloride, and these Examples include compounds in which “dichloride” of the compound is replaced with “difluoride”, “dibromide”, “diaiodide”, “dimethyl”, “diethyl”, “dimethoxide”, “diethoxide”, or “diphenoxide”. .

  Examples of the μ-oxo type transition metal compound of the transition metal compound represented by the formula [4] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [ Isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) Titanium chloride], μ-oxobis [isopro Liden (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], [Mu] -oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) titanium chlora And [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], and "chloride" of these compounds as "fluoride" , “Bromide”, “iodide”, “methyl”, “ethyl”, “isopropyl”, “phenyl”, “benzyl”, “methoxide”, “ethoxide”, “n-propoxide”, “isopropoxide”, Mention may be made of compounds substituted with “phenoxide” or “pentafluorophenoxide”.

As the transition metal compound (B) other than the compound represented by the formula [4], [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, and [Hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel chloride, as well as the “chloride” of these compounds can be referred to as “bromide”, “iodide”, “methyl”, “ethyl”, “allyl”, Mention may be made of compounds substituted with “methallyl”, “methoxide” or “ethoxide”.
In addition, in the above nickel compound, a compound in which “nickel” is replaced with “iron” or “cobalt” can be exemplified similarly.

  Examples of the compound in which the transition metal atom is a nickel atom include nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate, nickel acetate, nickel trifluoroacetate, nickel cyanide, Nickel oxalate, nickel acetylacetonate, bis (allyl) nickel, bis (1,5-cyclooctadiene) nickel, dichloro (1,5-cyclooctadiene) nickel, dichlorobis (acetonitrile) nickel, dichlorobis (benzonitrile) Nickel, carbonyltris (triphenylphosphine) nickel, dichlorobis (triethylphosphine) nickel, diacetbis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, dichloro [1,2-bi (Diphenylphosphino) ethane] nickel, bis [1,2-bis (diphenylphosphino) ethane] nickel, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis [1,3-bis (diphenyl) Mention may be made of phosphino) propane] nickel, tetraamine nickel nitrate, tetrakis (acetonitrile) nickel tetrafluoroborate, and nickel phthalocyanine.

Similarly, examples of the compound whose transition metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, and vanadium oxytrichloride.
Examples of the compound in which the transition metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran.
Examples of the compound in which the transition metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.
These transition metal compounds may be used alone or in combination of two or more.

Of the transition metal compounds exemplified above, the transition metal compound (B) used in the present invention is preferably a transition metal compound represented by the above formula [4]. Among them, a transition metal compound in which M ² in the above formula [4] is a Group 4 atom is preferable, and in particular, a transition metal compound having at least one group having a cyclopentadiene type anion skeleton as L ² in the formula [4]. preferable. Among them, a zirconium compound is more preferable, and L ² in the formula [4] has two groups having a cyclopentadiene type anion skeleton, and L ² has a carbon atom, a silicon atom, an oxygen atom, a sulfur atom or a phosphorus atom. Zirconium compounds linked via the residues they contain are particularly preferred.

A known organoaluminum compound can be used as the organoaluminum compound (C). An organoaluminum compound represented by the following formula [7] is preferable.
R ¹⁰ _d AlX ³ _3-d [7]
(Wherein R ¹⁰ represents a hydrocarbon group, and R ¹⁰ may be the same or different. X ³ represents a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, or an aralkyloxy group; X ³ may be the same or different, and d represents a number satisfying 0 <d ≦ 3.)

R ¹⁰ in the above formula [7] is preferably a hydrocarbon group having 1 to 24 carbon atoms, more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, and n-octyl group. An ethyl group, n-butyl group, isobutyl group, n-hexyl group or n-octyl group is preferred.

Examples of the halogen atom in X ³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
As the alkoxy group for X ^3, an alkoxy group having 1 to 24 carbon atoms is preferable, and specifically, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy Group, tert-butoxy group, n-pentoxy group, and n-icosoxy group, preferably methoxy group, ethoxy group or tert-butoxy group.

The aryloxy group for X ³ is preferably an aryloxy group having 6 to 24 carbon atoms. Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5- Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2, 3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy , Ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group , N-tetradecylphenoxy group, naphthoxy group, and anthracenoxy group.

The aralkyloxy group for X ³ is preferably an aralkyloxy group having 7 to 24 carbon atoms. Examples of the aralkyloxy group include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, and (2,3-dimethylphenyl) methoxy group. , (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5- (Dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,4) 5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) meth Si group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (N-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy Group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group, and anthracenylmethoxy group, preferably benzyloxy It is a group.

  Examples of the organoaluminum compound (C) represented by the formula [7] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, And trialkylaluminum such as tri-n-octylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum chloride Dialkylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n- Alkyl aluminum dichlorides such as til aluminum dichloride, isobutyl aluminum dichloride, and n-hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, and di Dialkylaluminum hydrides such as n-hexylaluminum hydride, methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, and alkyl (dialkoxy) aluminum such as methyl (di-tert-butoxy) aluminum, dimethyl (methoxy) aluminum, dimethyl (Ethoxy) aluminum and dimethyl ( alkyl (diaryloxy) aluminum such as dialkyl (alkoxy) aluminum such as ert-butoxy) aluminum, methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, and methylbis (2,6-diphenylphenoxy) aluminum, Moreover, dialkyl (aryloxy) aluminum, such as dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, and dimethyl (2,6-diphenylphenoxy) aluminum, and the like can be given.

Among them, preferred is trialkylaluminum, more preferred is trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum, particularly preferred. Triisobutylaluminum or tri-n-octylaluminum.
These organoaluminum compounds may be used alone or in combination of two or more.

The amount of the transition metal compound (B) is usually ^{1 × 10 -6 ~1 × 10 -3} mol to olefin polymerization catalyst component (A) 1 g, preferably 5 × 10 ^-6 ~1 × 10 ^{- 4} mol. Moreover, the usage-amount of an organoaluminum compound (C) is 0.01-10, as molar ratio (C) / (B) of the aluminum atom of the organoaluminum compound (C) with respect to the transition metal atom of a transition metal compound (B). 000 is preferable, 0.1 to 5,000 is more preferable, and 1 to 2,000 is most preferable.

  As the addition polymerization catalyst of the present invention, a reaction product obtained by previously contacting the component (A) and the transition metal compound (B), and in some cases, the organoaluminum compound (C) may be used. They may be used separately in the apparatus. When using the catalyst component for olefin polymerization (A), the transition metal compound (B) and the organoaluminum compound (C), any two of them are contacted in advance, and then the other component is contacted You may let them.

  When used in the olefin polymerization of the present invention, a prepolymerization catalyst obtained by polymerizing a small amount of olefin (hereinafter referred to as prepolymerization), for example, a catalyst component (A) for olefin polymerization, a transition metal compound ( A prepolymerized catalyst obtained by polymerizing a small amount of olefin using B) and the organoaluminum compound (C) can be used.

  The prepolymerization may be performed by any of batch, semi-batch and continuous methods. Furthermore, the prepolymerization may be performed by adding a chain transfer agent such as hydrogen.

  When the prepolymerization is performed by a slurry polymerization method, a saturated aliphatic hydrocarbon compound is usually used as the solvent, and examples thereof include propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane and the like. . These may be used alone or in combination of two or more. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or less at normal pressure, more preferably 90 ° C. or less at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal hexane. More preferred is cyclohexane.

  When the prepolymerization is performed by a slurry polymerization method, as the slurry concentration, the amount of the olefin polymerization catalyst component (A) per liter of solvent is usually 0.1 to 600 g, preferably 0.5 to 300 g. . The prepolymerization temperature is usually -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed, but the temperature at which the prepolymerization is started is preferably 45 ° C. or less, and preferably 40 ° C. or less. Moreover, the partial pressure of olefins in the gas phase part during prepolymerization is usually 0.001 to 2 MPa, preferably 0.01 to 1 MPa. The prepolymerization time is usually 2 minutes to 15 hours.

  Examples of the olefin used for the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene, cyclohexene and the like. These may be used alone or in combination of two or more, preferably ethylene alone, or ethylene and α-olefin in combination, more preferably ethylene alone, or 1-butene, 1-hexene and 1 -It is used in combination with at least one α-olefin selected from octene and ethylene.

  The content of the prepolymerized polymer in the prepolymerization catalyst component is usually 0.01 to 1000 g, preferably 0.05 to 500 g, more preferably 0.00, per 1 g of the promoter support (A). 1 to 200 g.

  Examples of the olefin used in the method for producing an olefin polymer of the present invention include α-olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, etc. Olefin can also be used.

  Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene and 1-nonene. Α-olefins such as 1-decene; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl- 1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl- 2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydro Diolefins such as phthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene; norbornene, 5-methylnorbornene, 5- Ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8 -Ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonor Cyclic olefins such as bornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, alkenylbenzene (2-phenylpropylene, 2-phenylbutene, 3 -Phenylpropylene, etc.), alkylstyrene (p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5- Dimethyl styrene, 3,4-dimethyl styrene, 3,5-dimethyl styrene, 3-methyl-5-ethyl styrene, p-tertiary butyl styrene, p-secondary butyl styrene, etc.), bisalkenylbenzene (divinylbenzene) Etc.), alkenylnaphthalene (1-vinylnaphthalene, etc.) Alkenyl aromatic hydrocarbons; α, such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid β-unsaturated carboxylic acid compounds; metal salts of α, β-unsaturated carboxylic acid compounds with sodium, potassium, lithium, zinc, magnesium, calcium, etc .; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic Α, β-unsaturation such as isopropyl acetate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Carboxylic acid ester compounds; unsaturated dicarbox such as maleic acid and itaconic acid Acid compounds; vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. And unsaturated carboxylic acid glycidyl ester compounds.

  The present invention is applied to homopolymerization or copolymerization of these olefins. Specific examples of the olefin constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, ethylene and 1-octene, propylene and 1-butene. And ethylene, 1-butene and 1-hexene, ethylene, 1-butene and 4-methyl-1-pentene.

  The olefin polymer produced in the present invention is particularly preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and among them, ethylene having a polyethylene crystal structure and α having 3 to 20 carbon atoms. -Copolymers with olefins are preferred. The α-olefin is more preferably an α-olefin having 3 to 8 carbon atoms, and specific examples include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The measured value of each item in an Example was measured with the following method.
(1) Density (Unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(2) Melt flow rate (MFR, unit: g / 10 minutes)
According to the method defined in JIS K7210-1995, the measurement was performed under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(3) Molecular weight distribution (Mw / Mn)
It measured on the following conditions by the gel permeation chromatography (GPC). A calibration curve was prepared using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Model: Millipo Waters 150C type Column: TSK-GEL GMH-HT 7.5 × 600 2 Measurement temperature: 140 ° C.
Solvent: Orthodichlorobenzene Solvent flow rate: 1.0 mL / min Measurement concentration: 5 mg / 5 ml
Detector: Differential refraction

(4) Proportion of deformed powder The proportion of deformed powder (proportion of powder such as cotton having deviated from the spherical shape) was obtained by collecting 1 kg of the obtained ethylene-α-olefin copolymer and visually observing it. Then, the weight ratio of the irregular shaped powder to the whole ethylene-α-olefin copolymer powder was determined.

[Example 1]
(1) Silica treatment In a reactor equipped with a nitrogen-replaced stirrer, 24 kg of toluene as a solvent and silica heat-treated at 300 ° C. under a nitrogen stream as a fine particle carrier (a) (Sypolol 948 manufactured by Devison; average particle diameter = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 2.81 kg was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.91, 1 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.43 kg of toluene was maintained in 32 minutes while maintaining the reactor temperature at 5 ° C. It was dripped. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3.3 hours. Thereafter, the obtained solid product was washed 6 times with 21 kg of toluene. Thereafter, 7.1 kg of toluene was added and allowed to stand overnight.

(2) Preparation of Olefin Polymerization Catalyst Component (A) To the toluene slurry obtained in Example 1 (1) above, 1.75 kg of a hexane solution of 50 wt% diethylzinc as compound (b) and 1.hexane as a solvent. 0 kg was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.78 kg of trifluorophenol as the compound (c) and 1.41 kg of toluene as the solvent was added dropwise over 61 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, the temperature was lowered to 22 ° C., and 0.11 kg of water was added dropwise as compound (d) over 1.5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 22 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. Stirring was stopped and the supernatant liquid was withdrawn until the remaining amount reached 16 liters, and 11.6 kg of toluene was added and stirred. The temperature was raised to 95 ° C. and stirred for 4 hours. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Then, the olefin polymerization catalyst component (A) was obtained by drying. As a result of elemental analysis, Zn = 11 wt%, Si = 30 wt%, F = 5.9 wt%, and N = 2.3 wt%.
From this, the proportion of the fine particle carrier (a) in the olefin polymerization catalyst component (A) was 64 wt%.

(3) Prepolymerization A reactor equipped with a stirrer with an internal volume of 210 liters, which was previously purged with nitrogen, was charged with 80 liters of butane at room temperature, and then 91.8 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. I put it in. Thereafter, the temperature in the reactor was increased to 50 ° C. and stirred for 2 hours. The temperature in the reactor was lowered to 30 ° C., and 0.1 kg of ethylene was added. Next, 695 g of the olefin polymerization catalyst component (A) obtained in Example 1 (2) was added. Thereafter, 0.1 liter of hydrogen was introduced at normal temperature and pressure. After the system was stabilized, 263 mmol of triisobutylaluminum was added to start prepolymerization.
After the start of the prepolymerization, the polymerization temperature in the reactor was operated at 30 ° C. for 0.5 hour, then the temperature was raised to 50 ° C. over 30 minutes, and then the polymerization was carried out at 50 ° C. For the first 0.5 hours, ethylene is supplied at 0.6 kg / hour, hydrogen is supplied at normal temperature and normal pressure at a rate of 0.6 liter / hour, and from 0.5 hours after the start of prepolymerization, ethylene is supplied. 4.45 kg / hour, hydrogen was supplied at normal temperature and normal pressure at a rate of 13.5 liters / hour, and prepolymerization was performed for a total of 6 hours. After completion of the prepolymerization, the reactor internal pressure was purged to 0.5 MPaG, the slurry prepolymerization catalyst was transferred to a dryer, and nitrogen circulation drying was performed to obtain a prepolymerization catalyst. The prepolymerization amount of the ethylene polymer in the prepolymerization catalyst was 29.8 g per 1 g of the olefin polymerization catalyst component.

(4) Gas phase polymerization Using a fluidized bed gas phase continuous polymerization reactor, polymerization temperature: 85 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 89.50 mol%, hydrogen 1.29 mol% 1-butene 1.95 mol%, 1-hexene 0.58 mol%, nitrogen 6.68 mol%, circulating gas linear velocity: 0.35 m / sec, prepolymerization catalyst supply amount: 35.9 g / hr, triethylamine supply A copolymerization of ethylene, 1-butene and 1-hexene was carried out under the conditions of an amount: 0.6 mmol / hr and a supply amount of triisobutylaluminum: 20 mmol / hr. A 1-butene-1-hexene copolymer powder was obtained. The deformed powder ratio in the ethylene-1-hexene copolymer powder was 18 wtppm. Further, the density of the ethylene-1-butene-1-hexene copolymer was 918.6 kg / m ³ , MFR was 0.55 g / 10 min, and Mw / Mn was 6.4.

[Comparative Example 1]
(1) Treatment of silica In a reactor equipped with a nitrogen-replaced stirrer, 24 kg of toluene as a solvent and silica heat-treated at 300 ° C. under a nitrogen stream as a fine particle carrier (a) (Sypolol 948 manufactured by Devison; average particle diameter = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 2.80 kg was added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.91, 1 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.43 kg of toluene was maintained in 23 minutes while maintaining the reactor temperature at 5 ° C. It was dripped. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3.3 hours. Thereafter, the obtained solid product was washed 6 times with 21 kg of toluene. Thereafter, 7.1 kg of toluene was added and allowed to stand overnight.

(2) Preparation of Olefin Polymerization Catalyst Component (A) To the toluene slurry obtained in Example 1 (1) above, 2.75 kg of a hexane solution of 50 wt% diethylzinc as compound (b) and 1.hexane as a solvent. 0 kg was added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 1.24 kg of trifluorophenol as the compound (c) and 2.29 kg of toluene as the solvent was added dropwise over 58 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, the temperature was lowered to 22 ° C., and 0.11 kg of water was added dropwise as compound (d) over 1.5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 22 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. Stirring was stopped and the supernatant liquid was withdrawn until the remaining amount reached 16 liters, and 11.6 kg of toluene was added and stirred. The temperature was raised to 95 ° C. and stirred for 4 hours. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Then, the olefin polymerization catalyst component (A) was obtained by drying. As a result of elemental analysis, Zn = 14 wt%, Si = 25 wt%, F = 8.3 wt%, and N = 1.9 wt%.
From this, the proportion of the fine particle carrier (a) in the olefin polymerization catalyst component (A) was 54 wt%.

(3) Prepolymerization Into a reactor equipped with a stirrer with an internal volume of 210 liters, which was previously purged with nitrogen, 80 liters of butane was charged at room temperature, and then 79.8 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. I put it in. Thereafter, the temperature in the reactor was increased to 50 ° C. and stirred for 2 hours. The temperature in the reactor was lowered to 30 ° C., and 0.1 kg of ethylene was added. 701 g of the above-mentioned catalyst component (A) for olefin polymerization was added. Thereafter, 0.1 liter of hydrogen was introduced at normal temperature and pressure. After the system was stabilized, 245 mmol of triisobutylaluminum was added to start prepolymerization.
After the start of the prepolymerization, the polymerization temperature in the reactor was operated at 30 ° C. for 0.5 hour, then the temperature was raised to 50 ° C. over 30 minutes, and then the polymerization was carried out at 50 ° C. For the first 0.5 hours, ethylene is supplied at 0.6 kg / hour, hydrogen is supplied at normal temperature and normal pressure at a rate of 0.5 liter / hour, and from 0.5 hours after the start of prepolymerization, ethylene is supplied. Hydrogen was supplied at a rate of 8.9 liters / hour at 3.0 kg / hour and normal temperature and pressure, and prepolymerization was carried out for a total of 4 hours. After completion of the prepolymerization, the reactor internal pressure was purged to 0.5 MPaG, the slurry prepolymerization catalyst was transferred to a dryer, and nitrogen circulation drying was performed to obtain a prepolymerization catalyst. The prepolymerization amount of the ethylene polymer in the prepolymerization catalyst was 14.2 g per 1 g of the olefin polymerization catalyst component.

(4) Gas phase polymerization Using a fluidized bed gas phase continuous polymerization reactor, polymerization temperature: 86 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 89.30 mol%, hydrogen 1.28 mol% 1-butene 1.93 mol%, 1-hexene 0.63 mol%, nitrogen 6.86 mol%, circulating gas linear velocity: 0.34 m / sec, prepolymerization catalyst supply amount: 20.5 g / hr, triethylamine supply When copolymerization of ethylene, 1-butene and 1-hexene was performed under the conditions of an amount: 0.6 mmol / hr and a supply amount of triisobutylaluminum: 20 mmol / hr, a production rate of about 22.5 kg / hr was obtained. Ethylene-1-butene-1-hexene copolymer powder was obtained. The deformed powder ratio in the ethylene-1-hexene copolymer powder was 185 wtppm. In addition, the density of the ethylene-1-butene-1-hexene copolymer was 918.6 kg / m ³ , MFR was 0.72 g / 10 min, and Mw / Mn was 6.1.

[Comparative Example 2]
(1) Treatment of silica In a reactor equipped with a nitrogen-replaced stirrer, 2739 g of toluene as a solvent and silica heat-treated at 300 ° C. under a nitrogen stream as particles (a) (Sypolol 948 manufactured by Devison; average particle size = 55 μm) Pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 322 g was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 103 g of 1,1,1,3,3,3-hexamethyldisilazane and 232 g of toluene was added dropwise over 30 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3 hours. Thereafter, the obtained solid product was washed 6 times with 2367 g of toluene. Then, 788g of toluene was added and left still overnight.

(2) Preparation of Olefin Polymerization Catalyst Component (A) To the toluene slurry obtained in Comparative Example 2 (1) above, 163 g of a 50 wt% diethylzinc hexane solution as compound (b) and 103 g of hexane as a solvent were added. , Stirred. Then, after cooling to 5 ° C., a mixed solution of 62 g of pentafluorophenol as compound (c) and 92 g of toluene as a solvent was added dropwise over 60 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 9.1 g of water as the compound (d) was added dropwise over 1.5 hours while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours and at 55 ° C. for 2 hours. Thereafter, 108 g of a 50 wt% diethylzinc hexane solution as a compound (b) and 69 g of hexane as a solvent were added at room temperature. After cooling to 5 ° C., a mixed solution of 33 g of 3,4,5-trifluorophenol as the compound (c) and 61 g of toluene as the solvent was added dropwise over 60 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 6.1 g of water as the compound (d) was added dropwise over 1.5 hours while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. Stirring was stopped and the supernatant liquid was extracted until the remaining amount became 1.6 liters, and 1320 g of toluene was added thereto and stirred. The temperature was raised to 95 ° C. and stirred for 4 hours. The obtained solid product was washed 4 times with 1320 g of toluene and 3 times with 2.74 liters of hexane. Then, the olefin polymerization catalyst component (A) was obtained by drying. As a result of elemental analysis, Si = 28 wt%, Zn = 16 wt%, F = 8.0 wt%, and N = 1.6 wt%. From this, the proportion of the fine particle carrier (a) in the olefin polymerization catalyst component (A) was 60 wt%.

(3) Prepolymerization To a reactor equipped with a stirrer with an internal volume of 210 liters that had been previously purged with nitrogen, 80 liters of butane was charged at room temperature, and then 49.5 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. I put it in. Thereafter, the temperature in the reactor was increased to 50 ° C. and stirred for 2 hours. The temperature in the reactor was lowered to 30 ° C., and 0.1 kg of ethylene was added. 448 g of the olefin polymerization catalyst component (A) obtained in Comparative Example 2 (2) was charged. Thereafter, 0.1 liter of hydrogen was introduced at normal temperature and pressure. After the system was stabilized, 68 mmol of triisobutylaluminum was added to start prepolymerization.
After the start of the prepolymerization, the polymerization temperature in the reactor was operated at 30 ° C. for 0.5 hour, then the temperature was raised to 50 ° C. over 30 minutes, and then the polymerization was carried out at 50 ° C. For the first 0.5 hours, ethylene is supplied at 0.4 kg / hour, hydrogen is supplied at a normal temperature and normal pressure at a rate of 0.7 liter / hour, and from 0.5 hours after the start of prepolymerization, ethylene is supplied. Hydrogen was supplied at a rate of 6.0 liters / hour at a normal temperature and a normal pressure of 2.2 kg / hour, and preliminary polymerization was carried out for a total of 4 hours. After completion of the prepolymerization, the reactor internal pressure was purged to 0.5 MPaG, the slurry prepolymerization catalyst was transferred to a dryer, and nitrogen circulation drying was performed to obtain a prepolymerization catalyst. The prepolymerization amount of the ethylene polymer in the prepolymerization catalyst was 12.1 g per 1 g of the olefin polymerization catalyst component (A).

(4) Gas phase polymerization Using a fluidized bed gas phase continuous polymerization reactor, polymerization temperature: 86 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 88.4 mol%, hydrogen 1.42 mol% 1-butene 1.97 mol%, 1-hexene 0.53 mol%, nitrogen 7.68 mol%, circulating gas linear velocity: 0.34 m / sec, prepolymerization catalyst supply amount: 56.5 g / hr, triethylamine supply When copolymerization of ethylene, 1-butene and 1-hexene was carried out under the conditions of an amount: 0.6 mmol / hr and a supply amount of triisobutylaluminum: 20 mmol / hr, ethylene- was produced at a production rate of about 24 kg / hr. A 1-butene-1-hexene copolymer powder was obtained. The deformed powder ratio in the ethylene-1-hexene copolymer powder was 786 wtppm. The density of the ethylene-1-butene-1-hexene copolymer was 919.4 kg / m ³ , the MFR was 0.65 g / 10 min, and the Mw / Mn was 11.3.

[Comparative Example 3]
(1) Silica treatment In a reactor equipped with a nitrogen-replaced stirrer, 24 kg of toluene as a solvent and silica heat-treated at 300 ° C. under a nitrogen stream as a fine particle carrier (a) (Sypolol 948 manufactured by Devison; average particle diameter = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 2.81 kg was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.91, 1 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.43 kg of toluene was maintained in 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3 hours. Thereafter, the obtained solid product was washed 6 times with 21 kg of toluene. Thereafter, 6.9 kg of toluene was added and allowed to stand overnight.

(2) Preparation of Olefin Polymerization Catalyst Component (A) To the toluene slurry obtained in the above Comparative Example 3 (1), 2.00 kg of a 50 wt% diethylzinc hexane solution as the compound (b) and hexane 1. 0 kg was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.77 kg of pentafluorophenol as the compound (c) and 1.14 kg of toluene as the solvent was added dropwise over 60 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.11 kg of water as the compound (d) was added dropwise over 1.5 hours while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours and at 55 ° C. for 2 hours. Thereafter, 1.35 kg of a 50 wt% diethylzinc hexane solution as compound (b) and 0.8 kg of hexane as a solvent were added at room temperature. After cooling to 5 ° C, a mixed solution of 0.41 kg of 3,4,5-trifluorophenol as the compound (c) and 0.76 kg of toluene as the solvent was added dropwise over 60 minutes while maintaining the reactor temperature at 5 ° C. did. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.076 kg of water as the compound (d) was added dropwise over 1.5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. Stirring was stopped and the supernatant liquid was withdrawn until the remaining amount reached 16 liters, and 11.6 kg of toluene was added and stirred. The temperature was raised to 95 ° C. and stirred for 4 hours. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Then, the olefin polymerization catalyst component (A) was obtained by drying. As a result of elemental analysis, Si = 24 wt%, Zn = 16 wt%, F = 9.4 wt%, and N = 1.5 wt%.
From this, the proportion of the fine particle carrier (a) in the olefin polymerization catalyst component (A) was 51 wt%.

(3) Prepolymerization Into a reactor with an internal volume of 210 liters that had been previously purged with nitrogen, 80 liters of butane was charged at room temperature, and then 72.1 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. I put it in. Thereafter, the temperature in the reactor was increased to 50 ° C. and stirred for 2 hours. The temperature in the reactor was lowered to 30 ° C., and 0.1 kg of ethylene was added. 702 g of the olefin polymerization catalyst component (A) obtained in Comparative Example 3 (2) was charged. Thereafter, 0.1 liter of hydrogen was introduced at normal temperature and pressure. After the system was stabilized, 105 mmol of triisobutylaluminum was added to start prepolymerization.
After the start of the prepolymerization, the polymerization temperature in the reactor was operated at 30 ° C. for 0.5 hour, then the temperature was raised to 50 ° C. over 30 minutes, and then the polymerization was carried out at 50 ° C. For the first 0.5 hour, ethylene is supplied at 0.6 kg / hour, hydrogen is supplied at a normal temperature and normal pressure at a rate of 0.7 liter / hour. Hydrogen was supplied at a rate of 8.6 liters / hour at a normal temperature and pressure of 3.4 kg / hour, and preliminary polymerization was carried out for a total of 4 hours. After completion of the prepolymerization, the reactor internal pressure was purged to 0.5 MPaG, the slurry prepolymerization catalyst was transferred to a dryer, and nitrogen circulation drying was performed to obtain a prepolymerization catalyst. The prepolymerization amount of the ethylene polymer in the prepolymerization catalyst was 16.0 g per 1 g of the olefin polymerization catalyst component (A).

(4) Gas phase polymerization Using a fluidized bed gas phase continuous polymerization reactor, polymerization temperature: 86 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 89.20 mol%, hydrogen 1.44 mol% 1-butene 1.95 mol%, 1-hexene 0.58 mol%, nitrogen 6.83 mol%, circulating gas linear velocity: 0.34 m / sec, prepolymerization catalyst supply amount: 30.3 g / hr, triethylamine supply When copolymerization of ethylene, 1-butene and 1-hexene was carried out under the conditions of an amount: 0.6 mmol / hr and a supply amount of triisobutylaluminum: 20 mmol / hr, the production rate was about 22.4 kg / hr. Ethylene-1-butene-1-hexene copolymer powder was obtained. The deformed powder ratio in the ethylene-1-hexene copolymer powder was 2439 wtppm. Moreover, the density of the ethylene-1-butene-1-hexene copolymer was 918.0 kg / m ³ , MFR was 0.59 g / 10 min, and Mw / Mn was 10.2.

Claims (5)

The following compound (a), (b), (c) and component (d) are contacted, and the molar ratio of the amounts of the compounds (a), (b), (c) used in the contact is (a ): (B): (c) = 1: When y: z, y and z are solid catalyst components for olefin polymerization satisfying the following formulas (1), (2) and (3), and the olefin Olefin polymerization in which the content of the component (d) contained in the polymerization catalyst component (A) is 57 to 80% by weight (provided the total weight of the olefin polymerization catalyst component (A) is 100% by weight) Catalyst component.
(A) Compound M ¹ L ¹ _m [1] represented by the following formula [1]
(B) Compound represented by the following formula [2]

[2]
(C) Compound R ³ _t-2 TH ₂ [3] represented by the following formula [3]
(D) Particles (wherein, in the above formulas [1] to [3], M ¹ is a typical metal atom of Group 1, 2 and 12 of the periodic table of elements, germanium atom, tin atom, lead atom, antimony atom, a bismuth atom, .L ¹ m is representative of a number corresponding to the valence of M ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ is R ¹ may be the same as or different from each other, R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and three R ¹ may be the same or different from each other and are adjacent to each other. Two R ¹ bonded to each carbon atom may be connected to each other to form a condensed ring structure adjacent to the benzene ring, R ² represents a hydrogen atom or a hydrocarbon group, and R ³ represents a hydrocarbon group. Or a halogenated hydrocarbon group, wherein T is independently Atom, phosphorus atom, an oxygen atom, a sulfur atom, t represents a number corresponding to the valence of T of each compound.)
| M−y−2z | ≦ 1 (1)
z ≧ −2.5y + 2.48 (2)
y <0.5m (3)
(However, in the above formulas (1) to (3), y and z represent a number larger than 0.)   An olefin polymerization catalyst obtained by contacting the catalyst component for olefin polymerization (A) according to claim 1 and a transition metal compound (B) of Group 3 to Group 11 or lanthanoid series of the periodic table.   A catalyst for olefin polymerization obtained by contacting the catalyst component for olefin polymerization (A) according to claim 1, the group 3 to group 11 of the periodic table or the lanthanoid series transition metal compound (B) and the organoaluminum compound (C). . The catalyst for olefin polymerization according to claim 2 or 3, wherein the group 3 to group 11 or lanthanoid series transition metal compound (B) in the periodic table is a transition metal compound represented by the following formula [4].
L ² _a M ² X ¹ _b [4]
(In the formula, M ² represents a transition metal atom of Group 3 to Group 11 of the periodic table of elements or a lanthanoid series. L ² represents a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, L ^{2 in the above} may be directly connected to each other, or may be connected via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and X ¹ is a halogen atom. Represents a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbon oxy group, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8. Represents.)   The manufacturing method of the olefin polymer which superposes | polymerizes an olefin using the catalyst for olefin polymerization in any one of Claims 2-4.