JPWO2019188644A1 - Method for producing transition metal compound, catalyst for olefin polymerization and olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method such as a transition metal compound useful for producing an olefin polymer having a high polymerization activity and a high molecular weight. [Solution] A transition metal compound represented by the following general formula [I] or [II]. [In the formula, R1 to R14 are hydrogen atoms, hydrocarbon groups, etc., and at least one or more of R5 to R12 are substituents represented by ZR (Z is an oxygen atom, etc., R is a hydrocarbon group, etc.) It is bonded to a fluorenyl ligand via Z.), A is a divalent hydrocarbon group, Y is a carbon atom, a silicon atom, etc., and M is a Group 4 transition metal atom in the periodic table. j is an integer of 1 to 4, Q is a halogen or the like. ]

Description

The present invention relates to novel transition metal compounds, catalysts for olefin polymerization, and methods for producing olefin polymers.

Ethylene / α-olefin rubber typified by ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) does not have an unsaturated bond in the main chain of its molecular structure, and therefore is widely used as a conjugated diene. Since it is superior in heat resistance and weather resistance to rubber, it is widely used in applications such as automobile parts, electric wire materials, building civil engineering materials, industrial material parts, and various resin modifiers.

Conventionally, ethylene / α-olefin / non-conjugated polyene copolymer rubbers such as EPDM generally use a catalyst system (so-called Ziegler-Natta catalyst system) composed of a titanium-based catalyst or a vanadium-based catalyst and an organoaluminum compound. Has been manufactured using. The biggest drawback of this catalyst system is its productivity, and because of its low polymerization activity and short catalyst life, it is forced to polymerize at a low temperature of around 0 to 50 ° C. For this reason, the high viscosity of the polymerization solution becomes an obstacle, the concentration of the olefin copolymer in the polymer cannot be sufficiently increased, and the productivity is remarkably low. Furthermore, since the polymerization activity is low, the amount of catalyst residue contained in the copolymer at the end of polymerization is large, and in many cases, the required performance of the product is not satisfied. Therefore, a decalcification process is required to remove it, which is a significant disadvantage in terms of production cost.

A so-called metallocene compound is well known as a homogeneous catalyst for olefin polymerization. The metallocene catalyst system, which has been actively studied since the 1980s, exhibits excellent polymerization activity and α-olefin copolymerization ability, and because it is a single-site catalyst, it is an olefin-based copolymer having a narrow molecular weight distribution and composition distribution. It enables the production of. In the polymerization of α-olefin using this metallocene compound as a catalyst, a substituent is introduced into the cyclopentadienyl ring of the ligand of the metallocene compound, or two cyclopentadienyl rings are crosslinked. , Polymerization activity, molecular weight of the obtained α-olefin polymer, etc. are known to change significantly, and many improved studies have been conducted.

As part of such studies, JA Ewen reported polymerization results with metallocene compounds with cyclopentadienyl and fluorenyl ligands (J. Am. Chem. Soc., 110, 6255). (1988)). Further, as an improvement of this metallocene compound, a metallocene compound in which a cyclopentadienyl ligand and a fluorenyl ligand are crosslinked via a divalent silicon-containing substituent has been reported (for example, Patent Document 1, Non-Patent Document 1). Patent Documents 1 and 2).

It has also been reported that various substituents are introduced into the fluorenyl ligand and the steric and electronic effects of the various fluorenyl ligands affect the polymerization result (Chem. Rev., 100, 1205 (2000). )etc). In these documents, as one of the substituent effects on fluorene, when a heteroatom-containing electron-donating group such as a methoxy group is held at the 4- or 5-position, the catalytic activity and the polymer molecular weight are improved, and 2,3, It has been reported that the polymerization activity is significantly reduced when it is held at the 6th or 7th position (for example, Patent Document 2, Non-Patent Documents 3 and 4).

In general, it is difficult to introduce a substituent at the 4th and 5th positions of fluorene. Therefore, considering the catalytic performance, production cost, production efficiency, etc. of the metallocene compound, the metallocene compound having a methoxy group on fluorene is suitable for commercial practical use. Is disadvantageous. Therefore, many existing metallocene compounds having a fluorenyl ligand have the 2,3,6 or 7 positions at which substituents are easily introduced modified with an alkyl group, and adjacent substituents form a ring structure. There are also reports that aim to realize an excellent olefin polymerization catalyst by forming it (Patent No. 4376688, etc.).

Many reports have also been made on methods for producing ethylene / α-olefin / non-conjugated polyene copolymers using a metallocene catalyst system.

In the method for producing an ethylene / α-olefin / non-conjugated polyene copolymer using a metallocene catalytic system, the polymerization activity is adaptable to a non-decalcification process, the molecular weight is high enough to withstand high temperature polymerization, and the monomer recovery process is not burdened. In order to solve problems in terms of production, cost, and physical properties such as non-conjugated polyene copolymerization ability and high monomer alternating copolymerization ability to show good low temperature characteristics in terms of physical properties, various improvements have been made to metallocene compounds in the past. It has been added.

For example, Patent Document 3 discloses a method for producing an ethylene / α-olefin / non-conjugated polyene copolymer using a catalyst containing a specific crosslinked cyclopentadienyl-fluorenylmetallocene compound, and this production method. To produce an ethylene / α-olefin / non-conjugated polyene copolymer having good polymerization activity, good non-conjugated polyene copolymerization ability, very high molecular weight, and strong monomer alternating copolymerization. Furthermore, it is described that the polymerization temperature can be set higher.

Japanese Unexamined Patent Publication No. 7-138275 Japanese Unexamined Patent Publication No. 6-172443 International Publication No. 2009/081794

J. Organomet. Chem., 497, 1 (1995) J. Organomet. Chem., 509, 63 (1996) J. Organomet. Chem., 501, 101 (1995) J. Organomet. Chem., 522, 39 (1996)

However, in the conventional method for producing an olefin polymer (for example, ethylene / α-olefin / non-conjugated polyene copolymer) using a metallocene catalytic system, the polymerization activity and the increase in the amount of the produced copolymer are increased. From the point of view, there was room for further improvement.

In view of such problems in the prior art, the present invention presents a method for producing an olefin polymer having a high polymerization activity and a high molecular weight (particularly ethylene / α-olefin / non-conjugated polyene copolymer), and such a method. An object of the present invention is to provide a metallocene compound useful for producing an olefin polymer and a catalyst for olefin polymerization.

As a result of diligent research, the present inventors have conducted a method for producing an olefin polymer using a catalyst for olefin polymerization containing a crosslinked metallocene compound having a specific structure, and a metallocene compound (transition) useful for producing such an olefin polymer. We have found that the above problems can be solved by using a metal compound) and a catalyst for olefin polymerization, and have completed the present invention. The gist of the present invention is as follows.

[1]
The transition metal compound [A] represented by the following general formula [I] or [II].

〔式［I］および［II］において、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ¹³およびＲ¹⁴は、それぞれ独立に、水素原子、炭素数１〜２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ¹からＲ⁴までの隣接した置換基は互いに結合して環を形成していてもよく、互いに結合していなくてもよく、Ｒ¹³およびＲ¹⁴は互いに結合して環を形成していてもよく、
Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、ＺＲで表される置換基（ただし、Ｚは酸素原子または硫黄原子であり、Ｒは炭素数１〜２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基およびハロゲン含有基からなる群から選ばれる置換基であり、Ｚを介してフルオレニル配位子と結合している。）、炭素数１〜２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基（ただし、ＺＲで表される置換基を除く。）、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ⁵からＲ¹²までの隣接した置換基は互いに結合して環を形成していてもよく、Ｒ⁵からＲ¹²のうち、少なくとも１つはＺＲで表される置換基であり、
Ｙは炭素原子、ケイ素原子、ゲルマニウム原子およびスズ原子から選ばれ、
Ａは芳香環を含んでいてもよい炭素原子数２〜２０の二価の飽和もしくは不飽和の炭化水素基であり、ＡはＹと共に形成する環を含めて２つ以上の環構造を含んでいてもよく、
Ｍはチタン原子、ジルコニウム原子またはハフニウム原子であり、
ｊは１〜４の整数であり、
Ｑは、ハロゲン原子、炭素数１〜２０の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から選ばれ、ｊが２以上の場合は、複数個あるＱは互いに同一であっても異なっていてもよい。〕
［２］
前記一般式［I］または［II］においてＺが酸素原子である前記［１］の遷移金属化合物［Ａ］。

[In equations [I] and [II]
R ¹ , R ² , R ³ , R ⁴ , R ¹³ and R ¹⁴ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, substituted aryl groups, silicon-containing groups, and nitrogen-containing groups, respectively. , An atom or substituent selected from the group consisting of an oxygen-containing group, a halogen atom and a halogen-containing group, and adjacent substituents R ¹ to R ⁴ may be bonded to each other to form a ring, or each other. It may not be bonded, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are independently represented by a hydrogen atom and a ZR (where Z is an oxygen atom or a sulfur atom). Yes, R is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group and a halogen-containing group, via Z. (It is bonded to a fluorenyl ligand), a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group (however, the substitution represented by ZR). (Excluding groups.), An atom or substituent selected from the group consisting of halogen atoms and halogen-containing groups, and adjacent substituents R ⁵ to R ¹² may be bonded to each other to form a ring. At least one of R ⁵ to R ¹² is a substituent represented by ZR.
Y is selected from carbon atom, silicon atom, germanium atom and tin atom,
A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A contains two or more ring structures including a ring formed with Y. May be
M is a titanium atom, a zirconium atom or a hafnium atom,
j is an integer from 1 to 4
Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair. When j is 2 or more, there are a plurality of Qs. May be the same as or different from each other. ]
[2]
The transition metal compound [A] of the above [1] in which Z is an oxygen atom in the general formula [I] or [II].

[3]
The transition metal compound [A] of the above [1] or [2] in which Y is a silicon atom in the general formula [I] or [II].

[4]
The transition metal compound [A] according to any one of the above [1] to [3], wherein M is a zirconium atom in the general formula [I] or [II].

[5]
A catalyst for olefin polymerization containing any of the transition metal compounds [A] of [1] to [4].

[6]
[B] [B-1] Organometallic compounds,
The above-mentioned [5] further containing at least one compound selected from the group consisting of the [B-2] organoaluminum oxy compound and the [B-3] transition metal compound [A] to form an ion pair. ] Catalyst for olefin polymerization.

[7]
A method for producing an olefin polymer, which comprises the step [P] of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to the above [5] or [6].

[8]
The method for producing an olefin polymer (that is, an ethylene polymer) according to the above [7], wherein the step [P] is a step of polymerizing ethylene.

[9]
The method for producing an olefin polymer according to the above [8], wherein the step [P] is a step of copolymerizing ethylene and a non-conjugated polyene.

[10]
The method for producing an olefin polymer according to the above [9], wherein the non-conjugated polyene is represented by the following general formula [III].

〔式中、ｍは０から２の整数であり、
Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷およびＲ¹⁸は、それぞれ独立に、水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、該炭化水素基は二重結合を有していてもよく、
Ｒ¹⁵からＲ¹⁸までのうちの任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹⁵とＲ¹⁶とで、またはＲ¹⁷とＲ¹⁸とでアルキリデン基を形成していてもよく、Ｒ¹⁵とＲ¹⁷とが、またはＲ¹⁶とＲ¹⁸とが互いに結合して二重結合を形成していてもよく、
以下の（i）から（iv）の要件の少なくとも一つが満たされる。
（i）Ｒ¹⁵からＲ¹⁸までの少なくとも一つは、二重結合を一つ以上有する炭化水素基である。
（ii）Ｒ¹⁵からＲ¹⁸までの任意の二つの置換基は互いに結合して環を形成し、該環は二重合を含んでいる。
（iii）Ｒ¹⁵とＲ¹⁶とで、またはＲ¹⁷とＲ¹⁸とでアルキリデン基を形成している。
（iv）Ｒ¹⁵とＲ¹⁷とが、またはＲ¹⁶とＲ¹⁸とが互いに結合して二重結合を形成している。〕
［１１］
前記非共役ポリエンが、５−エチリデン−２−ノルボルネン（ＥＮＢ）または５−ビニル−２−ノルボルネン（ＶＮＢ）であることを特徴とする、前記［１０］のオレフィン重合体の製造方法。

[In the formula, m is an integer from 0 to 2,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, respectively. The hydrocarbon group may have a double bond.
Any two substituents from R ¹⁵ to R ¹⁸ may be bonded to each other to form a ring, which ring may contain a double bond, with R ¹⁵ and R ¹⁶ . Alternatively, R ¹⁷ and R ¹⁸ may form an alkylidene group, R ¹⁵ and R ¹⁷ may be bonded to each other, or R ¹⁶ and R ¹⁸ may be bonded to each other to form a double bond.
At least one of the following requirements (i) to (iv) is met.
(I) At least one of R ¹⁵ to R ¹⁸ is a hydrocarbon group having one or more double bonds.
(Ii) Any two substituents from R ¹⁵ to R ¹⁸ bond to each other to form a ring, which contains dipolymerization.
(Iii) An alkylidene group is formed between R ¹⁵ and R ¹⁶ or between R ¹⁷ and R ¹⁸ .
(Iv) R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond. ]
[11]
The method for producing an olefin polymer according to the above [10], wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB).

[12]
The method for producing an olefin polymer according to any one of [9] to [11], wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene.

[13]
The method for producing the olefin polymer according to the above [12], wherein the α-olefin is propylene.

[14]
The method for producing an olefin polymer according to the above [8] to [13], wherein the polymerization temperature in the step [P] is 80 ° C. or higher.

[15]
The method for producing an olefin polymer according to the above [7], wherein the step [P] is a step of polymerizing an α-olefin having 3 to 20 carbon atoms.

[16]
The method for producing an olefin polymer according to the above [15], wherein the step [P] is a step of copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms.

[17]
The method for producing an olefin polymer according to the above [15] or [16], wherein the α-olefin is propylene.

According to the present invention, it is possible to produce an olefin polymer having a high molecular weight with high polymerization activity, particularly an ethylene / α-olefin / non-conjugated polyene copolymer.

The present invention will be described in more detail.

[Transition metal compound [A]]
The transition metal compound [A] according to the present invention (hereinafter, may be referred to as “crosslinked metallocene compound [A]” or “component (A)”) is represented by the following general formula [I] or [II]. To.

《Ｒ ¹ 〜Ｒ ¹⁴ 、Ｙ、Ａ》
前記一般式［I］および［II］において、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ¹³およびＲ¹⁴は、それぞれ独立に、水素原子、炭素数１〜２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ¹からＲ⁴までの隣接した置換基は互いに結合して環を形成していてもよく（ただし、シクロペンタジエニル基およびＲ¹〜Ｒ⁴によって形成される構造から、フルオレニル基および置換フルオレニル基は除く。）、互いに結合していなくてもよく、好ましくは互いに結合しておらず、Ｒ¹³およびＲ¹⁴は互いに結合して環を形成していてもよく、互いに結合していなくてもよく、
Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、ＺＲで表される置換基（ただし、Ｚは酸素原子または硫黄原子であり、Ｒは炭素数１〜２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基およびハロゲン含有基からなる群から選ばれる置換基であり、Ｚを介してフルオレニル配位子と結合している。）、炭素数１〜２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基（ただし、ＺＲで表される置換基を除く。）、ハロゲン原子およびハロゲン含有基からなる群から選ばれる原子または置換基であり、Ｒ⁵からＲ¹²までの隣接した置換基は互いに結合して環を形成していてもよく、互いに結合していなくてもよく、Ｒ⁵からＲ¹²のうち、少なくとも１つ以上はＺＲで表される置換基である。

<< R ^{1 to} R ¹⁴ , Y, A >>
In the general formulas [I] and [II],
R ¹ , R ² , R ³ , R ⁴ , R ¹³ and R ¹⁴ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, substituted aryl groups, silicon-containing groups, and nitrogen-containing groups, respectively. , An atom or substituent selected from the group consisting of an oxygen-containing group, a halogen atom and a halogen-containing group, and adjacent substituents R ¹ to R ⁴ may be bonded to each other to form a ring (provided that they form a ring). , Fluoropenyl group and substituted fluorenyl group are excluded from the structure formed by the cyclopentadienyl group and R ^{1 to} R ⁴ ), which may not be attached to each other, preferably not to each other, R ¹³ And R ¹⁴ may or may not be coupled to each other to form a ring.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are independently represented by a hydrogen atom and a ZR (where Z is an oxygen atom or a sulfur atom). Yes, R is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group and a halogen-containing group, via Z. (It is bonded to a fluorenyl ligand), a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group (however, the substitution represented by ZR). (Excluding groups.), An atom or substituent selected from the group consisting of halogen atoms and halogen-containing groups, and adjacent substituents R ⁵ to R ¹² may be bonded to each other to form a ring. It does not have to be bonded to each other, and at least one or more of R ⁵ to R ¹² are substituents represented by ZR.

The hydrocarbon group having 1 to 20 carbon atoms includes an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, and 3 carbon atoms. 20 to 20 cyclic unsaturated hydrocarbon groups are exemplified. Further, when adjacent substituents R ¹ to R ¹² are bonded to each other to form a ring, the hydrocarbon group having 1 to 20 carbon atoms to be bonded to each other to form a ring has 1 carbon number. Examples thereof include an alkylene group of ~ 20 and an arylene group having 6 to 20 carbon atoms.

The alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and n-heptyl group, which are linear saturated hydrocarbon groups. , N-octyl group, n-nonyl group, n-decanyl group, etc., which are branched saturated hydrocarbon groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group, neopentyl group, 3 -Methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-dipropylbutyl group, 1,1-dimethyl-2-methylpropyl Examples include a group, a 1-methyl-1-isopropyl-2-methylpropyl group, and a cyclopropylmethyl group. The alkyl group preferably has 1 to 6 carbon atoms.

Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, which are cyclic saturated hydrocarbon groups. 3-Methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4 which is a group in which the hydrogen atom of the cyclic saturated hydrocarbon group such as 2-adamantyl group is replaced with a hydrocarbon group having 1 to 17 carbon atoms. -Cyclohexylcyclohexyl group, 4-phenylcyclohexyl group and the like are exemplified. The cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.

Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include an alkenyl group, an ethenyl group (vinyl group), a 1-propenyl group, a 2-propenyl group (allyl group), and a 1-methylethenyl group (isopropenyl group). Examples thereof include an ethynyl group, which is an alkynyl group, a 1-propynyl group, and a 2-propynyl group (propargyl group). The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.

Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopentadienyl group, a norbornyl group, a phenyl group, a naphthyl group, an indenyl group, an azulenyl group, a phenanthryl group and an anthrasenyl group, which are cyclic unsaturated hydrocarbon groups. , 3-Methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), which is a group in which the hydrogen atom of the cyclic unsaturated hydrocarbon group is replaced with a hydrocarbon group having 1 to 15 carbon atoms. , 4-Ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group ( A benzyl group, which is a group in which the hydrogen atom of a linear hydrocarbon group or a branched saturated hydrocarbon group is replaced with a cyclic saturated hydrocarbon group having 3 to 19 carbon atoms or a cyclic unsaturated hydrocarbon group, such as a mesityl group. Examples include a Kumil group. The cyclic unsaturated hydrocarbon group preferably has 6 to 10 carbon atoms.

Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a dimethylmethylene group (isopropyridene group), an ethylmethylene group, a 1-methylethylene group, a 2-methylethylene group, and a 1,1-dimethylethylene group. Examples thereof include a 1,2-dimethylethylene group and an n-propylene group. The alkylene group preferably has 1 to 6 carbon atoms.

Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, and a 4,4'-biphenylylene group. The arylene group preferably has 6 to 12 carbon atoms.

As the aryl group, although it partially overlaps with the above-mentioned example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, it is a substituent derived from an aromatic compound, such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Examples thereof include a group, anthrasenyl group, phenanthrenyl group, tetrasenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like. As the aryl group, a phenyl group or a 2-naphthyl group is preferable.

Examples of the aromatic compound include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysen, pyrene, pyrene, inden, azulene, pyrrole, pyridine, furan, and thiophene. Will be done.

The substituted aryl group partially overlaps with the above-mentioned example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but one or more hydrogen atoms of the aryl group are hydrocarbon groups having 1 to 20 carbon atoms. Examples thereof include a group substituted with a substituent selected from an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and specifically, a 3-methylphenyl group (m-tolyl group). ), 4-Methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4- (trimethylsilyl) Phenyl group, 4-aminophenyl group, 4- (dimethylamino) phenyl group, 4- (diethylamino) phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxyphenyl Group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3- (trifluoromethyl) phenyl group, Examples include 4- (trifluoromethyl) phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, 2- (6-methyl) pyridyl group and the like. Will be done.

Examples of the silicon-containing group include alkyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and triisopropylsilyl group, which are groups in which carbon atoms are replaced with silicon atoms in hydrocarbon groups having 1 to 20 carbon atoms. Examples thereof include an arylsilyl group such as a silyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group and a t-butyldiphenylsilyl group, a pentamethyldisilanyl group and a trimethylsilylmethyl group. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

As the nitrogen-containing group, an amino group, a nitro group, and an N-morpholinyl group, and a group in which the CH-structural unit is replaced with a nitrogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group, -CH ₂ -A group in which the structural unit is replaced with a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, or -CH ₃ A nitrogen atom or nitrile to which a hydrocarbon group having 1 to 20 carbon atoms is bonded. Examples thereof include a dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, a pyridinyl group and the like which are groups replaced with a group. As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferable.

Oxygen-containing groups include hydroxyl groups, and the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, or nitrogen-containing groups in which -CH ₂ -structural units are replaced with oxygen atoms or carbonyl groups, or-. A methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsiloxy group, a methoxyethoxy group, and a hydroxymethyl group in which the CH ₃ structural unit is replaced with an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded. Group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl Group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl Examples thereof include a group, a carboxy group, a methoxycarbonyl group, a carboxymethyl group, an etocarboxymethyl group, a carbamoylmethyl group, a furanyl group and a pyranyl group. As the oxygen-containing group, a methoxy group is preferable.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, which are Group 17 elements.

Examples of the halogen-containing group include a trifluoromethyl group and a tribromo, which are groups in which a hydrogen atom is substituted with a halogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group or an oxygen-containing group. Examples thereof include a methyl group, a pentafluoroethyl group and a pentafluorophenyl group.

The substituent represented by ZR partially overlaps with the oxygen-containing group described above.

In the substituent represented by ZR, Z is an oxygen atom or a sulfur atom, preferably an oxygen atom.

R is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group and a halogen-containing group, and Z in R. The atom bonded to is a carbon atom or a silicon atom. Examples of these include those exemplified as ^{R 1 ~R 4, R 13,} R 14, preferably a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, tert -Alkyl groups having 1 to 20 carbon atoms such as butyl group, cyclohexyl group and cycloheptyl group, aryl groups such as phenyl group and 2-naphthyl group, substituted aryl groups such as m-tolyl group and p-tolyl group, Alkylsilyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triisopropylsilyl group, more preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , A tert-butyl group, etc., an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group.

The substituent represented by ZR is bound to the fluorenyl ligand via Z.

In the general formulas [I] and [II], Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom.

In the general formula [II], A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A is two including a ring formed with Y. The above ring structure may be included. Examples of the divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms include those exemplified as R ^{1 to} R ¹⁴ .

Cyclopentadienyl group:
Examples of the cyclopentadienyl group having substituents R ¹ to R ⁴ in the above general formulas [I] and [II] include an unsubstituted cyclopentadienyl group in which R ¹ to R ⁴ are hydrogen atoms, 3-t-. Butylcyclopentadienyl group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group Group, 3-position 1-substituted cyclopentadienyl group such as 3-cyclohexylcyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethylcyclopentadienyl Group, 3-phenyl-5-methylcyclopentadienyl group, 3,5-di-t-butylcyclopentadienyl group, 3,5-dimethylcyclopentadienyl group, 3-phenyl-5-methylcyclopenta Examples thereof include, but are not limited to, a 3,5-position 2-substituted cyclopentadienyl group such as a dienyl group and a 3-trimethylsilyl-5-methylcyclopentadienyl group. From the viewpoint of ease of synthesis of the crosslinked metallocene compound, production cost, and copolymerization ability of non-conjugated polyene, a cyclopentadienyl group which is unsubstituted (R ^{1 to} R ⁴ are hydrogen atoms) is preferable.

Substituted fluorenyl group:
In the above general formulas [I] and [II], at least one or more of R ⁵ to R ¹² is a substituent represented by ZR.

Of R ⁵ to R ¹² , preferably at least one of R ⁶ and R ¹¹ is ZR, and more preferably both R ⁶ and R ¹¹ are ZR.

R ⁵ , R ⁸ , R ⁹ and R ¹² are preferably hydrogen atoms from the viewpoint of easiness of synthesizing the crosslinked metallocene compound.

When R ⁷ and R ¹⁰ are not ZR, hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms are preferable from the viewpoint of ease of synthesis, and from the viewpoint of achieving higher polymerization activity. , Hydrogen atom is particularly preferable. Examples of the hydrocarbon group having 1 to 20 carbon atoms include those exemplified as the hydrocarbon group having 1 to 20 carbon atoms of R ^{1 to} R ¹⁴ , and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and the like. An alkyl group such as an n-butyl group or a tert-butyl group is preferable, and a tert-butyl group is more preferable.

Cross-linking part:
In the above general formula [I], R ¹³ and R ¹⁴ may be the same or different from each other. Examples of R ¹³ and R ¹⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group and m-. Tolyl group, p-tolyl group, 4-t-butylphenyl group, p-chlorophenyl group, 4-biphenyl group, 2-naphthyl group, xsilyl group, benzyl group, m-trifluoromethylphenyl group are high molecular weight ethylene. It is preferable because it produces a / α-olefin / non-conjugated polyene copolymer.

In the above general formula [II], A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and Y is bonded to this A, for example, the following. It constitutes a cycloalkylidene group such as a cyclohexylidene group represented by the formula [IIa] and a cyclomethylenecilylene group such as a cyclotetramethylenesilylene group (1-silacyclopentylidene group) represented by the following formula [IIb]. ..

（式［IIa］及び［IIb］において、●は、上記一般式［II］における（置換）シクロペンタジエニル基および置換フルオレニル基との結合点を表す。）
また、ＡはＹとともに形成する環を含めて二つ以上の環構造を含んでいてもよい。

(In the formulas [IIa] and [IIb], ● represents the bonding point with the (substituted) cyclopentadienyl group and the substituted fluorenyl group in the above general formula [II].)
Further, A may include two or more ring structures including a ring formed together with Y.

In addition to the cyclohexylidene group represented by [IIa] above, specifically, a cyclopropylidene group, a cyclobutylidene group, a cyclopentylidene group, a cycloheptylidene group, a cyclooctylidene group, and a bicyclo [3.3]. .1] Nonylidene group, norbornylidene group, adamantylidene group, tetrahydronaphthylidene group, dihydroindanilidene group and the like can be mentioned.

In addition to the cyclotetramethylene silylene group (1-silacyclopentylidene group) represented by [IIb] above, specifically, a cyclodimethylene silylene group, a cyclotrimethylene silylene group, a cyclopentamethylene silylene group, and a cyclohexamethylene group. Examples thereof include a silylene group and a cycloheptamethylene silylene group.

<< M, j, Q >>
In the general formulas [I] and [II], M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, and more preferably a zirconium atom.

j is an integer of 1 to 4, preferably 2.

Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair. When j is 2 or more, there are a plurality of Qs. May be the same as or different from each other.

Details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above. When Q is a halogen atom, a chlorine atom is preferable. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms.

Examples of the anion ligand include an alkoxy group such as a methoxy group, a t-butoxy group and a phenoxy group, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate.

Neutral ligands that can be coordinated with a lone electron pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, and the like. An ether compound and the like can be exemplified.

(Preferable embodiment of the transition metal compound [A])
A preferred embodiment of the transition metal compound [A], for example, dimethylsilylene (eta ⁵ - cyclopentadienyl) [η ⁵ - (2,7- dimethoxy-fluorenyl)] zirconium dichloride, dimethylsilylene (eta ⁵ - Cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] Zirconium dichloride, diethylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2) , 7-Dimethoxyfluorenyl)] zirconium dichloride, diethylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride , Di-n-propylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, di-n-propylsilylene (η ⁵ -cyclopentadienyl) [ η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, diisopropylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluolel) Nyl)] Zirconium dichloride, diisopropylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] Zirconium dichloride, di-n-butyl Silyrene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] Zirconium dichloride, di-n-butylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,, 7-Dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, diisobutylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, Diisobutylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, di-tert-butylsilylene (η ⁵ -cyclo) Pentazienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, di-tert-butylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,) 6-di-tert -Butylfluorenyl)] zirconium dichloride, dicyclopentylcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, dicyclopentylcilylene (η ^5- cyclopentadienyl) Enyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, dicyclohexylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-) Dimethoxyfluorenyl)] zirconium dichloride, dicyclohexylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, to dicyclo Puchilcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, dicycloheptylcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy) -3,6-di-tert-butylfluorenyl)] zirconium dichloride, diphenylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, diphenylsilylene (η ⁵ -cyclopentadienyl) η ^5- (cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, di-m-tolylcyrylene (η ⁵ -cyclopentadienyl) ) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, di-m-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di) -tert-butylfluorenyl)] zirconium dichloride, di-p-trilcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, di-p-tolyl Sirilen (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride, 1-silacyclopentylidene silylene (η ⁵ -cyclo) Pentazienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, 1-silacyclopentylidene silylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-di) Methoxy-3,6-di-tert-butylfluorenyl)] zirconium dichloride. In addition, di-p-tolylcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride, di-p-tolylcyrylene (η ⁵⁾ -Cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Zyrosine dimethyl, diphenylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-) Dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride, diphenylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dimethyl, Di-p-tolylcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-di-t-butyl-4-methoxyfluorenyl)] zirconium dichloride, and di-p-tolylcyrylene (η ⁵⁾ -Cyclopentadienyl) (η ⁵ -4,4,7,7-Tetramethyl-3,4,7,8,9,12-Hexahydro-2H-Cyclopenta- [2,1-g: 3,4- g'] dichromenyl) zirconium dichloride is also mentioned.

<< Production method of transition metal compound [A] >>
The transition metal compound [A] according to the present invention is prepared by using the production method described in, for example, International Publication No. 01/27124, pages 84 to 92, as a compound represented by the formula (12), of the formula (12). R ⁵ to R ¹² in is by carried out using compounds conforming respectively R ⁵ to R ¹² as defined in formula [I] or [II] described above in the present invention, can be produced.

[Catalyst for olefin polymerization]
The catalyst for olefin polymerization according to the present invention contains the transition metal compound [A] of the present invention.

The catalyst for olefin polymerization of the present invention is preferably
It is selected from the group consisting of [B] [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and compounds that react with [B-3] transition metal compounds [A] to form ion pairs. At least one compound (hereinafter, also referred to as "compound [B]")
Is further contained.

The catalyst for olefin polymerization of the present invention is preferably, if necessary.
(C) Further contains a carrier.

The catalyst for olefin polymerization of the present invention can be used as needed.
(D) The organic compound component may be further contained.

The catalyst for olefin polymerization according to the present invention can be used for polymerization of olefins (ethylene, α-olefin having 3 to 20 carbon atoms, etc.) described later.

Hereinafter, each component other than the transition metal compound [A] will be specifically described.

(Compound [B])
Compound [B] (hereinafter, may be referred to as “component (B)”) is
[B-1] Organometallic compound (hereinafter also referred to as "component (B-1)"), preferably an organoaluminum compound represented by the following general formula (B-1a) [B-1a], the following general formula ( A complex alkylated product of a Group 1 metal represented by B-1b) and aluminum [B-1b], or a dialkyl compound of a Group 2 or Group 12 metal represented by the following general formula (B-1c) [ B-1c],
R ^a _m Al (OR ^b ) _n H _p X _q … (B-1a)
[In the general formula (B-1a), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same or different from each other, where X represents a halogen atom and m is 0. <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. ]
_{^{M a AlR a 4 ... (B}} -1b)
[In the general formula (B-1b), M ^a represents a Li, Na or K, R ^a represents a hydrocarbon group having carbon atoms 1 to 15 (preferably 1 to 4). ]
R ^a _r M ^b R ^b _s X _t … (B-1c)
[In the general formula (B-1c), R ^a and R ^b represent hydrocarbon groups having 1 to 15 carbon atoms and may be the same or different from each other, and M ^b is derived from Mg, Zn and Cd. Selected, X represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ],
[B-2] Organoaluminium oxy compound (hereinafter, also referred to as "component (B-2)"), and [B-3] a compound that reacts with the transition metal compound [A] to form an ion pair (hereinafter, "component"). (B-3) "
It is at least one compound selected from the group consisting of.

<< Organometallic compound [B-1] >>
As an organoaluminum compound [B-1a],
Tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,
Tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum ,
Tricycloalkylaluminum, such as tricyclohexylaluminum, tricyclooctylaluminum,
Triarylaluminum, such as triphenylaluminum, tri (4-methylphenyl) aluminum,
Dialkylaluminum hydrides such as diethylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride,
For example, isoprenyl aluminum represented by the general formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (in the formula, x, y, z are positive numbers and z ≤ 2x). Alkenyl aluminum,
Alkoxides such as isobutylaluminum methoxydo and isobutylaluminum ethoxyoxide,
Dialkylaluminum alkoxides such as dimethylaluminum methoxydo, diethylaluminum ethoxide, dibutylaluminum butoxide,
Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxydo, butyl aluminum sesquibutoxide,
Partially alkoxylated alkylaluminum with an average composition represented by the general formula R ^a _2.5 Al (OR ^b ) _0.5 etc.
Alkylaluminum aryloxide, such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide),
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride,
Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide,
Partially halogenated alkylaluminum, such as alkylaluminum dihalide, such as ethylaluminum dichloride,
Alkylaluminum dihydrides such as ethylaluminum dihydrides, propylaluminum dihydrides and other partially hydrogenated alkylaluminum,
Examples thereof include partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, ethylaluminum ethoxybromid and the like. Similarly, the general formula ^{_{R a m Al (OR b)}} n H p X compounds similar to the compounds represented by _q can also be used, for example, organic aluminum in which two or more aluminum compounds via a nitrogen atom is bonded Compounds can be mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the complex alkylated product [B-1b] of a Group 1 metal and aluminum include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Examples of the group 2 or group 12 metal dialkyl compound [B-1c] include dimethylmagnesium, diethylmagnesium, din-butylmagnesium, ethyl n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, and din. -Butyl zinc, diphenyl zinc and the like.

Among these, the organoaluminum compound [B-1a] is preferable.

The organometallic compound [B-1] may be used alone or in combination of two or more.

<< Organoaluminium oxy compound [B-2] >>
The organoaluminum oxy compound [B-2] may be, for example, a conventionally known aluminoxane, and is insoluble or sparingly soluble in benzene as exemplified in JP-A-2-78687. It may be a compound. Conventionally known aluminoxane can be produced, for example, by the methods (1) to (4) below, and is usually obtained as a solution of a hydrocarbon solvent.

(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and first cerium chloride hydrate. A method in which an organic aluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as, and adsorbed water or water of crystallization is reacted with the organic aluminum compound.

(2) A method in which water, ice or water vapor is directly allowed to act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

(4) A compound produced by reacting an organic aluminum such as trialkylaluminum with an organic compound having a carbon-oxygen bond such as a tertiary alcohol, a ketone, and a carboxylic acid is non-hydrolyzable such as a thermal decomposition reaction. How to convert.

The aluminoxane may contain a small amount of an organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be distilled and removed from the recovered solution of aluminoxane, and then redissolved in the solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound [B-1a]. Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

In addition, examples of the organoaluminum oxy compound [B-2] include modified methylaluminoxane. The modified methylaluminoxane is an aluminoxane prepared by using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAO. MMAOs can be prepared by the methods set forth in US Pat. No. 4,960,878 and US Pat. No. 5,041,584. In addition, aluminoxane having an isobutyl group of R, which is prepared by using trimethylaluminum and triisobutylaluminum, is commercially produced by Tosoh Finechem Co., Ltd. and the like under the names of MMAO and TMAO.

Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, unlike the above-mentioned ones insoluble or sparingly soluble in benzene, aliphatic hydrocarbons and the like are used. It has the characteristic of being soluble in alicyclic hydrocarbons.

Further, as the organoaluminum oxy compound [B-2], for example, an organoaluminum oxy compound containing a boron atom and a halogen as exemplified in International Publication No. 2005/066191 and International Publication No. 2007/131010 are used. Included aluminoxane, ionic aluminoxane as exemplified in WO 2003/082879 can also be mentioned.

The organoaluminum oxy compound [B-2] may be used alone or in combination of two or more.

<< Compound [B-3] that forms an ion pair by reacting with transition metal compound [A] >>
Examples of the compound [B-3] (hereinafter, also referred to as “ionic compound [B-3]”) that reacts with the transition metal compound [A] to form an ion pair include JP-A No. 1-501950. , Japanese Patent Application Laid-Open No. 1-502036, Japanese Patent Application Laid-Open No. 3-179005, Japanese Patent Application Laid-Open No. 3-179006, Japanese Patent Application Laid-Open No. 3-207703, Japanese Patent Application Laid-Open No. 3-207704, US Pat. No. 5,321106, etc. Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in. In addition, heteropoly compounds and isopoly compounds can also be mentioned.

As the ionic compound [B-3], a compound represented by the general formula (B-3a) is preferable.

式（B-3a）中、Ｒ^e+としては、例えば、Ｈ⁺、カルベニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンが挙げられる。Ｒ^f〜Ｒⁱはそれぞれ独立に有機基、好ましくはアリール基である。

Wherein (B-3a), as R e ⁺ is, for example, H ^+, carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal. R ^{f to} R ⁱ are independently organic groups, preferably aryl groups.

Examples of the carbocation cation include a trisubstituted carbocation cation such as a triphenyl carbocation cation, a tris (methylphenyl) carbocation cation, and a tris (dimethylphenyl) carbocation cation.

Examples of the ammonium cation include trialkylammonary cations such as trimethylammonium cation, triethylammonary cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation; , N-dimethylanilinium cations, N, N-diethylanilinium cations, N, N-2,4,6-pentamethylanilinium cations and other N, N-dialkylanilinium cations; diisopropylammonium cations, dicyclohexylammonium cations And the like dialkylammonium cations.

Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

As R ^{e +} , for example, a carbenium cation and an ammonium cation are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

Examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-ditrifluoromethylphenyl) borate, and tris (4-methylphenyl). ) Carbenium tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate can be mentioned.

Examples of the ammonium salt include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, and a dialkylammonium salt.

Examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, and trimethylammonium tetrakis (o-). Trill) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethyl) Phenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3) , 5-Ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (O-trill) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, di Examples thereof include octadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, and dioctadecylmethylammonium.

Examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and N, N-dimethylanilinium tetrakis (3,). 5-Ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoro) Methylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate.

Examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

As the ionic compound [B-3], other ionic compounds disclosed in JP-A-2004-51676 can also be used without limitation.

The ionic compound [B-3] may be used alone or in combination of two or more.

<Carrier [C]>
Examples of the carrier [C] include inorganic or organic compounds, which are granular or fine particle solids. In the method for producing an olefin polymer of the present invention described later, the transition metal compound [A] is preferably used in the form of being supported on the carrier [C].

<< Inorganic compounds >>
As the inorganic compound in the carrier [C], a porous oxide, an inorganic chloride, clay, a clay mineral or an ion-exchange layered compound is preferable.

Examples of the porous oxide include oxides of SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc., or a composite containing these. A mixture can be used. For example, natural or synthetic zeolite, SiO ₂ −MgO, SiO ₂ −Al ₂ O ₃ , SiO ₂ −TiO ₂ , SiO ₂ −V ₂ O ₅ , SiO ₂ −Cr ₂ O ₃ , SiO ₂ −TiO ₂ −MgO Can be used. Among these, a porous oxide containing SiO ₂ and / or Al ₂ O ₃ as a main component is preferable.

The properties of porous oxides differ depending on the type and manufacturing method. The carrier preferably used in the present invention has a particle size of preferably 1 to 300 μm, more preferably 3 to 100 μm; and a specific surface area of preferably 50 to 1300 m ² / g, more preferably 200 to 1200 m ² / g. The pore volume is preferably 0.3 to 3.0 cm ³ / g, more preferably 0.5 to 2.0 cm ³ / g. Such a carrier is used by drying and / or calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary. The particle shape is not particularly limited, but is particularly preferably spherical.

As the inorganic chloride, for example, MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ are used. The inorganic chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a solvent in which an inorganic chloride is dissolved in a solvent such as alcohol and then precipitated in the form of fine particles with a precipitant.

Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used. Further, as the clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, or an ionic crystalline compound having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl ₂ type and CdI ₂ type can be used. It can be exemplified.

Clays and clay minerals include, for example, kaolin, bentonite, knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, dikite, etc. Examples include halloysite, pectrite, and teniolite.

The ion-exchange layered compounds, for _{example, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ- Crystalline acidic salts of polyvalent metals such as Ti (NH ₄ PO ₄ ) ₂ and H ₂ O can be mentioned.

It is also preferable to chemically treat clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic substance treatment and the like.

The ion-exchangeable layered compound may be a layered compound in a state in which the layers are expanded by utilizing the ion-exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation.

Examples of the guest compounds to be intercalated include, for example, TiCl _4, ZrCl ₄ cationic inorganic compounds such _{as, Ti (OR) 4, Zr} (OR) 4, PO (OR) 3, B (OR) 3 or the like of metal Metal hydroxides such as alkoxides (R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^+, etc. Material ions can be mentioned. These compounds may be used alone or in combination of two or more. In addition, when these compounds were intercalated, metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , and Ge (OR) ₄ (R is a hydrocarbon group, etc.) were hydrolyzed. A polymer, a colloidal inorganic compound such as SiO _2, etc. can coexist.

Examples of the pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them.

Among the carriers [C], a porous oxide containing SiO ₂ and / or Al ₂ O ₃ as a main component is preferable. Clays or clay minerals are also preferred, with particular preference being montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

《Organic compounds》
Examples of the organic compound in the carrier [C] include granular or fine particle solids having a particle size in the range of 5 to 300 μm. Specifically, the main components are (co) polymers, vinylcyclohexane, and styrene produced mainly of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene. Examples thereof include (co) polymers produced as components and variants thereof.

<Organic compound component [D]>
In the present invention, the organic compound component [D] is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of the organic compound [D] include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers and sulfonates.

<Usage and order of addition of each component>
In the case of olefin polymerization, the usage and addition order of each component are arbitrarily selected, and the following methods are exemplified. Hereinafter, the transition metal compound [A], the compound [B], the carrier [C], and the organic compound component [D] are also referred to as “components (A) to (D)”, respectively.
(1) A method of adding the component (A) alone to a polymerizer.
(2) A method of adding the component (A) and the component (B) to the polymerizer in an arbitrary order.
(3) A catalyst component in which the component (A) is supported on the component (C), and
A method of adding the component (B) to the polymerizer in an arbitrary order.
(4) A catalyst component in which the component (B) is supported on the component (C), and
A method of adding the component (A) to a polymerizer in an arbitrary order.
(5) A method of adding a catalyst component in which a component (A) and a component (B) are supported on the component (C) to a polymerizer.

In each of the above methods (2) to (5), at least two kinds of each catalyst component may be contacted in advance. In each of the above methods (4) and (5) in which the component (B) is supported, the component (B) in which the component (B) is not supported may be added in any order, if necessary. In this case, the component (B) may be the same or different. Further, the solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) are obtained even if the olefin is prepolymerized. Often, the catalyst component may be further supported on the prepolymerized solid catalyst component.

[Method for producing olefin polymer]
The method for producing an olefin polymer of the present invention is characterized by having a step [P] of polymerizing an olefin (ethylene, α-olefin having 3 or more and 20 or less carbon atoms, etc.) in the presence of the above-mentioned catalyst for olefin polymerization. There is. Here, "polymerization" is a general term for homopolymerization and copolymerization. Further, "polymerizing an olefin in the presence of an olefin polymerization catalyst" means that each component of the olefin polymerization catalyst is added to a polymerizer by an arbitrary method as in the methods (1) to (5) above. The aspect of polymerizing the olefin is included.

In the present invention, the polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane and the like. Aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more. Further, a so-called bulk polymerization method in which the liquefied olefin itself that can be supplied for polymerization is used as a solvent can also be used.

When polymerizing an olefin using a catalyst for olefin polymerization, the amount of each component that can constitute the catalyst for olefin polymerization is as follows. Further, in the catalyst for olefin polymerization, the content of each component can be adjusted as follows.

The component (A) is used in an amount usually 1 × 10 ^-10 to 1 × 10 ⁻² mol, preferably 1 × 10 ^-8 to 1 × 10 ^-3 mol, per liter of the reaction volume.

The molar ratio [(B-1) / M] of the component (B-1) to all the transition metal atoms (M) in the component (A) is usually 1 to 50,000, preferably 1 to 50,000. Can be used in an amount such that is 10 to 20,000, particularly preferably 50 to 10,000.

The molar ratio [Al / M] of the aluminum atom in the component (B-2) to the total transition metal atom (M) in the component (A) of the component (B-2) is usually 10 to 5,000, preferably 10 to 5,000. Can be used in an amount such that is 20 to 2,000.

The molar ratio [(B-3) / M] of the component (B-3) to all the transition metal atoms (M) in the component (A) is usually 1 to 1000, preferably 1. It can be used in an amount of up to 200.

When the component (C) is used, the weight ratio of the component (A) to the component (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5. , More preferably, it can be used in an amount such that it is 0.001 to 0.1.

When using component (D)
When the component (B) is the component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. ,
When the component (B) is the component (B-2), the molar ratio [(D) / (B-2)] is usually 0.005 to 2, preferably 0.01 to 1. ,
When the component (B) is the component (B-3), it is used in an amount such that the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5. be able to.

In the production method of the present invention, the polymerization temperature is usually −50 to + 200 ° C., preferably 0 to 200 ° C., more preferably 80 to 200 ° C., and the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal. Pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen or the like to be present in the polymerization system, changing the polymerization temperature, or adjusting the amount of the component (B) used.

In particular, hydrogen can be said to be a preferable additive because it may have an effect of improving the polymerization activity of the catalyst and an effect of increasing or decreasing the molecular weight of the polymer. When hydrogen is added into the system, the amount thereof is appropriately about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system includes a method of performing a reaction that produces or consumes hydrogen in the system, a method of separating hydrogen using a membrane, and some hydrogen-containing methods. It can also be adjusted by releasing the gas out of the system.

For the olefin polymer (for example, ethylene / α-olefin / non-conjugated polyene copolymer) obtained by the production method of the present invention, after synthesizing the olefin polymer by the above method, it is known as necessary. Post-treatment steps such as a catalyst deactivation treatment step, a catalyst residue removal step, and a drying step may be performed.

<Olefin>
In one embodiment of the production method of the present invention, the olefin supplied to the polymerization reaction is an α-olefin having 3 to 20 carbon atoms.

In this embodiment, ethylene may be homopolymerized, ethylene may be copolymerized with a non-conjugated diene, or ethylene may be copolymerized with an α-olefin having 3 or more and 20 or less carbon atoms and a non-conjugated diene. May be good.

Further, in another aspect of the production method of the present invention, the olefin supplied to the polymerization reaction is an α-olefin having 3 to 20 carbon atoms.

In this embodiment, ethylene may be copolymerized with an α-olefin having 3 or more and 20 or less carbon atoms, or an α-olefin having 3 or more and 20 or less carbon atoms and an unconjugated diene may be copolymerized with ethylene. And an α-olefin having 3 or more and 20 or less carbon atoms and a non-conjugated diene may be copolymerized with each other.

According to the production method of the present invention, it is possible to produce an olefin polymer having a high molecular weight with high polymerization activity, particularly an ethylene / α-olefin / non-conjugated polyene copolymer.

As the α-olefin, an α-olefin having 3 to 10 carbon atoms is particularly preferable.

Examples of the α-olefin having 3 or more carbon atoms used in the present invention include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 3-methyl-. Linear or branched α with 3 to 20 carbon atoms such as 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane -Olefin can be exemplified. As the α-olefin, α-olefins having 3 to 10 carbon atoms, for example, linear or branched α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene and 1-octene are preferable. More preferred, propylene is even more preferred. These α-olefins can be used alone or in combination of two or more. Further, the selection can be made so as to be the most desirable in terms of the characteristics of the produced copolymer. For example, the type of α-olefin can be selected so that the physical properties of the ethylene-based polymer obtained in the present invention or the mixture containing the copolymer are desired when vulcanized.

As the non-conjugated polyene, a compound having two or more non-conjugated unsaturated bonds can be used without limitation. Examples thereof include non-conjugated cyclic polyenes and non-conjugated chain polyenes described later, and one type alone or 2 It is possible to use a combination of seeds or more.

[Non-conjugated cyclic polyene]
Specific examples of the non-conjugated cyclic polyene include a compound represented by the following general formula [III].

式［III］において、ｍは０から２の整数であり、
Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷およびＲ¹⁸は水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹⁵からＲ¹⁸までの任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹⁵とＲ¹⁶とで、またはＲ¹⁷とＲ¹⁸とでアルキリデン基を形成していてもよく、Ｒ¹⁵とＲ¹⁷とが、またはＲ¹⁶とＲ¹⁸とが互いに結合して二重結合を形成していてもよく、
以下の（i）から（iv）の要件の少なくとも一つが満たされる。
（i）Ｒ¹⁵からＲ¹⁸の少なくとも一つは、二重結合を一つ以上有する炭化水素基である。
（ii）Ｒ¹⁸からＲ¹⁸までの任意の二つの置換基が互いに結合して環を形成し、該環が二重結合を含んでいる。
（iii）Ｒ¹⁵とＲ¹⁶とで、またはＲ¹⁷とＲ¹⁸とでアルキリデン基を形成している。
（iv）Ｒ¹⁵とＲ¹⁷とが、またはＲ¹⁶とＲ¹⁸とが互いに結合して二重結合を形成している。

In equation [III], m is an integer from 0 to 2.
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. The hydrocarbon groups may be the same or different, and the hydrocarbon groups may have a double bond.
Any two substituents from R ¹⁵ to R ¹⁸ may be bonded to each other to form a ring, which ring may contain a double bond, with R ¹⁵ and R ¹⁶ or with R. ¹⁷ and R ¹⁸ may form an alkylidene group, R ¹⁵ and R ¹⁷ may be bonded to each other, or R ¹⁶ and R ¹⁸ may be bonded to each other to form a double bond.
At least one of the following requirements (i) to (iv) is met.
(I) At least one of R ¹⁵ to R ¹⁸ is a hydrocarbon group having one or more double bonds.
(Ii) Any two substituents from R ¹⁸ to R ¹⁸ are bonded to each other to form a ring, and the ring contains a double bond.
(Iii) An alkylidene group is formed between R ¹⁵ and R ¹⁶ or between R ¹⁷ and R ¹⁸ .
(Iv) R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond.

In the above general formula [III], hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogens, which are listed as R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^18, are contained. Specific examples of the groups include specific examples of these atoms and substituents mentioned in the description of the above general formulas [I] and [II].

In the above general formula [III], when any one or more of R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ is a hydrocarbon group having one or more double bonds, the hydrocarbon group is an ethenyl group. (Vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,4-hexadienyl group Etc. are exemplified. For example, when R ¹⁵ is an ethenyl group (vinyl group), the compound of the above general formula [III] can be represented by the following general formula [III-I].

式［III-I］において、ｍは０から２の整数であり、
Ｒ¹⁶、Ｒ¹⁷およびＲ¹⁸は水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹⁶からＲ¹⁸の任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹⁷とＲ¹⁸とでアルキリデン基を形成していてもよく、Ｒ¹⁶とＲ¹⁸とが互いに結合して二重結合を形成していてもよい。

In equation [III-I], m is an integer from 0 to 2.
R ¹⁶ , R ¹⁷ and R ¹⁸ are atoms or substituents selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. Each may be the same or different, and the hydrocarbon group may have a double bond.
Any two substituents R ¹⁶ to R ¹⁸ may be bonded to each other to form a ring, the ring may contain a double bond, and R ¹⁷ and R ¹⁸ form an alkylidene group. R ¹⁶ and R ¹⁸ may be bonded to each other to form a double bond.

In the above general formula [III], when any two substituents R ¹⁵ to R ¹⁸ are bonded to each other to form a ring and the ring contains a double bond, the above general formula [III] The compound can be represented by, for example, the following general formula [III-II] or [III-III].

式［III-II］および［III-III］において、ｍは０から２の整数であり、
Ｒ¹⁶、Ｒ¹⁷およびＲ¹⁸は水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹⁶からＲ¹⁸の任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹⁷とＲ¹⁸とでアルキリデン基を形成していてもよく、Ｒ¹⁶とＲ¹⁸とが互いに結合して二重結合を形成していてもよい。

In equations [III-II] and [III-III], m is an integer from 0 to 2.
R ¹⁶ , R ¹⁷ and R ¹⁸ are atoms or substituents selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. Each may be the same or different, and the hydrocarbon group may have a double bond.
Any two substituents R ¹⁶ to R ¹⁸ may be bonded to each other to form a ring, the ring may contain a double bond, and R ¹⁷ and R ¹⁸ form an alkylidene group. R ¹⁶ and R ¹⁸ may be bonded to each other to form a double bond.

In the above general formula [III], when an alkylidene group is formed by R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ , the alkylidene group is usually an alkylidene group having 1 to 20 carbon atoms. Examples thereof include a methylene group (CH ₂ =), an ethylidene group (CH ₃ CH =), a propylidene group (CH ₃ CH ₂ CH =) and an isopropylidene group ((CH ₃ ) ₂ C =). For example, when an ethylidene group is formed by R ¹⁵ and R ¹⁶ , the compound of the above general formula [III] can be represented by the following general formula [III-IV].

式［III-IV］において、ｍは０から２の整数であり、
Ｒ¹⁷およびＲ¹⁸は水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹⁷とＲ¹⁸とは互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹⁷とＲ¹⁸とでアルキリデン基を形成していてもよい。

In equation [III-IV], m is an integer from 0 to 2.
R ¹⁷ and R ¹⁸ are atoms or substituents selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and they may be the same. They may be different and the hydrocarbon groups may have a double bond.
R ¹⁷ and R ¹⁸ may be bonded to each other to form a ring, the ring may contain a double bond, and R ¹⁷ and R ¹⁸ may form an alkylidene group.

In the general formula [III], when R ¹⁵ and R ¹⁷ or R ¹⁶ and R ⁸ are bonded to each other to form a double bond, the compound of the general formula [III] is described below, for example. It can be expressed by the general formula [III-V].

式［III-V］において、ｍは０から２の整数であり、
Ｒ¹⁶およびＲ¹⁸は水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹⁶とＲ¹⁸とは互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよい。

In equation [III-V], m is an integer from 0 to 2.
R ¹⁶ and R ¹⁸ are substituents selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and they are the same or different. The hydrocarbon group may have a double bond.
R ¹⁶ and R ¹⁸ may be bonded to each other to form a ring, and the ring may contain a double bond.

Among the non-conjugated cyclic polyenes represented by the general formula [III], as a compound in which at least one of R ¹⁵ to R ¹⁸ is a hydrocarbon group having one or more double bonds, for example, 5-vinyl-2-norbornene (VNB) and the following compounds are exemplified. Of these, 5-vinyl-2-norbornene (VNB) is preferred.

上記一般式［III］で表される非共役環状ポリエンのうち、Ｒ¹⁵からＲ¹⁸までの任意の二つの置換基が互いに結合して環を形成し、該環が二重結合を含んでいる化合物として、例えばジシクロペンタジエン（ＤＣＰＤ）、ジメチルジシクロペンタジエンおよび下記の化合物などが例示される。これらのうち、ジシクロペンタジエン（ＤＣＰＤ）が好ましい。

Among the non-conjugated cyclic polyenes represented by the above general formula [III], any two substituents R ¹⁵ to R ¹⁸ are bonded to each other to form a ring, and the ring contains a double bond. Examples of the compound include dicyclopentadiene (DCPD), dimethyldicyclopentadiene and the following compounds. Of these, dicyclopentadiene (DCPD) is preferred.

上記一般式［III］で表される非共役環状ポリエンのうち、Ｒ¹⁵とＲ¹⁶とで、またはＲ¹⁷とＲ¹⁸とでアルキリデン基を形成している化合物として、５−メチレン−２−ノルボルネン、５−エチリデン−２−ノルボルネン（ＥＮＢ）、５−イソプロピリデン−２−ノルボルネンおよび下記の化合物などが例示される。これらのうち、５−エチリデン−２−ノルボルネン（ＥＮＢ）が好ましい。

Among the non-conjugated cyclic polyenes represented by the above general formula [III], 5-methylene-2-norbornene is used as a compound forming an alkylidene group with R ¹⁵ and R ¹⁶ or with R ¹⁷ and R ^18. , 5-Etylidene-2-norbornene (ENB), 5-isopropylidene-2-norbornene and the following compounds are exemplified. Of these, 5-ethylidene-2-norbornene (ENB) is preferred.

上記一般式［III］で表される非共役環状ポリエンのうち、Ｒ¹⁵とＲ¹⁷とが、またはＲ¹⁶とＲ¹⁸とが互いに結合して二重結合を形成している化合物としては、下記のものが好ましい。

Among the non-conjugated cyclic polyenes represented by the above general formula [III], the compounds in which R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond are as follows. Is preferable.

上記一般式［III］で表される非共役環状ポリエンとしては、ｍが０の非共役環状ポリエンが好ましく、特に上記一般式［III］においてｍが０のアルキリデン基置換非共役環状ポリエン、上記一般式［III］においてｍが０の二重結合含有環置換非共役環状ポリエン、ｍが０の二重結合含有炭化水素基置換非共役環状ポリエンが好ましい。具体的には、５−エチリデン−２−ノルボルネン（ＥＮＢ）、ジシクロペンタジエン（ＤＣＰＤ）、５−ビニル−２−ノルボルネン（ＶＮＢ）がより好ましい。このうち５−エチリデン−２−ノルボルネン（ＥＮＢ）または５−ビニル−２−ノルボルネン（ＶＮＢ）が特に好ましい。

As the non-conjugated cyclic polyene represented by the general formula [III], a non-conjugated cyclic polyene having m of 0 is preferable, and in particular, an alkylidene group-substituted non-conjugated cyclic polyene having m of 0 in the general formula [III] is used. In the formula [III], a double bond-containing ring-substituted non-conjugated cyclic polyene having m of 0 and a double bond-containing hydrocarbon group-substituted non-conjugated cyclic polyene having m of 0 are preferable. Specifically, 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCPD), and 5-vinyl-2-norbornene (VNB) are more preferable. Of these, 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB) is particularly preferable.

[Non-conjugated chain polyene]
Specifically, as the non-conjugated chain polyene, for example, 1,4-hexadiene, 1,5-heptadiene, 1,6-octadien, 1,7-nonadien, 1,8-decadien, 1,12-tetradecadien. , 3-Methyl-1,4-Hexadien, 4-Methyl-1,4-Hexadien, 5-Methyl-1,4-Hexadien, 4-Ethyl-1,4-Hexadien, 3,3-Dimethyl-1,4 -Hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5 -Heptadien, 4-methyl-1,4-octadien, 5-methyl-1,4-octadien, 4-ethyl-1,4-octadien, 5-ethyl-1,4-octadien, 5-methyl-1,5 -Octadiene, 6-methyl-1,5-octadien, 5-ethyl-1,5-octadien, 6-ethyl-1,5-octadien, 6-methyl-1,6-octadien, 7-methyl-1,6 -Octadiene, 6-ethyl-1,6-octadien, 6-propyl-1,6-octadien, 6-butyl-1,6-octadien, 7-methyl-1,6-octadien, 6,7-dimethyl-1 , 6-Octaziene, 4-Methyl-1,4-Nonadiene, 5-Methyl-1,4-Nonadiene, 4-Ethyl-1,4-Nonadiene, 5-Ethyl-1,4-Nonadiene, 5-Methyl-1 , 5-Nonadiene, 6-Methyl-1,5-Nonadiene, 5-Ethyl-1,5-Nonadiene, 6-Ethyl-1,5-Nonadiene, 6-Methyl-1,6-Nonadiene, 7-Methyl-1 , 6-Nonadiene, 6-Ethyl-1,6-Nonadiene, 7-Ethyl-1,6-Nonadiene, 7-Methyl-1,7-Nonadiene, 8-Methyl-1,7-Nonadiene, 7-Ethyl-1 , 7-Nonadiene, 6,7-Dimethyl-1,6-Nonadiene, 5-Methyl-1,4-Decadien, 5-Ethyl-1,4-Decadien, 5-Methyl-1,5-Decadien, 6-Methyl -1,5-decadien, 5-ethyl-1,5-decadien, 6-ethyl-1,5-decadien, 6-methyl-1,6-decadien, 6-ethyl-1,6-decadien, 7-methyl -1,6-decadien, 7-ethyl-1,6-decadien, 7-methyl-1,7-decadien, 8-methyl-1,7-decadien, 7-ethyl-1,7-decadien, 8-ethyl -1,7-deca Diene, 8-Methyl-1,8-Decadien, 9-Methyl-1,8-Decadien, 8-Ethyl-1,8-Decadien, 6-Methyl-1,6-undecadien, 9-Methyl-1,8- Undekajien and the like.

Examples of other non-conjugated chain polyenes include α, ω-diene such as 1,7-octadiene and 1,9-decadien. Other non-conjugated chain polyenes include, for example, the following general formula [ IV-I] may be mentioned as a non-conjugated triene or a tetraene.

式［IV-I］において、ｐおよびrは、０または１（ただしｐとrとは同時に０ではない）、
qは０〜５の整数（ただしｐとrの両方が１の場合qは０ではない）、
sは１〜６の整数、
Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴およびＲ²⁵はそれぞれ独立して水素原子または炭素数１〜３のアルキル基、
Ｒ²⁶は炭素数１〜３のアルキル基、
Ｒ²⁷は水素原子、炭素数１〜３のアルキル基または−(ＣＨ₂)_n−ＣＲ²⁸＝Ｃ(Ｒ²⁹)Ｒ³⁰で表される基（ここでｎは１〜５の整数、Ｒ²⁸およびＲ²⁹はそれぞれ独立して水素原子または炭素数１〜３のアルキル基、Ｒ³⁰は炭素数１〜３のアルキル基である）
である。ただしｐとrの両方が１の場合、Ｒ²⁷は水素原子または炭素数１〜３のアルキル基である。

In formula [IV-I], p and r are 0 or 1 (but p and r are not 0 at the same time),
q is an integer from 0 to 5 (where q is not 0 if both p and r are 1),
s is an integer from 1 to 6,
R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are independent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, respectively.
R ²⁶ is an alkyl group having 1 to 3 carbon atoms,
R ²⁷ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a group represented by − (CH ₂ ) _n −CR ²⁸ = C (R ²⁹ ) R ³⁰ (where n is an integer of 1 to 5, R ^28). And R ²⁹ are independent hydrogen atoms or alkyl groups with 1 to 3 carbon atoms, and R ³⁰ is an alkyl group with 1 to 3 carbon atoms.
Is. However, when both p and r are 1, R ²⁷ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Among the non-conjugated trienes or tetraenes represented by the above general formula [IV-I], the non-conjugated triene represented by the following general formula [IV-II] is preferable.

式［IV-II］において、Ｒ²¹、Ｒ²²、Ｒ²⁵、Ｒ²⁶およびＲ²⁷はそれぞれ独立して水素原子、メチル基またはエチル基である。ただし、Ｒ²⁶とＲ²⁷とが同時に水素原子になることはない。

In formula [IV-II], R ²¹ , R ²² , R ²⁵ , R ²⁶ and R ²⁷ are independently hydrogen atoms, methyl groups or ethyl groups, respectively. However, R ²⁶ and R ²⁷ do not become hydrogen atoms at the same time.

The non-conjugated triene represented by the general formula [IV-II] is a non-conjugated triene or tetraene represented by the above general formula [IV-I], where p is 0, q is 0, r is 1, and s is 2. , R ²³ and R ²⁴ are unconjugated trienes that are hydrogen atoms. Further, among the non-conjugated trienes represented by the above general formula [IV-II], compounds in which both R ²⁵ and R ²⁷ are methyl groups are preferable.

Specific examples of the non-conjugated triene or tetraene represented by the general formula [IV-I] include the following compounds (however, the compounds contained in the general formula [IV-II] are excluded).

上記一般式［IV-II］で表される非共役トリエンとしては、具体的には下記化合物などが挙げられる。

Specific examples of the non-conjugated triene represented by the above general formula [IV-II] include the following compounds.

上記一般式［IV-I］で表される非共役トリエンまたはテトラエンは公知の方法で製造することができ、その方法は例えば本出願人による特開平９−２３５３２７号公報、特開２００１−１１４８３７号公報などに詳細に記載されている。

The non-conjugated triene or tetraene represented by the above general formula [IV-I] can be produced by a known method, and the method is, for example, JP-A-9-235327 and JP-A-2001-114837 by the present applicant. It is described in detail in publications and the like.

When copolymerization is carried out in step [P], the supply amount of each monomer is appropriately set according to the composition of the olefin polymer to be produced.

Hereinafter, the case where the olefin polymer produced by the production method of the present invention is an ethylene / α-olefin / non-conjugated polyene copolymer will be described.

The ethylene / α-olefin / non-conjugated polyene copolymer produced by the production method of the present invention has (i) a structural unit (ethylene unit) derived from ethylene and (ii) an α-olefin having 3 or more carbon atoms. The structural unit (α-olefin unit) derived from is expressed in a molar ratio [(i) / (ii)] and is usually contained in the range of 99/1 to 1/99, but is not particularly limited.

The content of the structural unit derived from ethylene of the ethylene / α-olefin / non-conjugated polyene copolymer produced by the production method of the present invention is usually 50 mol% or more.

The structural unit derived from the non-conjugated polyene compound of the ethylene / α-olefin / non-conjugated polyene copolymer produced by the production method of the present invention is not particularly limited, but is usually 0.1 to 49 mol in all structural units. %, preferably 0.2 to 8 mol%, more preferably 0.3 to 5 mol%.

The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene copolymer produced by the production method of the present invention measured in 135 ° C. decalin is preferably 2 dl / g or more, more preferably 4 dl. It is greater than or equal to / g, and its upper limit may be, for example, 20 dl / g.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

The structure of the crosslinked metallocene compound and its precursor was determined by measuring ¹ H NMR spectrum (270 MHz, JEOL GSH-270), FD-mass (hereinafter FD-MS) spectrum (JEOL SX-102A), etc. ..

The physical properties / properties of the ethylene / α-olefin / non-conjugated polyene copolymer were measured by the following methods.

[Ethylene content, propylene content, 5-ethylidene-2-norbornene (ENB) content]
Using o-dichlorobenzene / benzene-d ₆ (4/1 [vol / vol%]) as the measurement solvent, the measurement temperature was 120 ° C, the spectrum width was 250 ppm, the pulse repetition time was 5.5 seconds, and the pulse width was 4.7 μsec (45 ° pulse). Measurement conditions (100 MHz, JEOL ECX400P) or measurement temperature 120 ° C, spectrum width 250 ppm, pulse repetition time 5.5 seconds, pulse width 5.0 μsec (45 ° pulse) Measurement conditions (125 MHz, Bruker Biospin AVANCE IIIcryo) The ¹³ C NMR spectrum was measured and calculated at -500).

[Ultimate viscosity ([η])]
It was measured at 135 ° C. using a decalin solvent. About 20 mg of the polymer was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After diluting with 5 ml of decalin solvent added to this decalin solution, the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated twice more, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was adopted as the ultimate viscosity.
[Η] = lim (η _sp / C) (C → 0)

<Manufacturing of transition metal compounds>
[Example A1]
(I) Synthesis of di-p-tolylcyclopentadienyl (2,7-dimethoxyfluorenyl) silane After sufficient nitrogen replacement of a 100 mL three-necked flask equipped with a three-way cock and a magnetic stir bar, 2,7- 1.13 g (5.0 mmol) of dimethoxyfluorene was added, and 80 mL of diethyl ether was added. After gradually adding 3.4 mL of a 1.55 M n-butyllithium (5.3 mmol) / hexane solution while cooling in a dry ice / methanol bath, the slurry was obtained by stirring at room temperature for 6 hours under a nitrogen atmosphere. To this slurry, 1.3 mL (5.5 mmol) of di-p-tolyldichlorosilane was gradually added while cooling with a dry ice / methanol bath. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere to obtain a slurry. The slurry was washed with hexane to obtain 1.41 g of an ocher solid. Subsequently, a 200 mL two-necked flask equipped with a three-way cock and a magnetic stir bar was sufficiently replaced with nitrogen, 1.41 g (3.0 mmol) of the obtained ocher solid was added, and 40 mL of tetrahydrofuran was added. After adding 0.36 mL of 1,3-dimethyl-2-imidazolidinone (DMI), gradually add 1.65 mL of 2.0 M cyclopentadienyl sodium (3.3 mmol) / tetrahydrofuran solution while cooling in a dry ice / methanol bath. Added. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere to obtain a slurry. To this, 50 mL of an aqueous ammonium chloride solution and 30 mL of ethyl acetate were added, and the aqueous layer was removed using a 200 mL separatory funnel to obtain an organic layer. The organic layer was washed with 50 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered to remove magnesium sulfate, and the solvent of the filtrate was distilled off to obtain a pale orange solid. The pale orange solid was washed with methanol to give di-p-tolylcyclopentadienyl (2,7-dimethoxyfluorenyl) silane as a pale yellow solid (387 mg (0.773 mmol, 15%)). The measured values of the FD-MS spectrum of di-p-tolylcyclopentadienyl (2,7-dimethoxyfluorenyl) silane are shown below.
FD-MS: m / z = 500.2 (M ⁺ )

(Ii) Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] Synthetic zirconid dichloride 100 mL Schlenk with magnetic stir bar is sufficiently nitrogen After substitution, 351 mg (0.70 mmol) of di-p-tolylcyclopentadienyl (2,7-dimethoxyfluorenyl) silane was added, and 20 mL of toluene and 0.114 mL (1.4 mmol) of tetrahydrofuran were added. While cooling in an ice / salt bath, 0.91 mL of a 1.55 M n-butyllithium (1.4 mmol) / hexane solution was gradually added, and then the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. Then, the slurry was obtained by heating and stirring at 40 ° C. for 4 hours using an oil bath. The solvent was distilled off under reduced pressure, and the obtained solid was washed with hexane to obtain a yellow solid. The obtained yellow solid was placed in a 100 mL Schlenk equipped with a magnetic stir bar, and 20 mL of diethyl ether was added. After adding 163 mg (0.70 mmol) of zirconium tetrachloride while cooling in a methanol / dry ice bath, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere to obtain a slurry. The solid obtained by distilling off the solvent under reduced pressure is extracted with toluene and recrystallized from this toluene solution at about -20 ° C. as a yellow solid, di-p-tolylcyrylene (η ⁵ -cyclopentadienyl). Enyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was obtained. The yield was 30 mg (0.65 mmol) and the yield was 6.5%. Di-p-tolylcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] Zirconium dichloride was identified by ¹ H NMR and FD-MS spectra. The measurement results are shown below.

^{1 1} H NMR (270 MHz, CDCl ₃ )
2.42 (s, 6H), 3.30 (s, 6H), 5.98 (t, 2H, J = 2 Hz), 6.08 (d, 2H, J = 2 Hz), 6.75 (t, 2H, J = 2 Hz), 7.21 (dd, 2H, J = 8, 1 Hz), 7.38 (d, 4H, J = 7 Hz), 7.85 (d, 2H, J = 9 Hz), 8.05 (d, 4H, J = 8 Hz)
FD-MS: m / z = 658.0 (M ⁺ )

[Example A2]
(I) Synthesis of di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-di-tert-butylfluorenyl) silane A 100 mL three-necked flask equipped with a three-way cock and a magnetic stir bar is sufficient. After substitution with nitrogen, 711 mg (2.1 mmol) of 2,7-dimethoxy-3,6-di-tert-butylfluorene was added, and 30 mL of diethyl ether was added. After gradually adding 1.4 mL of 1.55 M n-butyllithium (2.2 mmol) / hexane solution while cooling in an ice bath, the slurry was obtained by stirring at room temperature for 23 hours under a nitrogen atmosphere. 0.55 mL (2.3 mmol) of di-p-tolyldichlorosilane was gradually added to this slurry while cooling in a dry ice / methanol bath. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 17 hours under a nitrogen atmosphere to obtain a slurry. The slurry was washed with hexane to give 550 mg of white solid. Subsequently, a 200 mL two-necked flask equipped with a three-way cock and a magnetic stir bar was sufficiently replaced with nitrogen, and then 550 mg (0.94 mmol) of the obtained white solid was added, and 30 mL of tetrahydrofuran was added. After adding 0.20 mL of 1,3-dimethyl-2-imidazolidinone (DMI), gradually add 0.94 mL of 2.0 M cyclopentadienyl sodium (1.89 mmol) / tetrahydrofuran solution while cooling in a dry ice / methanol bath. Added. After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere to obtain a slurry. To this, 50 mL of an aqueous ammonium chloride solution and 20 mL of ethyl acetate were added, and the aqueous layer was removed using a 200 mL separatory funnel to obtain an organic layer. The organic layer was washed with 50 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered to remove magnesium sulfate, and the solvent of the filtrate was distilled off to obtain a yellow solid. This yellow solid is purified by silica gel column chromatography (hexane: ethyl acetate = 50: 1), and the solvent is distilled off under reduced pressure to make a pale orange solid di-p-tolylcyclopentadienyl (2,7-dimethoxy). A -3,6-di-tert-butylfluorenyl) silane was obtained (306 mg (0.50 mmol, 24%)). The measured values of the FD-MS spectrum of di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-di-tert-butylfluorenyl) silane are shown below.
FD-MS: m / z = 612.4 (M ⁺ )

(Ii) Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] Synthetic magnetic stirrer for zirconium dichloride Di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-di-tert-butylfluorenyl) silane 306 mg (0.50 mmol) after sufficient nitrogen substitution of 100 mL Schlenk with. Was added, and 40 ml of diethyl ether was added. While cooling in a dry ice / methanol bath, 0.66 mL of a 1.55 M n-butyllithium (1.02 mmol) / hexane solution was gradually added, and then the mixture was stirred at room temperature for 23 hours under a nitrogen atmosphere to obtain a slurry. After adding 116 mg (0.50 mmol) of zirconium tetrachloride while cooling in a methanol / dry ice bath, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere to obtain a slurry. The solvent was distilled off under reduced pressure, the obtained solid was washed with hexane, and the residue was extracted with toluene. Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert) as a pale orange solid by distilling off toluene in the toluene solution under reduced pressure. -Butylfluorenyl)] Zirconium dichloride was obtained. The yield was 151 mg (0.30 mmol) and the yield was 39%. Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] Zirconium dichloride identification is based on the ¹ H NMR spectrum. And the FD-MS spectrum. The measurement results are shown below.

^{1 1} H NMR (270 MHz, CDCl ₃ )
1.44 (s, 18H), 2.41 (s, 6H), 3.24 (s, 6H), 5.83 (t, 2H, J = 2 Hz), 6.02 (s, 2H), 6.70 (t, 2H, J = 2 Hz) ), 7.38 (d, 4H, J = 8 Hz), 7.83 (s, 2H), 8.06 (d, 4H, J = 8 Hz)
FD-MS: m / z = 770.1 (M ⁺ )

[Example A3]
(I) Synthesis of di-p- tolylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane Under a nitrogen atmosphere, 2,7-dimethoxy-3,6 in a 100 ml two-necked flask -756 mg (2.97 mmol) of dimethylfluorene and 50 ml of dehydrated cyclopentyl methyl ether were added. 2.01 ml (3.12 mmol) of n-butyllithium / hexane solution (1.55 M) was gradually added while cooling to -78 ° C, and the mixture was stirred at room temperature for 18 hours. After adding 802 mg (3.27 mmol) of di-p-tolyldichlorosilane, the mixture was stirred for 22 hours and a half. The solvent was brought into a nitrogen box and distilled off under reduced pressure, and then washed with hexane. The obtained solid was dried under reduced pressure to obtain 957 mg of a white solid.

Subsequently, under a nitrogen atmosphere, 957 mg of the white solid obtained in the previous reaction and 50 ml of THF were added to a 100 ml three-necked flask. Cool to -78 ° C, add 0.415 ml (3.85 mmol) of 1,3-dimethyl-2-imidazolidinone (DMI) and 1.92 ml of 2.0 M sodium cyclopentadienyl sodium (3.84 mmol) tetrahydrofuran solution, gradually. The mixture was stirred for 23 hours while returning to room temperature. After stopping the reaction by adding an aqueous ammonium chloride solution under an ice bath, the mixture was extracted with ethyl acetate, the organic phase was washed with water and saturated brine, dried over magnesium sulfate, and concentrated to dryness. The obtained solid was washed with methanol and dried under reduced pressure to obtain a crude product (pale orange powder). Purification was performed by silica gel chromatography (developing solvent hexane → hexane: ethyl acetate = 50: 1) to obtain the desired product (white powder) (yield 449 mg, 2-step yield 29%). The measured values of the FD-MS spectrum of di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane are shown below.
FD-MS: m / z = 528.3 (M ⁺ )

(Ii) Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Synthetic zirconium dichloride Under a nitrogen atmosphere, 100 ml Schlenk Di-p-tolylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane 449 mg (0.850 mmol) and diethyl ether 40 ml were added to the tubes. The mixture was cooled to -78 ° C., 1.12 ml (1.74 mmol) of n-butyllithium / hexane solution (1.55 M) was added, and the mixture was stirred for 23 hours while gradually returning to room temperature. The mixture was cooled to -78 ° C., 198 mg (0.850 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 23 hours while gradually raising the temperature to room temperature. The solvent was distilled off under reduced pressure, the mixture was washed with hexane, and then extracted with toluene and dichloromethane using Celite. The solvent was distilled off under reduced pressure to obtain the desired product (yield 471 mg, yield 80%). Di-p-tolylcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Zirconium dichloride identification is based on ¹ H NMR spectra and FD-MS. Performed on the spectrum. The measurement results are shown below.

^{1 1} H NMR (270 MHz, CDCl ₃ )
2.38 (s, 6H), 2.41 (s, 6H), 3.25 (s, 6H), 5.84 (t, 2H, J = 2 Hz), 5.99 (s, 2H), 6.69 (t, 2H, J = 2 Hz) ), 7.37 (d, 4H, J = 8 Hz, 4H), 7.73 (s, 2H), 8.06 (d, 4H, J = 8 Hz)
FD-MS: m / z = 686.1 (M ⁺ )

[Example A4]
(Iii) Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Synthetic zirconium dimethyl under a nitrogen atmosphere, 100 ml Schlenk In a flask, di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconide dichloride prepared in Example A3 147 mg. (0.21 mmol), 50 ml of t-butyl methyl ether and 25 ml of toluene were added. The mixture was cooled in an ice bath, 0.42 ml (1.26 mmol) of methyl magnesium bromide / diethyl ether solution (3 M) was added, and the mixture was heated in an oil bath at 60 ° C. for 22 hours. The solvent was distilled off under reduced pressure, and the mixture was extracted with toluene using Celite. After distilling off the solvent under reduced pressure, the mixture was extracted with methylcyclohexane using Celite. The solvent was distilled off under reduced pressure, and the obtained solid was washed with hexane. The desired product was obtained by drying under reduced pressure. (Yield 53 mg, yield 39%). The target product was identified by ¹ H NMR spectrum and FD-MS spectrum. The measurement results are shown below.

^{1 1} H NMR (270 MHz, CDCl ₃ )
-1.57 (s, 6H), 2.36 (s, 6H), 2.37 (s, 6H), 3.21 (s, 6H), 5.69 (t, 2H, J = 2 Hz), 5.90 (s, 2H), 6.62 ( t, 2H, J = 2 Hz), 7.30 (d, 4H, J = 8 Hz), 7.77 (s, 2H), 8.02 (d, 2H, J = 8 Hz)
FD-MS: m / z = 646.2 (M ⁺ )

[Example A5]
(I) Synthesis of diphenylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane Under a nitrogen atmosphere, 2,7-dimethoxy-3,6-dimethylfluorene 1037 mg in a 100 ml Schlenk flask. (4.08 mmol) and 60 ml of dehydrated cyclopentyl methyl ether were added. 2.80 ml (4.34 mmol) of n-butyllithium / hexane solution (1.55 M) was gradually added while cooling to -78 ° C, and the mixture was stirred at room temperature for 17 hours. After adding 0.94 ml (4.47 mmol) of diphenyldichlorosilane, the mixture was stirred for 23 hours. After bringing it into a nitrogen box and distilling off the solvent under reduced pressure, it was washed with pentane. The obtained solid was dried under reduced pressure to obtain 990 mg of an orange solid.
Subsequently, under a nitrogen atmosphere, 990 mg of the orange solid obtained in the previous reaction and 50 ml of THF were added to a 100 ml Schlenk flask. After cooling to -78 ° C, add 0.46 ml (4.26 mmol) of 1,3-dimethyl-2-imidazolidinone (DMI) and 2.10 ml (4.20 mmol) of 2.0 M solution of cyclopentadienyl sodium tetrahydrofuran, gradually. The mixture was stirred for 21 hours while returning to room temperature. Under an ice bath, saturated aqueous ammonium chloride solution was added to stop the reaction, and the mixture was extracted with diethyl ether. The organic phase was washed with water and saturated brine. After drying over magnesium sulfate, it was concentrated to dryness. The obtained solid was purified by silica gel chromatography (developing solvent hexane → hexane: ethyl acetate = 20: 1) to obtain the desired product (yield 709 mg, 2-step yield 35%). Identification of the diphenylcyclopentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane was performed on the FD-MS spectrum. The measurement results are shown below.
FD-MS: m / z = 500.2 (M ⁺ )

(Ii) Diphenylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Synthetic zirconium dichloride Diphenylcyclo in a 100 ml Schlenk flask under a nitrogen atmosphere. 702 mg (1.40 mmol) of pentadienyl (2,7-dimethoxy-3,6-dimethylfluorenyl) silane and 55 ml of diethyl ether were added. The mixture was cooled to -78 ° C., 1.85 ml (2.87 mmol) of n-butyllithium / hexane solution (1.55 M) was gradually added, and the mixture was stirred for 23 hours while gradually returning to room temperature. The mixture was cooled to -78 ° C., 323 mg (1.39 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 23 hours while gradually raising the temperature to room temperature. The solvent was distilled off under reduced pressure, and the mixture was extracted with dichloromethane using Celite. The solvent was evaporated under reduced pressure, dissolved in a small amount of dichloromethane, and added dropwise to hexane. The obtained precipitate was collected by filtration and dried under reduced pressure. The obtained solid was washed with pentane and then dried under reduced pressure to obtain the desired product (yield 506 mg, 55% yield). The target product was identified by ¹ H NMR spectrum and FD-MS spectrum. The measurement results are shown below.

^{1 1} H NMR (270 MHz, CDCl ₃ )
2.38 (s, 6H), 3.23 (s, 6H), 5.86 (t, 2H, J = 2 Hz), 5.96 (s, 2H), 6.71 (t, 2H, J = 2 Hz), 7.55-7.57 (m) , 6H), 7.73 (s, 2H), 8.18-8.22 (m, 4H)
FD-MS: m / z = 658.0 (M ⁺ )

[Example A6]
(Iii) Diphenylcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Synthetic zirconium Dimethyl Performed in a 100 ml Schlenk flask under a nitrogen atmosphere. Diphenylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] zirconium dichloride 264 mg (0.40 mmol), t-butyl produced in Example A5. 30 ml of methyl ether was added. The mixture was cooled in an ice bath, 0.80 ml (2.40 mmol) of methyl magnesium bromide / diethyl ether solution (3 M) was added, and the mixture was heated under reflux for 22 hours. The solvent was distilled off under reduced pressure, and the mixture was extracted with toluene using Celite. After distilling off the solvent under reduced pressure, the mixture was extracted with methylcyclohexane using Celite. The solvent was distilled off under reduced pressure, and the obtained solid was dissolved in a small amount of dichclomethane and added dropwise to hexane. A part of the solvent was distilled off under reduced pressure, and the precipitate formed was recovered by filtration. The desired product was obtained by drying under reduced pressure. (Yield 113 mg, yield 45%). The target product was identified by ¹ H NMR spectrum and FD-MS spectrum. The measurement results are shown below.

^{1 1} H NMR (270 MHz, CDCl ₃ )
-1.56 (s, 6H), 2.35 (s, 6H), 3.20 (s, 6H), 5.71 (t, 2H, J = 2 Hz), 5.87 (s, 2H), 6.64 (t, 2H, J = 2) Hz), 7.47-7.51 (m, 6H), 7.78 (s, 2H), 8.13-8.17 (m, 4H)
FD-MS: m / z = 618.1 (M ⁺ )

[Example A7]
(I) Synthesis of di-p-tolylcyclopentadienyl (2,7-di-t-butyl-4-methoxyfluorenyl) silane Under a nitrogen atmosphere, 2,7-di-t in a 100 ml two-mouthed flask. -Butyl-4-methoxyfluorene 771 mg (2.50 mmol) and 50 ml of dehydrated cyclopentyl methyl ether were added. While cooling to -78 ° C, 1.69 ml (2.63 mmol) of n-butyllithium / hexane solution (1.55 M) was gradually added, and the mixture was stirred at room temperature for 18 hours. After adding 0.655 ml (2.75 mmol) of di-p-tolyldichlorosilane, the mixture was stirred for 22 hours and a half. The solvent was brought into a nitrogen box and distilled off under reduced pressure, and then washed with hexane. The obtained solid was dried under reduced pressure to obtain 1.20 g of a white solid.

Subsequently, under a nitrogen atmosphere, 1.20 g of the white solid obtained in the previous reaction and 50 ml of THF were added to a 100 ml three-necked flask. Cool to -78 ° C, add 0.467 ml (4.34 mmol) of 1,3-dimethyl-2-imidazolidinone (DMI) and 2.17 ml of 2.0 M sodium cyclopentadienyl (4.34 mmol) tetrahydrofuran solution, gradually. The mixture was stirred for 23 hours while returning to room temperature. After stopping the reaction by adding an aqueous ammonium chloride solution under an ice bath, the mixture was extracted with ethyl acetate, the organic phase was washed with water and saturated brine, dried over magnesium sulfate, and concentrated to dryness. The product (white powder) was obtained by washing with the obtained solid hexane (yield 625 mg, 2-step yield 43%). The measured values of the FD-MS spectrum of di-p-tolylcyclopentadienyl (2,7-di-t-butyl-4-methoxyfluorenyl) silane are shown below.
FD-MS: m / z = 582.3 (M ⁺ )

(Ii) Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-di-t-butyl-4-methoxyfluorenyl)] Synthetic of zirconium dichloride Under a nitrogen atmosphere, 100 To a ml Schlenk tube was added di-p-tolylcyclopentadienyl (2,7-di-t-butyl-4-methoxyfluorenyl) silane 350 mg (0.60 mmol) and diethyl ether 40 ml. The mixture was cooled to -78 ° C., 1.12 ml (1.74 mmol) of n-butyllithium / hexane solution (1.55 M) was added, and the mixture was stirred for 20 hours while gradually returning to room temperature. The mixture was cooled to -78 ° C, 140 mg (0.60 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 23 hours while gradually raising the temperature to room temperature. The solvent was distilled off under reduced pressure, the mixture was washed with hexane, and then extracted with toluene and dichloromethane using Celite. The solvent was distilled off under reduced pressure to obtain the desired product (yield 321 mg, yield 72%). Di-p-tolylcilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-di-t-butyl-4-methoxyfluorenyl)] Zirconium dichloride identification is based on ¹ H NMR spectra and FD. -The MS spectrum was used. The measurement results are shown below.

FD-MS: m / z = 740.2 (M ⁺ )
^{1 1} H NMR (270 MHz, CDCl ₃ )
1.01 (s, 18H), 2.42 (s, 6H), 4.01 (s, 3H), 5.79-5.84 (m, 2H), 6.30 (d, 1H, J = 1 Hz), 6.65-6.71 (m, 3H) , 6.89 (d, 1H, J = 1 Hz), 7.37 (d, 4H, J = 7 Hz), 7.61 (dd, 1H, J = 9, 2 Hz), 8.02-8.07 (m, 4H), 8.27 ( d, J = 9 Hz, 1H)

[Example A8]
(I) Dip-tolylcyclopentadienyl (4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2,1-g: 3,, Synthesis of 4-g'] dichromenyl) silane Under a nitrogen atmosphere, in a 100 ml Schlenk flask, 4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2 , 1-g: 3,4-g'] Dichromen 503 mg (1.42 mmol) and dehydrated tert-butyl methyl ether 20 ml were added. A n-butyllithium / hexane solution (1.57 M) of 1.00 ml (1.57 mmol) was gradually added to 0 ° C. under an ice bath, and the mixture was heated and stirred in a 70 ° C. oil bath for 5.5 hours. After adding 480 mg (1.71 mmol) of dip-tolyldichlorosilane at -78 ° C, the mixture was stirred for 17 hours while gradually returning to room temperature. After bringing it into a nitrogen box and distilling off the solvent under reduced pressure, it was washed with pentane. The obtained solid was dried under reduced pressure to obtain 688 mg of an off-white solid.

Subsequently, in a nitrogen atmosphere, the off-white solid obtained in the previous reaction was dissolved in 20 ml of tetrahydrofuran in a 100 ml Schlenk flask, and 1,3-dimethyl-2-imidazolidinone (DMI) 0.15 ml (1.39 mmol) was dissolved. Was added. After cooling to -78 ° C., 0.66 ml (1.32 mmol) of a 2.0 M solution of cyclopentadienyl sodium tetrahydrofuran was added, and the mixture was stirred for 17 hours while gradually returning to room temperature. After heating in an 80 ° C oil bath for 6 hours, at -30 ° C, 0.15 ml (1.39 mmol) of 1,3-dimethyl-2-imidazolidinone (DMI) and 2.0 M solution of cyclopentadienyl sodium in tetrahydrofuran 0.66 ml (1.32) mmol) was added, and the mixture was stirred for 16 hours while gradually returning to room temperature. The reaction was stopped by pouring into saturated aqueous ammonium chloride solution, and the mixture was extracted with hexane. The organic phase was washed with water and saturated brine. After drying over magnesium sulfate, it was concentrated to dryness. The obtained solid was washed with methanol to obtain the desired product (yield 425 mg, 2-step yield 49%). Dip-tolylcyclopentadienyl (4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2,1-g: 3,4-g The identification of'] dichromenyl) silane was performed on the FD-MS spectrum. The measurement results are shown below.
FD-MS: m / z = 608.4 (M ⁺ )

(Ii) di p- Torirushiriren (eta ⁵ - cyclopentadienyl) (η ⁵ -4,4,7,7- tetramethyl -3,4,7,8,9,12- hexahydro -2H- cyclopenta - [2,1-g: 3,4-g'] Dichromenyl) Synthesis of zirconium dichloride Under a nitrogen atmosphere, dip-tolylcyclopentadienyl (4,4,7,7-tetramethyl-3) was placed in a 100 ml Schlenk flask. , 4,7,8,9,12-Hexahydro-2H-Cyclopenta- [2,1-g: 3,4-g'] dichromenyl) Silane 425 mg (0.698 mmol) and diethyl ether 20 ml were added. The mixture was cooled to -78 ° C., 0.92 ml (1.44 mmol) of n-butyllithium / hexane solution (1.57 M) was gradually added, and the mixture was stirred for 18 hours while gradually returning to room temperature. The mixture was cooled to -78 ° C., 150 mg (0.644 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 23 hours while gradually raising the temperature to room temperature. The solvent was distilled off under reduced pressure, and the residue dichloromethane extract was filtered through Celite. The filtrate was concentrated under reduced pressure, washed 3 times each with a small amount of hexane and pentane in another place, and dried under reduced pressure to obtain the desired product (yield 300 mg, yield 51%).

The target product was identified by ¹ H NMR spectrum and FD-MS spectrum. The measurement results are shown below.

^{1 1} H NMR (270 MHz, CDCl ₃ ):
1.45 (s, 6H), 1.52 (s, 6H), 1.81-1.84 (m, 4H), 2.40 (s, 6H), 4.11-4.16 (m, 4H), 5.87 (t, 2H, J = 2.3 Hz) , 6.13 (s, 2H), 6.67-6.69 (t, 2H, J = 2.3 Hz), 7.31 (d, 4H, J = 7.6 Hz), 7.91 (s, 2H), 7.93 (d, 4H, J = 7.6) Hz)
FD-MS: m / z = 766.2 (M ⁺ )

＜エチレン／プロピレン／ＥＮＢ共重合体の製造＞
［実施例Ｂ１］
充分に窒素置換した内容積２Ｌのステンレス製オートクレーブにヘキサン１０３０ｍL、エチリデンノルボルネン（ＥＮＢ）１２ｍＬを装入し、系内の温度を９４℃に昇温した後、プロピレンを分圧で０．９０ＭＰａ分装入し、エチレンを供給することにより全圧を１．６ＭＰａ−Ｇとした。次に、トリイソブチルアルミニウム０．３ｍｍｏｌ、実施例Ａ１で製造したジ-p-トリルシリレン(η⁵-シクロペンタジエニル)[η⁵-(2,7-ジメトキシフルオレニル)]ジルコニウムジクロリド０．０００１２ｍｍｏｌおよびトリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート０．０００４８ｍｍｏｌを窒素で圧入し、攪拌回転数を２５０ｒｐｍにすることにより重合を開始した。その後、エチレンのみを連続的に供給することにより全圧を１．６ＭＰａ−Ｇに保ち、９５℃で１５分間重合を行った。少量のエタノールを系内に添加することにより重合を停止した後、未反応のエチレンをパージした。得られたポリマー溶液を、大過剰のメタノール／アセトン混合溶液中に投入することにより、ポリマーを析出させた。ポリマーをろ過により回収し、１２０℃の減圧下で一晩乾燥した。The structural formulas of the transition metal compounds produced in Examples A1 to A8 are shown below.

<Manufacturing of ethylene / propylene / ENB copolymer>
[Example B1]
Hexane 1030 mL and ethylidene norbornene (ENB) 12 mL were charged into a stainless steel autoclave with an internal volume of 2 L sufficiently substituted with nitrogen, the temperature inside the system was raised to 94 ° C, and then propylene was divided into 0.90 MPa by partial pressure. The total pressure was adjusted to 1.6 MPa-G by supplying ethylene. Next, 0.3 mmol of triisobutylaluminum, di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride prepared in Example A1. Polymerization was initiated by press-fitting 00012 mmol and 0.00048 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate with nitrogen and setting the stirring speed to 250 rpm. Then, by continuously supplying only ethylene, the total pressure was maintained at 1.6 MPa-G, and polymerization was carried out at 95 ° C. for 15 minutes. After terminating the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The polymer was precipitated by putting the obtained polymer solution into a large excess of methanol / acetone mixed solution. The polymer was collected by filtration and dried under reduced pressure at 120 ° C. overnight.

As a result, 11.2 g of an ethylene / propylene / ENB copolymer having an ethylene content of 80.7 mol%, an ENB content of 1.5 mol% and an ultimate viscosity [η] of 4.3 dl / g was obtained. The polymerization activity was 374.3 kg / mmol-Zr / h.

[Example B2]
Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in Example A2 and 0.00008 mmol of di-p-tolylcilylene. (η ⁵ -Cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-di-tert-butylfluorenyl)] Zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate 0. The same operation as in Example B1 was carried out except that the value was changed to 00032 mmol.

As a result, 4.49 g of an ethylene / propylene / ENB copolymer having an ethylene content of 80.8 mol%, an ENB content of 1.8 mol% and an ultimate viscosity [η] of 4.44 dl / g was obtained. The polymerization activity was 224.5 kg / mmol-Zr / h.

[Example B3]
Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in Example A3 at 0.00008 mmol of di-p-tolylcyrylene. (η ⁵ -Cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) Borate changed to 0.00032 mmol The same operation as in Example B1 was performed except for the above.

As a result, 10.1 g of an ethylene / propylene / ENB copolymer having an ethylene content of 82.9 mol%, an ENB content of 1.8 mol% and an ultimate viscosity [η] of 5.59 dl / g was obtained. The polymerization activity was 502.5 kg / mmol-Zr / h.

[Example B4]
Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in Example A4 and 0.0001 mmol of di-p-tolylcyrylene. (η ⁵ -Cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Zirconium dimethyl, triphenylcarbenium tetrakis (pentafluorophenyl) borate changed to 0.0004 mmol The same operation as in Example B1 was performed except for the above.

As a result, 2.21 g of an ethylene / propylene / ENB copolymer having an ethylene content of 84.3 mol%, an ENB content of 1.9 mol% and an ultimate viscosity [η] of 5.63 dl / g was obtained. The polymerization activity was 88.4 kg / mmol-Zr / h.

[Example B5]
Di -p- Torirushiriren (eta ⁵ - cyclopentadienyl) [η ⁵ - (2,7- dimethoxy-fluorenyl)] zirconium dichloride, the 0.0001mmol prepared in Example A5 diphenylsilylene (eta ⁵ - Cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate changed to 0.0004 mmol The same operation as in Example B1 was performed.

As a result, 8.06 g of an ethylene / propylene / ENB copolymer having an ethylene content of 83.4 mol%, an ENB content of 1.9 mol% and an ultimate viscosity [η] of 5.08 dl / g was obtained. The polymerization activity was 322.4 kg / mmol-Zr / h.

[Example B6]
Di -p- Torirushiriren (eta ⁵ - cyclopentadienyl) [η ⁵ - (2,7- dimethoxy-fluorenyl)] zirconium dichloride, the 0.0001mmol prepared in Example A6 diphenylsilylene (eta ⁵ - Cyclopentadienyl) [η ^5- (2,7-dimethoxy-3,6-dimethylfluorenyl)] Zirconium dimethyl, triphenylcarbenium tetrakis (pentafluorophenyl) borate changed to 0.0004 mmol The same operation as in Example B1 was performed.

As a result, 7.97 g of an ethylene / propylene / ENB copolymer having an ethylene content of 82.2 mol%, an ENB content of 2.0 mol% and an ultimate viscosity [η] of 5.21 dl / g was obtained. The polymerization activity was 318.8 kg / mmol-Zr / h.

[Example B7]
Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride was prepared in Example A7 and 0.00008 mmol of di-p-tolylcilylene. (η ⁵ -Cyclopentadienyl) [η ^5- (2,7-di-t-butyl-4-methoxyfluorenyl)] Zirconium dichloride, triphenylcarbenium tetrakis (pentafluorophenyl) borate 0.00032 mmol The same operation as in Example B1 was performed except that it was changed to.

As a result, 2.84 g of an ethylene / propylene / ENB copolymer having an ethylene content of 73.7 mol%, an ENB content of 1.9 mol% and an ultimate viscosity [η] of 3.06 dl / g was obtained. The polymerization activity was 142.0 kg / mmol-Zr / h.

[Example B8]
Di-p-tolylcyrylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] Zirconium dichloride was prepared in Example A8 with 0.0001 mmol of di-p-tolylcyrylene (η ⁵ -tolylcyrylene). η ⁵ -cyclopentadienyl) (η ⁵ -4,4,7,7-tetramethyl-3,4,7,8,9,12-hexahydro-2H-cyclopenta- [2,1-g: 3,, The same operation as in Example B1 was carried out except that 4-g'] dichromenyl) zirconium dichloride and triphenylcarbenium tetrakis (pentafluorophenyl) borate were changed to 0.0004 mmol.

As a result, 6.46 g of an ethylene / propylene / ENB copolymer having an ethylene content of 79.5 mol%, an ENB content of 2.3 mol% and an ultimate viscosity [η] of 6.30 dl / g was obtained. The polymerization activity was 129.2 kg / mmol-Zr / h.

[Comparative Example B1]
Di-p-tolylsilylene (η ⁵ -cyclopentadienyl) [η ^5- (2,7-dimethoxyfluorenyl)] zirconium dichloride, 0.0001 mmol of diphenylsilylene (η ⁵ -cyclopentadienyl) ( The same operation as in Example B1 was carried out except that η ⁵ -fluorenyl) zirconium dichloride and triphenylcarbenium tetrakis (pentafluorophenyl) borate were changed to 0.0004 mmol.

As a result, 9.49 g of an ethylene / propylene / ENB copolymer having an ethylene content of 75.0 mol%, an ENB content of 2.0 mol% and an ultimate viscosity [η] of 2.63 dl / g was obtained. The polymerization activity was 379.6 kg / mmol-Zr / h.

Claims (17)

The transition metal compound [A] represented by the following general formula [I] or [II].

[In equations [I] and [II]
R ¹ , R ² , R ³ , R ⁴ , R ¹³ and R ¹⁴ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, substituted aryl groups, silicon-containing groups, and nitrogen-containing groups, respectively. , An atom or substituent selected from the group consisting of an oxygen-containing group, a halogen atom and a halogen-containing group, and adjacent substituents R ¹ to R ⁴ may be bonded to each other to form a ring, or each other. It may not be bonded, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are independently represented by a hydrogen atom and a ZR (where Z is an oxygen atom or a sulfur atom). Yes, R is a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group and a halogen-containing group, via Z. (It is bonded to a fluorenyl ligand), a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group (however, the substitution represented by ZR). (Excluding groups.), An atom or substituent selected from the group consisting of halogen atoms and halogen-containing groups, and adjacent substituents R ⁵ to R ¹² may be bonded to each other to form a ring. At least one of R ⁵ to R ¹² is a substituent represented by ZR.
Y is selected from carbon atom, silicon atom, germanium atom and tin atom,
A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A contains two or more ring structures including a ring formed with Y. May be
M is a titanium atom, a zirconium atom or a hafnium atom,
j is an integer from 1 to 4
Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair. When j is 2 or more, there are a plurality of Qs. May be the same as or different from each other. ] The transition metal compound [A] according to claim 1, wherein Z is an oxygen atom in the general formula [I] or [II]. The transition metal compound [A] according to claim 1 or 2, wherein Y is a silicon atom in the general formula [I] or [II]. The transition metal compound [A] according to any one of claims 1 to 3, wherein M is a zirconium atom in the general formula [I] or [II]. A catalyst for olefin polymerization containing the transition metal compound [A] according to any one of claims 1 to 4. [B] [B-1] Organometallic compounds,
5. Claim 5 further containing at least one compound selected from the group consisting of [B-2] organoaluminum oxy compounds and [B-3] transition metal compounds [A] to form ion pairs. The catalyst for olefin polymerization according to. A method for producing an olefin polymer, which comprises the step [P] of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 5 or 6. The method for producing an olefin polymer according to claim 7, wherein the step [P] is a step of polymerizing ethylene. The method for producing an olefin polymer according to claim 8, wherein the step [P] is a step of copolymerizing ethylene and a non-conjugated polyene. The method for producing an olefin polymer according to claim 9, wherein the non-conjugated polyene is represented by the following general formula [III].

[In the formula, m is an integer from 0 to 2,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are independently selected from hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, respectively. The hydrocarbon group may have a double bond.
Any two substituents from R ¹⁵ to R ¹⁸ may be bonded to each other to form a ring, which ring may contain a double bond, with R ¹⁵ and R ¹⁶ . Alternatively, R ¹⁷ and R ¹⁸ may form an alkylidene group, R ¹⁵ and R ¹⁷ may be bonded to each other, or R ¹⁶ and R ¹⁸ may be bonded to each other to form a double bond.
At least one of the following requirements (i) to (iv) is met.
(I) At least one of R ¹⁵ to R ¹⁸ is a hydrocarbon group having one or more double bonds.
(Ii) Any two substituents from R ¹⁵ to R ¹⁸ bond to each other to form a ring, which contains dipolymerization.
(Iii) An alkylidene group is formed between R ¹⁵ and R ¹⁶ or between R ¹⁷ and R ¹⁸ .
(Iv) R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond. ] The method for producing an olefin polymer according to claim 10, wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB). The method for producing an olefin polymer according to any one of claims 9 to 11, wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. The method for producing an olefin polymer according to claim 12, wherein the α-olefin is propylene. The method for producing an olefin polymer according to any one of claims 8 to 13, wherein the polymerization temperature in the step [P] is 80 ° C. or higher. The method for producing an olefin polymer according to claim 7, wherein the step [P] is a step of polymerizing an α-olefin having 3 to 20 carbon atoms. The method for producing an olefin polymer according to claim 15, wherein the step [P] is a step of copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms. The method for producing an olefin polymer according to claim 15 or 16, wherein the α-olefin is propylene.