JP7175692B2 - Catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst, a method for producing an olefin polymer using the catalyst, and a cyclic olefin copolymer.
The present invention also relates to a novel transition metal compound, more specifically, a novel transition metal compound that can be used as an olefin polymerization catalyst, an olefin polymerization catalyst containing the compound, and an olefin polymer using the catalyst. It relates to a manufacturing method.
Furthermore, the present invention relates to novel cyclic olefin copolymers.

Conventionally, a catalyst comprising a metallocene compound and a cocatalyst such as an organoaluminumoxy compound is known as a catalyst for producing an olefin polymer such as an ethylene/α-olefin copolymer.

Various types of transition metal compounds such as metallocene compounds have been actively developed. For example, Patent Document 1 discloses a transition metal compound (A) represented by the following general formula:

（式中、ＭはＴｉ等の周期律表４族の遷移金属を表し、Ｌは周期律表１５族の元素が配位原子となる１価のアニオン性配位子を表し、Ｘはハロゲン等を表し、ｍは１～３の整数を表し、Ｒ¹～Ｒ⁵は、水素、ハロゲン又は炭素原子数１～２０のアルキル基等を表す。）
ならびに有機アルミニウムオキシ化合物および有機ホウ素化合物から選ばれる１種以上の活性化剤（Ｂ）からなる重合触媒の存在下、エチレンおよび／または炭素原子数３～２０のα－オレフィンと少なくとも１種類の環状オレフィン化合物との共重合を行う環状オレフィン系共重合体の製造方法が記載され、遷移金属化合物（Ａ）の具体例としては、ＣｐＴｉ（ｔ－Ｂｕ₂Ｃ＝Ｎ）Ｃｌ₂、およびＣｐ^*Ｔｉ（２，６－ⁱＰｒ₂ＰｈＯ）Ｃｌ₂が挙げられている。（Ｃｐはシクロペンタジエニル基を、Ｃｐ^*はη⁵－ペンタメチルシクロペンタジエニル基を表す。）。また、その実施例で得られる共重合体は、エチレン／ノルボルネン共重合体であり、ノルボルネン由来単位の含有率が最高で６５．８モル％であり、ガラス転移温度（Ｔｇ）は１６７℃である。

(In the formula, M represents a transition metal of Group 4 of the periodic table such as Ti, L represents a monovalent anionic ligand whose coordinated atom is an element of Group 15 of the periodic table, and X represents a halogen, etc. , m represents an integer of 1 to 3, and R ¹ to R ⁵ represent hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or the like.)
and ethylene and/or an α-olefin having 3 to 20 carbon atoms and at least one cyclic A method for producing a cyclic olefin copolymer by copolymerization with an olefin compound is described, and specific examples of the transition metal compound (A) include CpTi(t-Bu ₂ C═N)Cl ₂ and Cp ^* Ti. (2,6- ⁱ Pr ₂ PhO)Cl ₂ is mentioned. (Cp represents a cyclopentadienyl group, and Cp ^* represents an η ⁵ -pentamethylcyclopentadienyl group). In addition, the copolymer obtained in the example is an ethylene/norbornene copolymer having a maximum content of norbornene-derived units of 65.8 mol% and a glass transition temperature (Tg) of 167°C. .

Further, Non-Patent Document 1 describes that ethylene and norbornene or the like were copolymerized in the presence of a transition metal compound represented by the following formula and methylaluminoxane (MAO). The content of norbornene-derived units in the copolymers described as experimental examples is up to about 50 mol %, and the corresponding Tg is up to 145.1°C to 160.5°C.

また、エチレンとノルボルネンや、エチレンとテトラシクロドデセン等との共重合体などの環状オレフィン共重合体は、医療用の材料の他、ＤＶＤのピックアップレンズやスマートフォンのカメラレンズなど、その透明性と高いガラス転移温度を生かし、ガラスの代替材料を代表例とする各種の用途に用いられている。
このような重合体は、古くは１９８０年代からの報告されている（例えば、特許文献２や特許文献３）が、そのガラス転移温度が１７０℃以下の様である。

In addition, cyclic olefin copolymers such as copolymers of ethylene and norbornene, ethylene and tetracyclododecene, etc., are used not only for medical materials, but also for DVD pickup lenses and smartphone camera lenses due to their transparency and Taking advantage of its high glass transition temperature, it is used in various applications, typically as a substitute material for glass.
Such polymers have been reported since the 1980s (for example, Patent Documents 2 and 3), and their glass transition temperature seems to be 170° C. or less.

Japanese Patent Application Laid-Open No. 2007-63409 JP-A-62-252407 JP-A-62-215611

Macromolecules 2011, 44, 1986-1998

(Problems of the first present invention)
However, conventional olefin polymerization using a transition metal compound as a catalyst has room for further improvement in terms of catalytic activity, increasing the molecular weight of the polymer, and the like. Further, if the glass transition temperature of the cyclic olefin copolymer can be increased and the heat resistance can be brought closer to that of glass, further expansion of applications can be expected.

In view of such prior art, the first present invention provides an olefin polymerization catalyst containing a transition metal compound, which is highly active and capable of producing an olefin polymer having a high molecular weight. It is intended to

A further object of the first aspect of the present invention is to provide an olefin polymerization catalyst or the like capable of producing an α-olefin/cyclic olefin copolymer with high copolymerizability.

(Problem of the second present invention)
When the transition metal compound described in Non-Patent Document 1 is used as an olefin polymerization catalyst as a metallocene compound, it has been found that there is room for further improvement in terms of catalytic activity, copolymerizability, increasing the molecular weight of the polymer, and the like. rice field.

In view of such prior art, the second object of the present invention is to provide a novel transition metal compound, especially a novel transition metal compound that can be used as an olefin polymerization catalyst.

A second aspect of the present invention provides a highly active olefin polymerization catalyst capable of producing a high-molecular-weight olefin polymer, and a novel transition metal that can be used in such an olefin polymerization catalyst. The purpose is to provide chemical compounds and the like.

Furthermore, a second aspect of the present invention is an olefin polymerization catalyst capable of producing an α-olefin/cyclic olefin copolymer with high copolymerizability, and can be used for such an olefin polymerization catalyst. The purpose is to provide novel transition metal compounds and the like.

(Problem of the third present invention)
The third aspect of the present invention has a glass transition temperature higher than that of conventional α-olefin/cyclic olefin addition copolymers, particularly conventional copolymers having the same ratio of structural units derived from cyclic olefins. An object of the present invention is to provide a novel α-olefin/cyclic olefin addition copolymer. Moreover, it aims at expanding the use of a cyclic olefin copolymer by this.

(First invention)
The first present invention relates to the following [1] to [13].
[1]
(A) a transition metal compound;
(B) (B-1) an organometallic compound (B-2) an organoaluminum oxy compound, and (B-3) at least one selected from the group consisting of a compound that forms an ion pair by reacting with the transition metal compound (A) a compound;
(C) (C-1) an alcohol compound; and (C-2) at least one compound selected from a phenol compound.

[2]
The olefin polymerization catalyst of [1], wherein the transition metal compound (A) is a compound represented by the following general formula [A-1].

〔式［A-1］において、
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、
ｎは１～４の整数であり、
Ｘはそれぞれ独立に水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基、またはジエン系二価誘導体基であり、
Ｒ¹～Ｒ⁸はそれぞれ独立に水素原子、炭素原子数１～２０の炭化水素基、ハロゲン原子、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基、イオウ含有基、またはリン含有基であり、Ｒ¹～Ｒ⁵のうち隣接する基同士は互いに結合して環を形成していてもよい。〕

[In formula [A-1],
M is a titanium atom, a zirconium atom, or a hafnium atom;
n is an integer from 1 to 4,
Each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene is a divalent derivative group,
R ¹ to R ⁸ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group; and adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring. ]

[3]
In the general formula [A-1],
M is a titanium atom or a zirconium atom,
each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group;
R ¹ to R ⁵ and R ⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, or a silicon-containing group, and adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring,
The olefin polymerization catalyst according to [2] above, wherein R ⁶ and R ⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms.

[4]
In the general formula [A-1],
M is a titanium atom,
R ¹ to R ⁵ and R ⁸ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and adjacent groups among R ¹ to R ⁵ are bonded to each other to form a ring. may be
The olefin polymerization catalyst according to [3] above, wherein R ⁶ and R ⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms.

[5]
The olefin polymerization catalyst according to any one of [1] to [4], wherein the compound (C) contains the alcohol compound (C-1) having 1 to 20 carbon atoms.

[6]
The olefin polymerization catalyst according to any one of [1] to [5], wherein the compound (C) contains the phenol compound (C-2) having 6 to 20 carbon atoms.

[7]
The alcohol compound (C-1) is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol. The olefin polymerization catalyst of [5] above, which is one or two or more.

[8]
The phenol compound (C-2) is 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 4-nonylphenol, 4-hexylphenol, 4-isopropylphenol, 3, 5-dimethylphenol, 2,3,6-trimethylphenol, 2,3,5-trimethylphenol, 2,4-di-tert-butylphenol, 2-isopropylphenol, 2-tert-butylphenol, p-dodecylphenol, 2 - The olefin polymerization catalyst of [6], which is one or more selected from the group consisting of phenylphenol and p-phenylphenol.

[9]
(Z-1) a linear or branched α-olefin having 2 to 30 carbon atoms;
(Z-2) The above used for copolymerization with a cyclic olefin represented by the following general formula [ZI], general formula [Z-II], general formula [Z-III] or general formula [Z-IV] The olefin polymerization catalyst according to any one of [1] to [8].

〔式［Z-I］中、ｕは０または１であり、
ｖは０または正の整数であり、
ｗは０または１であり、
Ｒ⁶¹～Ｒ⁷⁸ならびにＲ^a1およびＲ^b1は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁷⁵～Ｒ⁷⁸は、互いに結合して単環または、多環を形成していてもよく、かつ該単環または多環が二重結合を有していてもよく、またＲ⁷⁵とＲ⁷⁶とで、またはＲ⁷⁷とＲ⁷⁸とでアルキリデン基を形成していてもよい。〕

[In the formula [ZI], u is 0 or 1,
v is 0 or a positive integer;
w is 0 or 1;
R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and R ⁷⁵ to R ⁷⁸ are bonded together to form a monocyclic or polycyclic ring; and the monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. . ]

〔式［Z-II］中、ｘおよびｄは０または１以上の整数であり、
ｙおよびｚは０、１または２であり、
Ｒ⁸¹～Ｒ⁹⁹は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁸⁹およびＲ⁹⁰が結合している炭素原子と、Ｒ⁹³が結合している炭素原子またはＲ⁹¹が結合している炭素原子とは、直接あるいは炭素原子数１～３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ⁹⁵とＲ⁹²またはＲ⁹⁵とＲ⁹⁹とは互いに結合して単環または多環の芳香族環を形成していてもよい。〕

[In the formula [Z-II], x and d are 0 or an integer of 1 or more,
y and z are 0, 1 or 2;
R ⁸¹ to R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, the carbon atom to which R ⁹³ is bonded, or R ⁹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ]

〔式［Z-III］中、Ｒ¹⁰⁰およびＲ¹⁰¹は、それぞれ独立に水素原子または炭素原子数１～５の炭化水素基であり、ｆは１≦ｆ≦１８である。〕

[In formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18. ]

〔一般式［Z-IV］中、ｘは０または１以上の整数であり、
Ｒ¹¹¹～Ｒ¹¹⁸は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、
Ｒ¹²¹～Ｒ¹²⁴は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、隣接する２つの基は互いに結合し単環または複環の芳香族環を形成していてもよい。〕

[In the general formula [Z-IV], x is an integer of 0 or 1 or more,
R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group;
R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ]

[10]
The α-olefin (Z-1) is ethylene, and the cyclic olefin (Z-2) is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, the olefin polymerization catalyst of the above [9].

[11]
A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of [1] to [10].

[12]
The olefin polymer of [11], wherein the olefin polymerization catalyst is the olefin polymerization catalyst of [9], and the olefin comprises the α-olefin (Z-1) and the cyclic olefin (Z-2). manufacturing method.

[13]
The α-olefin (Z-1) is ethylene, and the cyclic olefin (Z-2) is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene A method for producing the olefin polymer of [12] above.

(Second invention)
The second invention relates to the following [14] to [25].

[14]
A transition metal compound represented by the following general formula [A-1'-1].

〔式［A-1'-1］において、
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、
ｎは１～４の整数であり、
Ｘはそれぞれ独立に水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基、またはジエン系二価誘導体基であり、
Ｒ¹～Ｒ⁵およびＲ⁸はそれぞれ独立に水素原子、炭素原子数１～２０の炭化水素基、ハロゲン原子、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基、イオウ含有基、またはリン含有基であり、Ｒ¹～Ｒ⁵のうち隣接する基同士は互いに結合して環を形成していてもよく、
Ｒ⁶およびＲ⁷はそれぞれ独立にハロゲン原子またはハロゲン含有基である。〕

[In the formula [A-1'-1],
M is a titanium atom, a zirconium atom, or a hafnium atom;
n is an integer from 1 to 4,
Each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene is a divalent derivative group,
R ¹ to R ⁵ and R ⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, wherein adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring;
R6 and ^R7 are each independently a halogen atom or a halogen ^- containing group. ]

[15]
The transition metal compound of the above [14], wherein in the general formula [A-1'-1], M is a titanium atom.

[16]
The transition metal compound according to the above [15], wherein in the general formula [A-1'-1], R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ² to R ⁵ are hydrogen atoms.

[17]
The transition metal compound of the above [16], wherein in the general formula [A-1'-1], R ⁶ and R ⁷ are each independently a halogen-containing group.

[18]
A transition metal compound represented by the following general formula [A-1'-2].

〔式［A-1'-2］において、
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、
ｎは１～４の整数であり、
Ｘはそれぞれ独立に水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基、またはジエン系二価誘導体基であり、
Ｒ¹¹～Ｒ²⁰はそれぞれ独立に水素原子、炭素原子数１～２０の炭化水素基、ハロゲン原子、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基、イオウ含有基、またはリン含有基であり、これらのうち隣接する基同士は互いに結合して環を形成していてもよい。〕

[In the formula [A-1'-2],
M is a titanium atom, a zirconium atom, or a hafnium atom;
n is an integer from 1 to 4,
Each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene is a divalent derivative group,
R ¹¹ to R ²⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group; and adjacent groups among these may be bonded to each other to form a ring. ]

[19]
The transition metal compound of the above [18], wherein in the general formula [A-1'-2], M is a titanium atom.

[20]
The transition metal compound of the above [19], wherein in the general formula [A-1'-2], R ¹¹ to R ¹⁷ are hydrogen atoms.

[21]
The transition metal compound of the above [20], wherein in the general formula [A-1'-2], R ¹⁸ and R ¹⁹ are each independently a hydrocarbon group having 1 to 20 carbon atoms.

[22]
(A-1′) the transition metal compound according to any one of [14] to [21];
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and (B-3) an olefin containing at least one compound selected from the group consisting of compounds that form an ion pair by reacting with the transition metal compound (A-1′) Polymerization catalyst.

[23]
A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst of the above [22].

[24]
The olefin is
(Z-1) a linear or branched α-olefin having 2 to 30 carbon atoms, and (Z-2) the following general formula [ZI], general formula [Z-II], general formula [Z-III ] or the method for producing the olefin polymer of the above [23] containing a cyclic olefin represented by the general formula [Z-IV].

〔式［Z-I］中、ｕは０または１であり、
ｖは０または正の整数であり、
ｗは０または１であり、
Ｒ⁶¹～Ｒ⁷⁸ならびにＲ^a1およびＲ^b1は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁷⁵～Ｒ⁷⁸は、互いに結合して単環または、多環を形成していてもよく、かつ該単環または多環が二重結合を有していてもよく、またＲ⁷⁵とＲ⁷⁶とで、またはＲ⁷⁷とＲ⁷⁸とでアルキリデン基を形成していてもよい。〕

[In the formula [ZI], u is 0 or 1,
v is 0 or a positive integer;
w is 0 or 1;
R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and R ⁷⁵ to R ⁷⁸ are bonded together to form a monocyclic or polycyclic ring; and the monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. . ]

〔式［Z-II］中、ｘおよびｄは０または１以上の整数であり、
ｙおよびｚは０、１または２であり、
Ｒ⁸¹～Ｒ⁹⁹は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁸⁹およびＲ⁹⁰が結合している炭素原子と、Ｒ⁹³が結合している炭素原子またはＲ⁹¹が結合している炭素原子とは、直接あるいは炭素原子数１～３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ⁹⁵とＲ⁹²またはＲ⁹⁵とＲ⁹⁹とは互いに結合して単環または多環の芳香族環を形成していてもよい。〕

[In the formula [Z-II], x and d are 0 or an integer of 1 or more,
y and z are 0, 1 or 2;
R ⁸¹ to R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, the carbon atom to which R ⁹³ is bonded, or R ⁹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ]

〔式［Z-III］中、Ｒ¹⁰⁰およびＲ¹⁰¹は、それぞれ独立に水素原子または炭素原子数１～５の炭化水素基であり、ｆは１≦ｆ≦１８である。〕

[In formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18. ]

〔一般式［Z-IV］中、ｘは０または１以上の整数であり、
Ｒ¹¹¹～Ｒ¹¹⁸は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、
Ｒ¹²¹～Ｒ¹²⁴は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、隣接する２つの基は互いに結合し単環または複環の芳香族環を形成していてもよい。〕

[In the general formula [Z-IV], x is an integer of 0 or 1 or more,
R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group;
R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ]

[25]
The α-olefin (Z-1) is ethylene, and the cyclic olefin (Z-2) is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene A method for producing the olefin polymer of [24] above.

(Third invention)
The third invention relates to the following [26] to [29].
[26]
Structural unit (z-1') represented by the following general formula [Z'], and the following general formula [Z-I'], general formula [Z-II'], general formula [Z-III'] or general Structural unit (z-2') represented by formula [Z-IV']
A cyclic olefin copolymer containing and satisfying the following requirements [I].

〔式［Ｚ'］中、Ｒ³⁰⁰は水素原子又は炭素原子数１～２９の直鎖状または分岐状の炭化水素基を示す。〕

[In the formula [Z′], R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. ]

〔式［Z-I'］中、ｕは０または１であり、
ｖは０または正の整数であり、
ｕ＋ｖ≧１を満たし、
ｗは０または１であり、
Ｒ⁶¹～Ｒ⁷⁸ならびにＲ^a1およびＲ^b1は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁷⁵～Ｒ⁷⁸は、互いに結合して単環または、多環を形成していてもよく、かつ該単環または多環が二重結合を有していてもよく、またＲ⁷⁵とＲ⁷⁶とで、またはＲ⁷⁷とＲ⁷⁸とでアルキリデン基を形成していてもよい。〕

[In the formula [Z-I'], u is 0 or 1,
v is 0 or a positive integer;
satisfies u+v≧1,
w is 0 or 1;
R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and R ⁷⁵ to R ⁷⁸ are bonded together to form a monocyclic or polycyclic ring; and the monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. . ]

〔式［Z-II'］中、ｘおよびｄは０または１以上の整数であり、
ｙおよびｚは０、１または２であり、
Ｒ⁸¹～Ｒ⁹⁹は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁸⁹およびＲ⁹⁰が結合している炭素原子と、Ｒ⁹³が結合している炭素原子またはＲ⁹¹が結合している炭素原子とは、直接あるいは炭素原子数１～３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ⁹⁵とＲ⁹²またはＲ⁹⁵とＲ⁹⁹とは互いに結合して単環または多環の芳香族環を形成していてもよい。〕

[In the formula [Z-II'], x and d are 0 or an integer of 1 or more,
y and z are 0, 1 or 2;
R ⁸¹ to R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, the carbon atom to which R ⁹³ is bonded, or R ⁹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ]

〔式［Z-III'］中、Ｒ¹⁰⁰およびＲ¹⁰¹は、それぞれ独立に水素原子または炭素原子数１～５の炭化水素基であり、ｆは１≦ｆ≦１８である。〕

[In the formula [Z-III′], R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18. ]

〔一般式［Z-IV'］中、ｘは０または１以上の整数であり、
Ｒ¹¹¹～Ｒ¹¹⁸は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、
Ｒ¹²¹～Ｒ¹²⁴は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、隣接する２つの基は互いに結合し単環または複環の芳香族環を形成していてもよい。〕
要件［I］：前記オレフィン［ＣＯ］由来の構造単位の二連子連鎖構造（［ＣＯ］－［ＣＯ］）の割合が０．５～３０モル％である。
〔ただし、前記構造単位（ｚ－１’）の二連子連鎖構造（［Ｅ］－［Ｅ］）の割合、前記構造単位（ｚ－１’）と前記構造単位（ｚ－２’）との連結構造（［Ｅ］－［ＣＯ］）の割合、および前記構造単位（ｚ－２’）の二連子連鎖構造（［ＣＯ］－［ＣＯ］）の割合の合計を１００モル％とする。〕

[In the general formula [Z-IV'], x is an integer of 0 or 1 or more,
R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group;
R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ]
Requirement [I]: The ratio of the biad chain structure ([CO]-[CO]) of the structural unit derived from the olefin [CO] is 0.5 to 30 mol%.
[However, the ratio of the double chain structure ([E]-[E]) of the structural unit (z-1′), the ratio of the structural unit (z-1′) and the structural unit (z-2′), The ratio of the linked structure ([E]-[CO]) and the ratio of the double chain structure ([CO]-[CO]) of the structural unit (z-2′) is 100 mol%. . ]

[27]
The cyclic olefin copolymer of [26] above, which satisfies the following requirements [II].
Requirement [II]: The molecular weight determined by gel permeation chromatography (GPC) is 5×10 ⁴ or more and 10×10 ⁵ or less.

[28]
Ethylene and tetracyclo [4.4.0.1 ^2,5 . The cyclic olefin copolymer of [26] or [27], which is an addition copolymer with 1 ^7,10 ]-3-dodecene.

[29]
The cyclic olefin copolymer according to any one of [26] to [28], which has a glass transition temperature of 180°C to 300°C.

(Effect of the first invention)
By using the olefin polymerization catalyst of the present invention, a highly active and high-molecular-weight olefin polymer can be produced.

Furthermore, according to one aspect of the present invention, an α-olefin/cyclic olefin copolymer can be produced with high copolymerizability.
Moreover, it is also possible to create a cyclic olefin copolymer with an unprecedentedly high glass transition temperature. Such polymers have unprecedented characteristic structures and physical properties.

(Effect of the second invention)
A second aspect of the present invention provides a novel transition metal compound.
The transition metal compound of the second invention can be used, inter alia, as an olefin polymerization catalyst.

Further, according to an aspect of the second present invention, a highly active olefin polymerization catalyst capable of producing a high-molecular-weight olefin polymer, and a novel catalyst that can be used for such an olefin polymerization catalyst Transition metal compounds and the like can be provided.

Furthermore, according to a second aspect of the present invention, an olefin polymerization catalyst capable of producing an α-olefin/cyclic olefin copolymer with high copolymerizability, and use in such an olefin polymerization catalyst It is possible to provide a novel transition metal compound that can be

(Effect of the third invention)
Since the cyclic olefin copolymer according to the third aspect of the present invention has a glass transition temperature higher than that of the conventional technology, it can be expected to expand its applications.

FIG. 1 shows the relationship between the composition and the glass transition temperature (Tg) of the cyclic olefin copolymers produced in Examples and Comparative Examples.

Hereinafter, the olefin polymerization catalyst and the like according to the present invention will be described in more detail.
[First invention]
[Catalyst for olefin polymerization]
The olefin polymerization catalyst of the first invention is
(A) a transition metal compound;
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from the group consisting of compounds that form an ion pair by reacting with the transition metal compound (A);
(C) (C-1) an alcohol compound and (C-2) at least one compound selected from a phenol compound.

<Transition metal compound (A)>
Examples of the transition metal compound (A) include transition metal compounds contained in conventional olefin polymerization catalysts, and specific examples thereof include the following transition metal complexes (1) to (9).

(Transition metal complex (1))
Transition metal complex (1) is a compound represented by the following general formula [A1].

<R ¹ to R ⁸ >
In formula [A1], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen atom, hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen selected from containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups, which may be the same or different, and adjacent groups are bonded together to form a ring; may be formed.

Hydrocarbon groups include, for example, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups and arylalkyl groups. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, neopentyl group and n-hexyl group. , n-octyl, nonyl, dodecyl and eicosyl groups. Cycloalkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl groups. Alkenyl groups include, for example, vinyl groups, propenyl groups and cyclohexenyl groups. Aryl groups include, for example, phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, α- or β-naphthyl group, methylnaphthyl group, anthracenyl group, phenanthryl group, benzyl A phenyl group, a pyrenyl group, an acenaphthyl group, a phenalenyl group, an acanthrilenyl group, a tetrahydronaphthyl group, an indanyl group and a biphenylyl group. Arylalkyl groups include, for example, benzyl, phenylethyl and phenylpropyl groups.

<Y>
In formula [A1], Y is a divalent group that bonds two ligands, specifically a divalent group, a hydrocarbon group having 1 to 20 carbon atoms, and a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, preferably a C 1-20 divalent hydrocarbon group or a divalent silicon-containing group.

The divalent hydrocarbon group includes an alkylene group, a substituted alkylene group and an alkylidene group, specific examples of which are
Alkylene groups such as methylene, ethylene, propylene and butylene;
Isopropylidene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolyl substituted alkylene groups such as methylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene and 1-ethyl-2-methylethylene; and cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexyl Cycloalkylidene groups such as sylidene, cycloheptylidene, bicyclo[3.3.1]nonylidene, norbornylidene, adamantylidene, tetrahydronaphtylidene and dihydroindanidene and alkylidene groups such as ethylidene, propylidene and butylidene .

As a divalent silicon-containing group,
silylene; and methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolylsilylene, methylnaphthylsilylene, dinaphthyl Alkylsilylene groups such as silylene, cyclodimethylsilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene and cycloheptamethylenesilylene, and particularly preferably dimethylsilylene and dibutylsilylene. and dialkylsilylene groups such as

〈M〉
In formula [A1], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, particularly preferably Zr.

<X>
In formula [A1], each X is independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. is an atom or group, preferably a halogen atom or a hydrocarbon group. Halogen atoms include fluorine, chlorine, bromine and iodine, particularly preferably chlorine.
Specific examples of the transition metal complex (1) include compounds listed in [0077] of JP-A-2013-224408.

(Transition metal complex (2))
The transition metal complex (2) is a compound represented by the following general formula [A2].

<R ¹ to R ⁶ and R ¹¹ to R ¹⁶ >
In formula [A2], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, selected from hydrocarbon groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups, whether identical or different; Alternatively, two adjacent groups may be linked together to form a ring.

Examples of the hydrocarbon group include the hydrocarbon groups exemplified as R ¹ to R ⁸ in the above formula [A1].
R ¹ to R ⁶ and R ¹¹ to R ¹⁶ are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

<Y>
In formula [A2], Y is a divalent group that binds two ligands, specifically a divalent group, a hydrocarbon group having 1 to 20 carbon atoms, and a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, preferably a C 1-20 divalent hydrocarbon group or a divalent silicon-containing group.
These groups include the divalent groups exemplified as Y in the above formula [A1].

〈M〉
In formula [A2], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, particularly preferably Zr.

<X>
In formula [A2], each X is independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group. is an atom or group, preferably a halogen atom or a hydrocarbon group. Halogen atoms include fluorine, chlorine, bromine and iodine, particularly preferably chlorine.
Specific examples of the transition metal complex (2) include compounds listed in [0071] of JP-A-2013-224408.

(Transition metal complex (3))
The transition metal complex (3) is a compound represented by the following general formula [A3].

< ^R1 to ^R14 >
In formula [A3], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently is a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and any two of the substituents R ¹ to R ⁴ are bonded to each other to form a ring any two of the substituents R ⁵ to R ¹² may be bonded together to form a ring, and R ¹³ and R ¹⁴ may be bonded together to form a ring may be

Hydrocarbon groups for R ¹ to R ¹⁴ include, for example, one or more of linear hydrocarbon groups, branched hydrocarbon groups, saturated cyclic hydrocarbon groups, unsaturated cyclic hydrocarbon groups, and saturated hydrocarbon groups. is substituted with a cyclic unsaturated hydrocarbon group. The number of carbon atoms in the hydrocarbon group is usually 1-20, preferably 1-15, more preferably 1-10.

Linear hydrocarbon groups include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl straight-chain alkyl groups such as groups, n-decanyl groups; and straight-chain alkenyl groups such as allyl groups.

Branched hydrocarbon groups include, for example, isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group and other branched alkyl groups.

Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and methylcyclohexyl group; polycyclic groups such as norbornyl group, adamantyl group and methyladamantyl group. be done.

Examples of cyclic unsaturated hydrocarbon groups include phenyl, tolyl, naphthyl, biphenyl, phenanthryl, anthracenyl and other aryl groups; cyclohexenyl and other cycloalkenyl groups; 5-bicyclo[2.2. 1] polycyclic unsaturated alicyclic groups such as hept-2-enyl group.

Examples of the group obtained by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group, a triphenylmethyl group, and the like. A group obtained by substituting one or more hydrogen atoms of the alkyl group of with an aryl group.

Examples of heteroatom-containing hydrocarbon groups for R ¹ to R ¹⁴ include alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy, and oxygen-containing hydrocarbon groups such as furyl; N-methylamino; amino groups such as N,N-dimethylamino group and N-phenylamino group; nitrogen atom-containing hydrocarbon groups such as pyryl group; and sulfur atom-containing hydrocarbon groups such as thienyl group. The carbon number of the heteroatom-containing hydrocarbon group is generally 1-20, preferably 2-18, more preferably 2-15. However, heteroatom-containing hydrocarbon groups exclude silicon-containing groups.

Examples of silicon-containing groups for R ¹ to R ¹⁴ include trimethylsilyl, triethylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, and triphenylsilyl groups of the formula —SiR ₃ (wherein a plurality of R independently an alkyl group having 1 to 15 carbon atoms or a phenyl group).

Any two substituents among R ¹ to R ¹⁴ , for example, two adjacent substituents (e.g., R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ ) are bonded together to form a ring; good too. The ring formation may occur at two or more sites in the molecule.

In the present specification, the ring (additional ring) formed by bonding two substituents to each other includes, for example, an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specific examples include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; benzene ring. Moreover, such a ring structure may further have a substituent such as an alkyl group on the ring.

R ⁵ , R ⁸ , R ⁹ and R ¹² are preferably hydrogen atoms.
R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group or a nitrogen atom-containing hydrocarbon group, more preferably a hydrocarbon group. R ⁶ and R ⁷ may be bonded together to form a ring, and R ¹⁰ and R ¹¹ may be bonded together to form a ring. Examples of the structure of the fluorenyl group moiety as described above include those represented by the following formulas.

Ｒ¹³およびＲ¹⁴は、好ましくは炭化水素基、ヘテロ原子含有炭化水素基またはケイ素含有基であり、さらに好ましくはアリール基または置換アリール基（ヘテロ原子含有炭化水素基またはケイ素含有基を有するアリール基）である。

R ¹³ and R ¹⁴ are preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, more preferably an aryl group or a substituted aryl group (an aryl group having a heteroatom-containing hydrocarbon group or a silicon-containing group ).

<Y>
In formula [A3], Y is a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom.

<M, Q, j>
In formula [A3], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf.
Q is a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair. When j is an integer of 2 or more, Q may be selected in the same or different combinations.

Halogen atoms for Q include, for example, fluorine, chlorine, bromine, and iodine.
Examples of the hydrocarbon group for Q include the same groups as the hydrocarbon groups for R ¹ to R ¹⁴ , preferably alkyl groups such as linear alkyl groups and branched alkyl groups.

Examples of anionic ligands in Q include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; , methylanilide, and diphenylamide.

Examples of neutral ligands that can be coordinated with a lone pair in Q include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, 1,2- Ethers such as dimethoxyethane are included.

At least one of Q is preferably a halogen atom or an alkyl group.
j is an integer of 1 to 4, preferably 2; When j is an integer of 2 or more, Q may be selected in the same or different combination.

Specific examples of the transition metal complex (3) include compounds listed on pages 29 to 43 of WO 2004/87775 and compounds listed on pages 9 to 37 of WO 2006/25540. , compounds listed in [0117] of WO2015/122414, and compounds listed in [0143] of WO2015/122415.

(Transition metal complex (4))
Transition metal complex (4) is a compound represented by the following general formula [A4].

< ^R1 to ^R16 >
^In formula [A4], ^R1 , ^R2 , R3 ^{, R4} , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , R10, ^R11 , ^R12 , ^R13 , ^R14 , ^R15 and R ¹⁶ are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and any two substituents among R ¹ to R ¹⁶ are bonded together A ring may be formed.

The hydrocarbon group, heteroatom-containing hydrocarbon group and silicon ^{-containing group for R 1 to} R ¹⁶ include the hydrocarbon groups, ^heteroatom -containing hydrocarbon groups and silicon containing groups.

Of the substituents R ¹ to R ¹⁶ , two adjacent substituents (e.g. R ¹ and R ² , R ² and R ³ ,
^R4 and ^R6 , ^R4 and ^R7 , ^R5 and ^R6 , ^R5 and ^R7 , ^R6 and ^R8 , ^R7 and ^R8 , ^R9 and ^R10 , ^R10 and ^R11 , ^R11 and R ¹² , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ ) may combine with each other to form a ring, and R ⁴ and R ⁵ may combine with each other to form a ring R ⁶ and R ⁷ may be bonded together to form a ring, R ¹ and R ⁸ may be bonded together to form a ring, R ³ and R ⁴ may be bonded together They may combine to form a ring, or R ³ and R ⁵ may combine to form a ring. The ring formation may occur at two or more sites in the molecule.

In the present specification, the ring (additional ring) formed by bonding two substituents to each other includes, for example, an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specific examples include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; benzene ring. Moreover, such a ring structure may further have a substituent such as an alkyl group on the ring.

R ¹ and R ³ are preferably hydrogen atoms.
R ² is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, more preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, It is more preferably not an aryl group, and most preferably a linear hydrocarbon group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group. ) is a tertiary carbon substituent.

Specific examples of R ² include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group and a 1-adamantyl group, and more preferably. is a tert-butyl group, tert-pentyl group, 1-methylcyclohexyl group, 1-adamantyl group, and the like. butyl group.

One preferred form of R ⁴ is a hydrogen atom when the transition metal complex (4) is represented by the following general formula [A4′].

この場合、前記遷移金属錯体（４）は、本発明の趣旨を逸脱しない範囲で、一般式［A4'］で表される遷移金属錯体の全ての鏡像異性体、例えば一般式［A4''］で表される遷移金属錯体を包含する。

In this case, the transition metal complex (4) is any enantiomer of the transition metal complex represented by general formula [A4′], for example, general formula [A4″], without departing from the scope of the present invention. The transition metal complex represented by is included.

式［A4'］および［A4''］の表記において、ＭＱ_j部分が紙面手前に、架橋部が紙面奥側に存在するものとする。すなわち、これらの遷移金属錯体では、シクロペンタジエン環のα位（架橋部位が置換した炭素原子を基準とする）に、中心金属側に向いた水素原子（Ｒ⁴）が存在する。

In the expressions [A4′] and [A4″], the MQ _j portion is assumed to be in front of the page, and the bridging portion is in the back of the page. That is, in these transition metal complexes, there is a hydrogen atom (R ⁴ ) facing the central metal at the α-position of the cyclopentadiene ring (based on the carbon atom substituted by the bridging site).

On the other hand, in the general formula [A4] described above, it is not specified whether the MQ _j portion and the cross-linking portion are present on the front side of the page or on the back side of the page. That is, the transition metal compound (A4) represented by general formula [A4] includes a transition metal compound having a specific structure and enantiomers thereof.

At least one selected from R ⁴ , R ⁵ , R ⁶ and R ⁷ is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and R ⁴ and R ⁵ are a hydrogen atom or a hydrocarbon R ⁵ is more preferably an alkyl group such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group, and an alkyl group having 1 to 10 carbon atoms. is particularly preferred. Moreover, from the viewpoint of synthesis, it is also one of the preferred forms that both R ⁴ and R ⁵ are alkyl groups, and alkyl groups having 1 to 10 carbon atoms are particularly preferred. Similarly, from the viewpoint of synthesis, R ⁶ and R ⁷ are also preferably hydrogen atoms. It is more preferable that R ⁵ and R ⁷ are bonded together to form a ring, and it is particularly preferable that the ring is a 6-membered ring such as a cyclohexane ring.

R ⁸ is preferably a hydrocarbon group, particularly preferably an alkyl group such as a methyl group.
In general formula [A4], the fluorene ring portion is not particularly limited as long as it has a structure obtained from a known fluorene derivative. R ⁹ , R ¹² , R ¹³ and R ¹⁶ are preferably hydrogen atoms.

R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ are preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group or a nitrogen atom-containing hydrocarbon group, more preferably a hydrocarbon group, still more preferably a hydrocarbon group having 1 to 20 carbon atoms, such as 2,7-di-tert-butylfluorenyl group, 3,6-di-tert-butylfluorenyl group, 2,7-diphenyl-3, A 6-di-tert-butylfluorenyl group can be mentioned, and a 2,7-di-tert-butylfluorenyl group is particularly preferred.

R ¹⁰ and R ¹¹ may combine to form a ring, and R ¹⁴ and R ¹⁵ may combine to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2 ,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl-2,3, 6,7,8,10-hexahydro-1H-dicyclopenta[b,h]fluorenyl group, 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta [b,h]fluorenyl group, particularly preferably 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- A 1H-dibenzo[b,h]fluorenyl group can be mentioned.

<M, Q, j>
In formula [A4], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, particularly preferably Zr.

Q is a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair.
The halogen atom, hydrocarbon group, anionic ligand and lone electron pair-coordinable neutral ligand in Q include the halogen atom, hydrocarbon group, anionic ligand and lone ligand in the above formula [A3]. Examples of neutral ligands that can be coordinated by an electron pair include those exemplified.

j is an integer of 1 to 4, preferably 2; When j is an integer of 2 or more, Q may be selected in the same or different combination.
Specific examples of the transition metal complex (4) include compounds listed on pages 11 to 15 of WO 2006/68308, and compounds listed on [0075] to [0086] of WO 2014/50816. and the compounds listed in [0072]-[0084] of JP-A-2008/50816.

(Transition metal complex (5))
The transition metal complex (5) is a metal complex corresponding to the following general formula [A5] described in JP-T-2000-516228.

（式中、Ｍは、元素の周期律表の３－１３族の１、ランタニド又はアクチニドからの金属であり、それは＋２、＋３又は＋４形式酸化状態にあり、そして５個の置換基、即ちＲ^A、（Ｒ^B）_j－Ｔ（但し、ｊは０、１又は２である）、Ｒ^C、Ｒ^D及びＺ（但し、Ｒ^A、Ｒ^B、Ｒ^C及びＲ^DはＲ基である）を有する環状の非局在化π－結合リガンド基である１個のシクロペンタジエニル（Ｃｐ）基にπ結合しており、さらに
Ｔは、ｊが１又は２であるとき、Ｃｐ環そしてＲ^Bに共有結合しているヘテロ原子であり、さらにｊが０のとき、ＴはＦ、Ｃｌ、Ｂｒ又はＩであり；ｊが１のとき、ＴはＯ又はＳ、又はＮ又はＰであり、そしてＲ^BはＴへの二重結合を有し；ｊが２のとき、ＴはＮ又はＰであり、さらに
Ｒ^Bは、それぞれの場合独立して、水素であるか、又はヒドロカルビル、ヒドロカルビルシリル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリルヒドロカルビル、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ヒドロカルビルオキシである１－８０個の非水素原子を有する基であり、各Ｒ^Bは任意にそれぞれの場合独立して１－２０個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ（ヒドロカルビルシリル）アミノ、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ジ（ヒドロカルビル）ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビル又は１－２０個の非水素原子を有する非干渉基である１個以上の基により置換されていてもよく；そして
Ｒ^A、Ｒ^C及びＲ^Dのそれぞれは、水素であるか、又はヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル、ヒドロカルビルシリルヒドロカルビルである１－８０個の非水素原子を有する基であり、Ｒ^A、Ｒ^C及びＲ^Dのそれぞれは、任意にそれぞれの場合独立して１－２０個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ（ヒドロカルビルシリル）アミノ、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ジ（ヒドロカルビル）ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビルであるか、又は１－２０個の非水素原子を有する非干渉基である１個以上の基により置換されていてもよく；又は任意に、Ｒ^A、Ｒ^B、Ｒ^C及びＲ^Dの２個以上は、互いに共有結合してそれぞれのＲ基について１－８０個の非水素原子を有する１個以上の縮合環又は環系を形成し、１個以上の縮合環又は環系は、置換されていないか、又はそれぞれの場合独立して１－２０個の非水素原子を有するヒドロカルビルオキシ、ヒドロカルビルシロキシ、ヒドロカルビルシリルアミノ、ジ（ヒドロカルビルシリル）アミノ、ヒドロカルビルアミノ、ジ（ヒドロカルビル）アミノ、ジ（ヒドロカルビル）ホスフィノ、ヒドロカルビルスルフィド、ヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルビルシリル又はヒドロカルビルシリルヒドロカルビル、又は１－２０個の非水素原子を有する非干渉基である１個以上の基により置換されており；
Ｚはσ結合を介してＣｐ及びＭの両者に結合している２価の基であり、Ｚは硼素であるか又は元素の周期律表の１４族の一員であり、さらに窒素、燐、硫黄又は酸素からなり；
Ｘは、環状の非局在化π結合リガンド基であるリガンドの群を除く、６０個以内の原子を有するアニオン性又はジアニオン性リガンド基であり；
Ｘ'は、それぞれの場合独立して２０個以内の原子を有する中性のルイス塩基配位結合性化合物であり；
ｐは０、１又は２であり、そしてＸがアニオン性リガンドであるときＭの形式酸化状態より２少なく；Ｘがジアニオン性リガンドであるとき、ｐは１であり；そして
ｑは０、１又は２である。）
前記遷移金属錯体（５）の具体例としては、特表２０００－５１６２２８号公報の３５～９９頁に列挙された化合物が挙げられる。

(wherein M is a metal from groups 3-13 of the Periodic Table of the Elements, lanthanides or actinides, which are in the +2, +3 or +4 formal oxidation state, and five substituents, namely R ^A , (R ^B ) _j —T (where j is 0, 1 or 2), R ^C , R ^D and Z (where R ^A , R ^B , R ^C and R ^D are R groups) is π-bonded to one cyclopentadienyl (Cp) group, which is a cyclic delocalized π-bonded ligand group having a heteroatom covalently bonded to ^B , and when j is 0, T is F, Cl, Br, or I; when j is 1, T is O or S, or N or P; and RB has a double bond to ^T ; when j is 2, T is N or ^P , and RB is independently in each instance hydrogen or hydrocarbyl, hydrocarbylsilyl , halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, hydrocarbylamino, di(hydrocarbyl)amino, hydrocarbyloxy, each R ^B having 1 to 80 non-hydrogen atoms optionally in each case independently having 1-20 non-hydrogen atoms, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, substituted with one or more groups that are hydrocarbyl sulfides, hydrocarbyls, halogen-substituted hydrocarbyls, hydrocarbyloxy-substituted hydrocarbyls, hydrocarbylamino-substituted hydrocarbyls, hydrocarbylsilyls or hydrocarbylsilyl hydrocarbyls or non-interfering groups having 1-20 non-hydrogen atoms; and each of R ^A , R ^C and R ^D is hydrogen or hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilyl hydrocarbyl 1-80 groups having 1-20 non-hydrogen atoms, and each of R ^A , R ^C and R ^D is optionally independently in each instance hydrocarbyloxy, hydrocarbyl, having 1-20 non-hydrogen atoms. lucyloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or optionally substituted by one or more groups which are hydrocarbylsilyl hydrocarbyl or non-interfering groups having 1-20 non-hydrogen atoms; or optionally R ^A , R ^B , R ^C and R Two or more of ^D are covalently bonded to each other to form one or more fused rings or ring systems having 1-80 non-hydrogen atoms for each R group, wherein the one or more fused rings or ring systems are , hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, unsubstituted or having 1-20 non-hydrogen atoms in each case independently, di(hydrocarbyl)phosphino, hydrocarbyl sulfide, hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilyl hydrocarbyl, or one non-interfering group having 1-20 non-hydrogen atoms is substituted with the following groups;
Z is a divalent group attached to both Cp and M via a σ bond, Z is boron or a member of Group 14 of the Periodic Table of the Elements, and nitrogen, phosphorus, sulfur or consisting of oxygen;
X is an anionic or dianionic ligand group having up to 60 atoms, excluding the group of ligands that are cyclic delocalized pi-bonded ligand groups;
X′ is a neutral Lewis base coordinating compound having up to 20 atoms independently in each case;
p is 0, 1 or 2 and is 2 less than the formal oxidation state of M when X is an anionic ligand; p is 1 when X is a dianionic ligand; and q is 0, 1 or 2. )
Specific examples of the transition metal complex (5) include compounds listed on pages 35 to 99 of JP-T-2000-516228.

(Transition metal complex (6))
The transition metal complex (6) is an ansabis (μ-substituted) group 4 metal and aluminum compound of the periodic table corresponding to the following general formula [A6], which is described in JP-T-2002-522551.

（式中、Ｌ´はπ－結合した基であり、
Ｍは周期律表４族金属であり、
Ｊは窒素又は燐であり、
Ｚは２価の橋かけ結合基であり、
Ｒ´は不活性の１価のリガンドであり、
ｒは１又は２であり、
Ｘはそれぞれの場合独立してμ－橋かけ結合リガンド基を形成できるルイス塩基性リガンド基であり、所望により２個のＸ基は一緒に結合してもよく、そして
Ａ´はそれぞれの場合独立して水素を除いて５０個以内の原子のアルミニウム含有ルイス酸化合物であり、該化合物はμ－橋かけ結合基により金属錯体との付加物を形成し、所望により２個のＡ´基は一緒に結合しそれにより単一の２官能性ルイス酸含有化合物を形成してもよい。）

(wherein L′ is a π-bonded group,
M is a Group 4 metal of the periodic table,
J is nitrogen or phosphorus;
Z is a divalent bridging group,
R' is an inert monovalent ligand,
r is 1 or 2;
X is each independently a Lewis basic ligand group capable of forming a μ-bridging ligand group, optionally two X groups may be joined together, and A′ is each independently is an aluminum-containing Lewis acid compound of up to 50 atoms excluding hydrogen, said compound forming an adduct with a metal complex through a μ-bridging group, and optionally two A' groups together to thereby form a single bifunctional Lewis acid-containing compound. )

Specific examples of the transition metal complex (6) include compounds listed in [0025] to [0027] of JP-T-2002-522551.

(Transition metal complex (7))
The transition metal complex (7) is a metal complex corresponding to the following general formula [A7-1], [A7-2] or [A7-3] described in Japanese Patent Application Publication No. 2003-501433.

（式中、Ｍは元素周期律表の３～１３族ランタニド又はアクチニドの１つから選ばれる金属である；
Ｚはホウ素、又は元素周期律表の１４族の１員をもち、且つ窒素、リン、硫黄又は酸素をもつ２価の基である；
Ｘは水素を算入せずに６０以下の原子をもつアニオン性リガンド基であり、所望により２個のＸ基はいっしょになって２価のアニオン性リガンド基を形成している；
Ｘ'はそれぞれの場合独立に２０以下の原子をもつ中性ルイス塩基リガンドである；
ｐは０～５の数であって、Ｍの形式酸化状態より２少ない；
ｑは０、１又は２である；
Ｅはケイ素又は炭素である；
Ｒ^A はそれぞれの場合独立に水素又はＲ^B である；
Ｒ^B はＢＲ^C ₂ であるか、又はヒドロカルビル、ヒドロカルビルシリル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ジ（ヒドロカルビル）アミノ置換ヒドロカルビル、ＢＲ^C ₂ －置換ヒドロカルビル、ヒドロカルビルシリルヒドロカルビル、ジ（ヒドロカルビル）アミノ、ヒドロカルバジイルアミノ、又はヒドロカルビルオキシ基であり、各Ｒ^B は水素を算入せずに１～１８の原子をもち、そして所望により２個のＲ^B 基は共有結合して１以上の縮合環を形成していてもよい；
Ｒ^C はそれぞれの場合独立にヒドロカルビル、ハロゲン置換ヒドロカルビル、ヒドロカルビルオキシ置換ヒドロカルビル、ジヒドロカルビルアミノ置換ヒドロカルビル、ヒドロカルバジイルアミノ置換ヒドロカルビル、ヒドロカルビルシリル、ヒドロカルビルシリルヒドロカルビル、又はＲ^D である；
Ｒ^D はそれぞれの場合独立にジヒドロカルビルアミノ又はヒドロカルビルオキシ基で水素を算入せずに１～２０の原子をもち、そして所望により単一のホウ素上の２個のＲ^D 基はいっしょになってホウ素に結合した両原子価をもつヒドロカルバジイルアミノ－、ヒドロカルバジイルオキシ－、ヒドロカルバジイルジアミノ－、又はヒドロカルバジイルオキシ－基を形成している；
但し少なくとも１の場合においてＲ^A はＢＲ^C ₂ 、ＢＲ^C ₂ －置換ヒドロカルビル基、及びそれらが合体した誘導体から選ばれると共に、少なくとも１のＲ^CはＲ^D である；
Ｒ^F はそれぞれの場合独立に水素、又はシリル、ヒドロカルビル、ヒドロカルビルオキシ及びそれらの組合せから選ばれる基であって、該Ｒ^F は３０以下の炭素又はケイ素原子をもっている；そして ｘは１～８であるか、又は所望により（Ｒ^F ₂ Ｅ）_x が－Ｔ'Ｚ'－又は－（Ｔ'Ｚ'）₂ －であり、ここでＴ'はそれぞれの場合独立にホウ素又はアルミニウムであり、そしてＺ'はそれぞれの場合独立に

(wherein M is a metal selected from one of the lanthanides or actinides of Groups 3-13 of the Periodic Table of the Elements;
Z is boron or a divalent radical having a member of Group 14 of the Periodic Table of the Elements and having nitrogen, phosphorus, sulfur or oxygen;
X is an anionic ligand group having 60 or fewer atoms not counting hydrogen, optionally two X groups taken together to form a divalent anionic ligand group;
X' is independently in each instance a neutral Lewis base ligand having up to 20 atoms;
p is a number from 0 to 5, 2 less than the formal oxidation state of M;
q is 0, 1 or 2;
E is silicon or carbon;
^RA is independently hydrogen or ^RB at each occurrence;
R ^B is BR ^C2 or hydrocarbyl, hydrocarbylsilyl, halogen _- substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, di(hydrocarbyl)amino _- substituted hydrocarbyl, BR ^C2 -substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, di(hydrocarbyl)amino, a hydrocarbadiylamino or hydrocarbyloxy group, each R ^B having from 1 to 18 atoms not counting hydrogen, and optionally two R ^B groups covalently linked to form one or more fused rings; may form;
R ^C is independently at each occurrence hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dihydrocarbylamino-substituted hydrocarbyl, hydrocarbaziylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilyl hydrocarbyl, or R ^D ;
R ^D is each independently a dihydrocarbylamino or hydrocarbyloxy group having from 1 to 20 atoms not counting hydrogen, and optionally two R ^D groups on a single boron taken together forming hydrocarbadiylamino-, hydrocarbadiyloxy-, hydrocarbadiyldiamino-, or hydrocarbadiyloxy- groups with both valences attached to boron;
provided that in at least one instance R ^A is selected from BR ^C ₂ , BR ^C ₂ -substituted hydrocarbyl groups, and combined derivatives thereof, and at least one R ^C is R ^D ;
R ^F is in each instance independently hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R ^F having up to 30 carbon or silicon atoms; or optionally (R ^F ₂ E) _x is -T'Z'- or -(T'Z') ₂ -, where T' is independently boron or aluminum in each instance, and Z' is independently in each case

であり；
Ｒ¹ はそれぞれの場合独立に水素、ヒドロカルビル基、トリヒドロカルビルシリル基、又はトリヒドロカルビルシリルヒドロカルビル基であり、該Ｒ¹ 基は炭素を算入せずに２０以下の原子をもち、そして２個のこれらＲ¹ 基は所望によりいっしょになって環構造を形成していてもよい；そして
Ｒ⁵ はＲ¹ 又はＮ（Ｒ¹ ）₂ である。）

is;
R ¹ is in each instance independently hydrogen, a hydrocarbyl group, a trihydrocarbylsilyl group, or a trihydrocarbylsilylhydrocarbyl group, said R ¹ group having 20 or fewer atoms, not counting carbons, and two of these The R ¹ groups may optionally be taken together to form a ring structure; and R ⁵ is R ¹ or N(R ¹ ) ₂ . )

Specific examples of the transition metal complex (7) include the compounds listed in [0030] of JP-T-2003-501433.

(Transition metal complex (8))
Transition metal complex (8) is a compound represented by the following general formula [A8].

〈M〉
In the formula [A8], M represents a transition metal atom of Groups 4 and 5 of the periodic table, preferably a transition metal atom of Group 4. Specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc. are preferred, titanium, zirconium and hafnium are more preferred, and titanium or zirconium is particularly preferred.
A dotted line connecting N and M in formula [A8] generally indicates that N is coordinated to M, but in the present invention, it may or may not be coordinated.

<m>
In formula [A8], m represents an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 2.

<R ¹ to R ⁵ >
In formula [A8], R ¹ to R ⁵ may be the same or different, and are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group. , a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked together to form a ring.

Halogen atoms include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include the hydrocarbon groups exemplified as R ¹ to R ¹⁴ in the above formula [A3], particularly
1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, preferably 1 to 20 linear or branched alkyl groups;
an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as a phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group;
These aryl groups have substituents such as halogen atoms, alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, or aryloxy groups. A substituted aryl group with 1 to 5 substitutions is preferred.

R ¹ is a linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a A group selected from an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred.

Heterocyclic compound residues include residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples thereof include groups in which the compound residue is further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

Oxygen-containing groups include alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic acid anhydride groups and the like.

Nitrogen-containing groups include amino group, imino group, amide group, imido group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group and amino group. Ammonium salts and the like can be mentioned.

Boron-containing groups include boranediyl, boranetriyl, and diboranyl groups.
Sulfur-containing groups include mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups, thioacyl groups, thioether groups, thiocyanate groups, isocyanate groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, sulfenyl group and the like.

Phosphorus-containing groups include phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, and the like.
Silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, hydrocarbon-substituted siloxy groups, etc. More specifically, methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, and diethylsilyl groups. , triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl(pentafluorophenyl)silyl group and the like. Hydrocarbon-substituted siloxy groups include trimethylsiloxy groups and the like.
Germanium-containing groups and tin-containing groups include groups obtained by substituting germanium or tin for silicon in the above silicon-containing groups.

< R6 ^>
In formula [A8], R ⁶ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting only of primary or secondary carbon atoms, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, a single It is selected from cyclic or bicyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups and halogen atoms. Among these, from the viewpoint of olefin polymerization catalyst activity, from the viewpoint of providing a high molecular weight olefin polymer, and from the viewpoint of resistance to hydrogen during polymerization, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, It is preferably a group selected from monocyclic or bicyclic alicyclic hydrocarbon groups and aromatic hydrocarbon groups, more preferably a branched hydrocarbon group such as t-butyl group; benzyl group, 1- Aryl-substituted alkyl groups such as methyl-1-phenylethyl group (cumyl group), 1-methyl-1,1-diphenylethyl group and 1,1,1-triphenylmethyl group (trityl group); hydrocarbon at position 1 cyclohexyl group, adamantyl group, norbornyl group, tetracyclododecyl group, etc., having 6 to 15 carbon atoms or an alicyclic hydrocarbon group having a multiple ring structure.

<n>
In formula [A8], n is a number that satisfies the valence of M.

<X>
In formula [A8], X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic represents a compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X groups may combine with each other to form a ring.
As each group such as a halogen atom and a hydrocarbon group, the same groups as those exemplified in the above description of R ¹ to R ⁵ can be mentioned. Among these, halogen atoms and hydrocarbon groups are preferred.

(Transition metal complex (9))
Transition metal complex (9) is a compound represented by the following general formula [A9].

〈M〉
In formula [A9], M represents a transition metal atom of groups 4 to 11 of the periodic table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, manganese, iron, cobalt, nickel, palladium, etc. is preferably a metal atom of Groups 4 to 7 and 10, specifically titanium, zirconium, hafnium, vanadium, chromium, manganese and nickel, more preferably titanium and nickel.
The dotted line connecting N and M in formula [A9] generally indicates that N is coordinated to M, but in the present invention, it may or may not be coordinated.

<m>
In formula [A9], m represents an integer of 1 to 4, preferably 2.

<R ¹ to R ⁵ >
In formula [A9], R ¹ to R ⁵ may be the same or different, and are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group. , a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked together to form a ring.

Halogen atoms include fluorine, chlorine, bromine and iodine.
Hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups include those of the above formula [ A8] include those exemplified as R ¹ to R ⁵ .

A preferred embodiment of R ¹ is an aromatic group, more preferably an aryl group represented by the following general formula [A9-1] or an optionally substituted pyrrole.

In general formula [A9-1], R ^1A to R ^1E may be the same or different from each other, and may be bonded to each other to form a ring, a hydrogen atom, a hydrocarbon group, a heterocyclic compound residue, , oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups. Hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups include those of the above formula [ A9] include those exemplified as R ¹ to R ⁵ .

< R6 ^>
In formula [A9], R ⁶ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting only of primary or secondary carbon atoms, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group-substituted alkyl group, a single It is selected from cyclic or bicyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups and halogen atoms.

R ⁶ is an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl and anthranyl;
linear or branched (secondary) alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, isobutyl, sec-butyl, neopentyl;
Cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, etc. having 3 to 30 carbon atoms , preferably ³ to 20 cyclic saturated hydrocarbon groups. -bistrifluoromethylphenyl and the like are particularly preferred.

<n>
In formula [A9], n is a number satisfying the valence of M, specifically 0 to 5, preferably 1 to 4, more preferably 2.

<X>
In formula [A9], X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic represents a compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X groups may combine with each other to form a ring.

As each group such as a halogen atom and a hydrocarbon group, the same groups as those exemplified in the above description of R ¹ to R ⁵ can be mentioned.
Specific examples of the transition metal complex (9) include compounds listed in [0079] to [0088] of JP-A-2011-231291.

The transition metal compound (A) is not limited to the above-described transition metal complexes (1) to (9). [0030] to [0051] of 50256, [0016] of JP 2010-150246, [0133] of International Publication No. 2013/184579, [0006] of JP 2013-534934, JP 2009- Examples include transition metal compounds described in [0001] of JP-A-534517 and [0009] to [0017] of JP-T-2001-516776.

(Transition metal compound (A-1))
Further, the transition metal compound (A) preferably includes a transition metal compound (A-1) represented by the following general formula [A-1].

《M》
In formula [A-1], M represents a titanium atom, a zirconium atom, or a hafnium atom, preferably a titanium atom or a zirconium atom, more preferably a titanium atom.

《 ^R1 ～ ^R8 》
In formula [A-1], R ¹ to R ⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, It is a sulfur-containing group or a phosphorus-containing group, and adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring.

Examples of the halogen atoms include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. having 1 to 20 carbon atoms, preferably 1 to 10 linear or branched alkyl groups;
linear or branched alkenyl groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl, allyl, isopropenyl;
linear or branched alkynyl groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms such as ethynyl and propargyl;
cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl;
cyclic unsaturated hydrocarbon groups having 5 to 20 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; 6-10 aryl groups; and alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl.

Further, the hydrocarbon group may have a hydrogen atom substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and cumyl.
Examples of the cyclopentadienyl moiety having a ring formed by bonding adjacent groups among R ¹ to R ⁵ include the following ring structures, and the ring structures further have substituents. may be

Examples of the halogen-containing groups include halogenated hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl.

Examples of said silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. Specific examples of hydrocarbon-substituted silyl groups among these include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl(pentafluoro phenyl)silyl and the like. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferred. Trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are particularly preferred. Specific examples of hydrocarbon-substituted siloxy groups include trimethylsiloxy and the like.

Examples of said oxygen-containing groups include alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic anhydride groups, and furyl groups.

Among oxygen-containing groups, preferred examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy,
Preferred examples of aryloxy groups include phenoxy, 2,6-dimethylphenoxy and 2,4,6-trimethylphenoxy,
Preferred examples of ester groups include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, and p-chlorophenoxycarbonyl;
Preferred examples of acyl groups include formyl, acetyl, benzoyl, p-chlorobenzoyl, and p-methoxybenzoyl groups.

Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate group, an isothiocyanate group, a sulfoneester group, a sulfonamide group, Thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, and sulfenyl groups are included.

Among sulfur-containing groups, preferred examples of thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl.
Preferred examples of alkylthio groups include methylthio and ethylthio,
Preferred examples of arylthio groups include phenylthio, methylphenylthio, naphthylthio,
Preferred examples of sulfone ester groups include methyl sulfonate, ethyl sulfonate, phenyl sulfonate,
Preferred examples of sulfonamide groups include phenylsulfonamide, N-methylsulfonamide, N-methyl-p-toluenesulfonamide.

Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imide group, a pyrrolidino group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, Ammonium salts of diazo groups and amino groups are included.

Among nitrogen-containing groups, preferred examples of amino groups include dimethylamino, ethylmethylamino, and diphenylamino,
Preferred examples of imino groups include methylimino, ethylimino, propylimino, butylimino, and phenylimino,
Preferred examples of amide groups include acetamide, N-methylacetamide, and N-methylbenzamide,
Preferred examples of imido groups include acetimido and benzimide.

Examples of said phosphorus-containing groups include phosphide groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups.
As R ¹ to R ⁵ and R ⁸ ,
Hydrogen Atom A straight chain having 1 to 20, preferably 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl or branched alkyl group;
aryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl;
Hydrocarbon groups having 1 to 20 carbon atoms such as substituted aryl groups in which one or more hydrogen atoms of these aryl groups are substituted with halogen atoms, alkyl groups, alkoxy groups, aryl groups or aryloxy groups are preferred. Adjacent groups of ¹ to R ⁵ may combine with each other to form a ring.
Hydrocarbon groups having 1 to 20 carbon atoms are particularly preferred as R ⁶ and R ⁷ .

《n》
In formula [A-1], n is an integer of 1 to 4, and depending on the valence of M and the type of X, it is selected so that the transition metal compound (A-1) as a whole is electrically neutral. be done.

《X》
In formula [A-1], each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group , an aluminum-containing group, or a diene-based divalent derivative group.

Specific embodiments of these halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, and phosphorus-containing groups are the halogens as R ¹ to R ⁸ described above. As are specific embodiments of atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, and phosphorus-containing groups.

Examples of the boron-containing groups include boranediyl, boranetriyl, diboranyl, and groups such as alkyl-substituted boron, aryl-substituted boron, boron halide, and alkyl-substituted boron halide.

Examples of alkyl-substituted boron are represented by (Et) _2B- , (iPr) _2B- , (iBu) _2B- , (Et) _3B , (iPr) _3B , or (iBu) _3B . and
Examples of aryl-substituted boron include ( _C6H5 ) _2B- , _{( C6H5} ) _3B , _{( C6F5} ) _3B , or ( _{3,5- ( CF3} ) _2C6 a group represented by H ₃ ) ₃ B,
Examples of boron halides include groups represented by BCl ₂ — or BCl ₃ ,
Examples of alkyl group-substituted boron halides include groups represented by (Et)BCl-, (iBu)BCl- and (C ₆ H ₅ ) ₂ BCl. Of these, trisubstituted boron may be in a coordinated state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

Examples of the aluminum-containing group include groups such as alkyl group-substituted aluminum, aryl group-substituted aluminum, halogenated aluminum, and alkyl group-substituted aluminum halide.

Examples of alkyl-substituted aluminum are represented by (Et) ₂ Al-, (iPr) ₂ Al-, (iBu) ₂ Al-, (Et) ₃ Al, (iPr) ₃ Al, or (iBu) ₃ Al. and
Examples of aryl group-substituted aluminum include groups represented by (C ₆ H ₅ ) ₂ Al-,
Examples of aluminum halides include groups represented by AlCl ₂ — or AlCl ₃ ,
Examples of alkyl group-substituted aluminum halides include groups represented by (Et)AlCl-- and (iBu)AlCl--. Of these, trisubstituted aluminum may be in a coordinated state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

Examples of the diene-based divalent derivative groups include a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, a piperylenyl (1,3-pentadienyl) group, a 2,4-hexadienyl group, metallocyclopentene groups such as 1,4-diphenyl-1,3-pentadienyl group and cyclopentadienyl group;

Further, X may have a structure in which the groups listed as specific examples of X are bonded to each other and form a ring together with M. For example, X may be an alkylene group having a structure in which two alkyl groups are bonded, and this alkylene group and M may form a ring.

As the transition metal compound (A-1) represented by the general formula [A-1],
In formula [A-1],
M is a titanium atom, a zirconium atom, or a hafnium atom;
n is an integer from 1 to 4,
Each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene is a divalent derivative group,
R ¹ to R ⁸ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group; and a transition metal compound (A-1a) in which adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring is preferred.

As the transition metal compound (A-1a),
In the general formula [A-1],
M is a titanium atom,
R ¹ to R ⁵ and R ⁸ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and adjacent groups among R ¹ to R ⁵ are bonded to each other to form a ring. A transition metal compound (A-1b) in which R ⁶ and R ⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms is preferred.

Examples of the transition metal compound (A-1) also include the transition metal compound (A-1′) according to the second aspect of the present invention described below.
Specific examples of the transition metal compound (A-1) include compounds exemplified as specific examples of the transition metal compound (A-1′) according to the second aspect of the present invention described later. compounds that are

By polymerizing an α-olefin and a cyclic olefin in the presence of the transition metal compound (A-1), an α-olefin/cyclic olefin copolymer can be produced with high copolymerizability (that is, contains many structural units derived from cyclic olefins). The reason for this is not entirely clear, but it is believed that the planarity of the cyclopentadienyl or indenyl ligands is involved, maintaining ion separation from the cocatalyst so that the polymerization reaction can continue. It is presumed that the cyclic olefins can be polymerized more efficiently because the steric barrier is low against the cyclic olefins that are coordinated and inserted while exhibiting moderate steric effects.

( Method for producing transition metal compound (A))
The transition metal compound (A) can be produced by combining known methods. An example of a representative synthesis route of the transition metal compound (A-1) among the transition metal compounds (A) is shown below, but the production method is not particularly limited. As a manufacturing method, for example,
A pyrazolato compound (a-1) represented by the following general formula [a-1] and an alkyllithium (a-2) are reacted to form an anion body (a-1) of the pyrazolato compound represented by the following general formula [a-3]. A step (1-1) for producing a-3), and reacting the anion (a-3) with a compound (a-4) represented by the following general formula [a-4] to obtain Step (1-2) for producing a transition metal compound (A-1) represented by [A-1]
A manufacturing method comprising:

〔式［a-1］、式［a-3］および式［a-4］中、Ｒ¹～Ｒ⁸、Ｍ、Ｘおよびｎは、それぞれ式［A-1］中のＲ¹～Ｒ⁸、Ｍ、Ｘおよびｎと同義である。〕

[In formula [a-1], formula [a-3] and formula [a-4], R ¹ to R ⁸ , M, X and n are respectively R ¹ to R ⁸ in formula [A-1] , M, X and n. ]

First, various cyclopentadiene compounds can be produced by known methods, and the production method is not particularly limited. For example, JP-A-2000-136195, JP-A-2009-24019, Japanese Patent No. 3674509, WO1998/015510, WO2000/049029, "J. Organomet. Chem. 1999, 577, 211." "J. Organomet. Chem. 2003, 677, 133.", "Organometallics 1988, 7, 1828.", "Organometallics 1996, 15, 4857." 2004, 126, 2089.”, “Macromol. Chem. Phys. 2004, 205, 2275.”, “Org. Lett. Rev. 1992, 92, 965., Science 2012, 338, 504., Organometallics 2006, 25, 3824., and the like.

Methods for deriving compound (a-4) from various cyclopentadiene compounds are known, and the production method is not particularly limited. As known production methods, for example, "Organometallics 2006, 25, 631.", "Macromolecules 2000, 33, 2796.", "J. Organomet. Chem. 1995, 489, 195." , 118, 1906.” and “Organometallics 2006, 25, 3824.”.

The pyrazolato compound (a-1) can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include "J. Org. Chem. 1985, 50, 4736.", "Inorg. Chem. 2012, 51, 150." be done.

The anion form (a-3) of the pyrazolato compound can be produced by a known method, and the production method is not particularly limited. Synth. Catal. 2005, 347, 463.”, “Organometallics, 1997, 16, 2709.”, “Organometallics, 2000, 19.” , 2707.” and “Inorg. Chem. 2009, 48, 5011.”.

The transition metal compound (A-1) can be produced by a known method using a compound (a-4) represented by general formula [a-4] and an anion (a-3) of a pyrazolato compound. . However, at this time, the anion form (a-3) of the pyrazolato compound and the compound (a-4) are selected in a specific combination so as to correspond to the structure of the desired transition metal compound (A-1). In order to react the two, known production methods can be referred to. Examples of such production methods include the method for producing the anion form of the pyrazolato compound, as well as "Macromolecules, 2011, 44, 1986." and the manufacturing method described in.

<Compound (B)>
《Organometallic compounds (B-1》
The organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") includes, for example, an organoaluminum compound (B-1a) represented by general formula (B-1a), general formula ( Complex alkylation product (B-1b) of Group 1 metal and aluminum represented by B-1b), dialkyl compound of Group 2 or Group 12 metal represented by general formula (B-1c) (B- Organometallic compounds of groups 1, 2 and 12, 13, such as 1c).

(B-1a): _{RamAl ( ORb} ) _nHpXq
In formula (B-1a), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is 0<m≦3, n is 0≦n<3, p is 0≦p<3, q is a number satisfying 0≦q<3, and m+n+p+q=3. Examples of the organoaluminum compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminums.

(B-1b): _M2AlRa4
In formula (B-1b), M2 is Li, Na or K, and Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Complex alkylated products (B-1b) include, for example, LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

(B-1c): RaRbM3
In formula (B-1c), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M3 is Mg, Zn or Cd. Examples of the compound (B-1c) include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, di-n-butylzinc and diphenylzinc.
Among the organometallic compounds (B-1), the organoaluminum compound (B-1a) is preferred.
The organometallic compound (B-1) may be used singly or in combination of two or more.

<<Organoaluminum oxy compound (B-2)>>
As the organoaluminumoxy compound (B-2) (hereinafter also referred to as "component (B-2)"), conventionally known aluminoxanes can be used as they are. Specifically, the following general formula [B2-1]

および／または下記一般式［B2-2］

and/or the following general formula [B2-2]

（式中、Ｒは炭素数１から１０の炭化水素基、ｎは2以上の整数を示す）
で表わされる化合物、特開平2-78687号公報、特開平2-167305号公報に記載れたベンゼン不溶性の有機アルミニウムオキシ化合物、特開平3-103407号公報に記載されている二種類以上のアルキル基を有するアルミノキサンが挙げられる。

(Wherein, R is a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 2 or more)
A compound represented by JP-A-2-78687, a benzene-insoluble organoaluminum oxy compound described in JP-A-2-167305, two or more alkyl groups described in JP-A-3-103407 aluminoxanes having

Examples of the organoaluminumoxy compound (B-2) include modified methylaluminoxane represented by the following general formula [B2-3].

（式中、Ｒは炭素数１から１０の炭化水素基、ｍおよびｎはそれぞれ独立に２以上の整数を示す。）

(Wherein, R is a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer of 2 or more.)

The modified methylaluminoxanes are prepared using trimethylaluminum and alkylaluminums other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by methods set forth in US Pat. No. 4,960,878 and US Pat. No. 5,041,584.

Furthermore, the organoaluminumoxy compound (B-2) may also include an organoaluminumoxy compound containing boron represented by the following general formula [B2-4].

（式中、Ｒ^cは炭素数１から１０の炭化水素基を示す。Ｒ^dは、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子または炭素数１から１０の炭化水素基を示す。）

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d , which may be the same or different, represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms. )

As the organoaluminumoxy compound (B-2), methylaluminoxane, which is commercially available and readily available, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferable. Among these, MMAO with improved solubility in various solvents and improved storage stability is particularly preferred.

<<Compound (B-3) that forms an ion pair by reacting with transition metal complex (A)>>
As the compound (B-3) (hereinafter also referred to as “ionic compound (B-3)” or “component (B-3)”) that reacts with the transition metal complex (A) to form an ion pair, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, etc. Lewis acids, ionic compounds, borane compounds and carborane compounds described in . In addition, heteropolycompounds and isopolycompounds may also be mentioned. However, the aforementioned (B-2) organoaluminumoxy compound is not included.

The ionic compound (B-3) preferably includes a boron compound represented by the following general formula [B3-1].

式中、Ｒ^e+としては、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などが挙げられる。Ｒ^fからＲⁱは、互いに同一でも異なっていてもよく、炭素数１から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、好ましくは置換アリール基である。

In the formula, R ^e+ includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^f to R ⁱ may be the same or different, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. , preferably a substituted aryl group.

Examples of the boron compound represented by the general formula [B3-1] include those described in [0133] to [0144] of WO 2015/122414.
The ionic compound (B-3) may be used alone or in combination of two or more.

<Compound (C)>
The olefin polymerization catalyst of the present invention, in addition to the transition metal compound (A) and the compound (B), is at least one selected from the group consisting of an alcohol compound (C-1) and a phenol compound (C-2). as an essential component.

Examples of the alcohol compound (C-1) include alcohol compounds having 1 to 20 carbon atoms. In such an alcohol compound, the portion other than the hydroxy group in the molecule is preferably composed only of carbon atoms and hydrogen atoms. Specific examples of such compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, Ethanol is preferred.

Examples of the phenol compound (C-2) include phenol compounds having 6 to 20 carbon atoms. In such a phenol compound, the portion other than the hydroxy group in the molecule is preferably composed only of carbon atoms and hydrogen atoms. Specific examples of such compounds include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 4-nonylphenol, 4-hexylphenol, 4-isopropylphenol, 3,5-dimethylphenol, 2,3,6-trimethylphenol, 2,3,5-trimethylphenol, 2,4-di-tert-butylphenol, 2-isopropylphenol, 2-tert-butylphenol, p-dodecylphenol , 2-phenylphenol, p-phenylphenol, preferably 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl -4-methylphenol is particularly preferred.

It is generally known that methylaluminoxanes used as cocatalysts contain trialkylaluminum species. Since the compound (C) is expected to have the effect of deactivating trialkylaluminum species known to act as polymerization inhibitors and chain transfer agents, the olefin polymerization catalyst of the present invention containing the compound (C) When olefin polymerization is carried out in the presence of, a highly active, high-molecular-weight olefin polymer can be produced, and further according to one aspect of the present invention, an α-olefin/cyclic olefin copolymer with high copolymerizability It is speculated that coalescence can be produced.
The olefin polymerization catalyst of the present invention may further contain (D) a carrier and may further contain (E) an organic compound, if necessary.

(Carrier (D))
The carrier (D) is an inorganic or organic compound, is a granular or fine particle solid, and is conventionally used in olefin polymerization using a transition metal complex and a carrier as catalyst components. Those described in [0110] to [0122] of 2011-122146 can be used.

(Organic compound component (E))
As a component of the olefin polymerization catalyst, an organic compound component (E) may be used as necessary. The organic compound component (E) is used for the purpose of improving polymerization performance and physical properties of the produced polymer. Examples of the organic compound component (E) include carboxylic acids, phosphorus compounds, amides, polyethers and sulfonates.

The olefin polymerization catalyst of the present invention is useful as a catalyst for polymerizing olefins, for example, as a catalyst for copolymerizing an α-olefin (Z-1) and a cyclic olefin (Z-2) which will be described later.

[Method for producing olefin polymer]
The first method for producing an olefin polymer of the present invention is characterized by polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst of the present invention.

In the method for producing an olefin polymer of the present invention, an olefin homopolymer may be produced by polymerizing one kind of olefin, or an olefin copolymer may be produced by copolymerizing two or more kinds of olefins. good. In the present specification, polymerization and copolymerization are also referred to as "polymerization" without particular distinction, and olefin homopolymers and olefin copolymers are also referred to as "olefin polymers" without particular distinction.

In polymerization, the method of using each component constituting the catalyst for olefin polymerization of the present invention and the order of addition to the polymerization vessel are arbitrarily selected, but the following methods are exemplified. Hereinafter, the transition metal complex (A), compound (B), compound (C), carrier (D) and organic compound component (E) are also referred to as "components (A) to (E)" respectively.
(1) A method of adding component (A), component (B) and component (C) to a polymerization vessel in any order. (2) A method in which a catalyst component in which component (A) is supported on component (D), component (B), and component (C) are added in any order to a polymerization vessel.
(3) A method of adding the catalyst component in which the component (B) is supported on the component (D), the component (A), and the component (C) in an arbitrary order to the polymerization vessel.
(4) A method of adding the catalyst component in which the component (C) is supported on the component (D), the component (A), and the component (B) to the polymerization vessel in any order.
(5) A method of adding the catalyst component in which the component (A) and the component (B) are supported on the component (D) and the component (C) in an arbitrary order to the polymerization reactor.
(6) A method of adding a catalyst component in which component (A), component (B) and component (C) are supported on component (D) to a polymerization reactor.

In each of the above methods, component (E) may be added at any stage.
In each of the above methods, at least two of each catalyst component may be pre-contacted.
In each of the above methods (3) and (4) in which component (B) is supported, the unsupported component (B) may be added in any order, if desired. In this case, the components (B) may be the same or different. Further, the solid catalyst component in which the component (A) is supported on the component (D), and the solid catalyst component in which the component (A) and the component (B) are supported on the component (D), even if the olefin is prepolymerized A further catalyst component may be supported on the prepolymerized solid catalyst component.

Olefin polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Examples of inert hydrocarbon media 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. aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. The inert hydrocarbon medium may be used singly or in combination of two or more.

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, the transition metal compound (A) is generally 1×10 ⁻¹² to 1×10 ⁻² mol, preferably 1 mol per liter of reaction volume. It is used in an amount such that it becomes ×10 ^-10 to 1×10 ^-3 mol.

The organometallic compound (B-1) has a molar ratio [(B-1)/M] between the organometallic compound (B-1) and all the transition metal atoms (M) in the transition metal compound (A). It is used in an amount of 0.01 to 50,000, preferably 0.05 to 10,000.

The organoaluminumoxy compound (B-2) has a molar ratio of the aluminum atoms in the organoaluminumoxy compound (B-2) to the total transition metal (M) in the transition metal compound (A) [(B-2) /M] is usually 10 to 5,000, preferably 20 to 2,000.

The ionized ionic compound (B-3) has a molar ratio [(B-3)/M] between the ionized ionic compound (B-3) and the transition metal atom (M) in the transition metal compound (A). , usually from 1 to 10,000, preferably from 1 to 5,000.

The compound (C) is used in an amount such that the molar ratio of the compound (C) to the organometallic compound (B-1) is generally 0.1-10, preferably 0.25-2.
The molar ratio of the compound (C) to the organoaluminumoxy compound (B-2) relative to the aluminum atoms in the organoaluminumoxy compound (B-2) is generally 0.1 to 10, preferably 0.25 to 2 is used.

The compound (C) is used in an amount such that the molar ratio of the compound (C) to the ionic compound (B-3) is generally 0.1-100, preferably 0.2-5.
When the carrier (D) is used, the weight ratio [(A)/(D)] of the transition metal compound (A) and the carrier (D) is preferably 0.0001 to 1, more preferably 0.0005 to 0. .5, more preferably 0.001 to 0.1.

In the production method of the present invention, the polymerization temperature in the polymerization step is usually −50 to +200° C., preferably 0 to 180° C.; 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 in any of a batch system, a semi-continuous system and a continuous system. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen to exist in the polymerization system, by changing the polymerization temperature, or by adjusting the amount of compound (B) used. When hydrogen is added, the appropriate amount thereof is about 0.001 to 5,000 NL per 1 kg of the olefin polymer produced.

Examples of olefins to be subjected to the polymerization reaction in the method for producing an olefin polymer of the present invention include linear or branched α-olefins and cyclic olefins.
The olefin polymerization catalyst of the present invention can be preferably used for copolymerization (addition polymerization) of linear or branched α-olefins and cyclic olefins, particularly copolymerization of olefins and cyclic olefins. Furthermore, it can be preferably used for copolymerization of ethylene and cyclic olefins. In particular, the embodiment using the transition metal compound (A-1) is preferably used for the copolymerization of olefins, especially ethylene and cyclic olefins.

(Z-1) Linear or branched α-olefin having 2 to 30 carbon atoms As the linear or branched α-olefin having 2 to 30 carbon atoms, linear or branched α-olefin having 2 to 30 carbon atoms Examples include α-olefins (Z-1).
The α-olefin (Z-1) preferably has 2 to 20 carbon atoms.
Specific examples of the α-olefin (Z-1) include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

(Z-2) at least one cyclic selected from the group consisting of compounds represented by general formula [ZI], general formula [Z-II], general formula [Z-III] or general formula [Z-IV] Olefin As the cyclic olefin, at least one selected from the group consisting of compounds represented by the following general formula [ZI], general formula [Z-II], general formula [Z-III] or general formula [Z-IV] cyclic olefins (Z-2).

〔式［Z-I］中、ｕは０または１であり、
ｖは０または正の整数であり、
ｗは０または１であり、
Ｒ⁶¹～Ｒ⁷⁸ならびにＲ^a1およびＲ^b1は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁷⁵～Ｒ⁷⁸は、互いに結合して単環または、多環を形成していてもよく、かつ該単環または多環が二重結合を有していてもよく、またＲ⁷⁵とＲ⁷⁶とで、またはＲ⁷⁷とＲ⁷⁸とでアルキリデン基を形成していてもよい。〕

[In the formula [ZI], u is 0 or 1,
v is 0 or a positive integer;
w is 0 or 1;
R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and R ⁷⁵ to R ⁷⁸ are bonded together to form a monocyclic or polycyclic ring; and the monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. . ]

〔式［Z-II］中、ｘおよびｄは０または１以上の整数であり、
ｙおよびｚは０、１または２であり、
Ｒ⁸¹～Ｒ⁹⁹は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁸⁹およびＲ⁹⁰が結合している炭素原子と、Ｒ⁹³が結合している炭素原子またはＲ⁹¹が結合している炭素原子とは、直接あるいは炭素原子数１～３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ⁹⁵とＲ⁹²またはＲ⁹⁵とＲ⁹⁹とは互いに結合して単環または多環の芳香族環を形成していてもよい。〕

[In the formula [Z-II], x and d are 0 or an integer of 1 or more,
y and z are 0, 1 or 2;
R ⁸¹ to R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, the carbon atom to which R ⁹³ is bonded, or R ⁹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ]

〔式［Z-III］中、Ｒ¹⁰⁰およびＲ¹⁰¹は、それぞれ独立に水素原子または炭素原子数１～５の炭化水素基であり、ｆは１≦ｆ≦１８である。〕

[In formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18. ]

〔一般式［Z-IV］中、ｘは０または１以上の整数であり、
Ｒ¹¹¹～Ｒ¹¹⁸は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、
Ｒ¹²¹～Ｒ¹²⁴は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、隣接する２つの基は互いに結合し単環または複環の芳香族環を形成していてもよい。〕
以下、一般式［Z-I］、一般式［Z-II］、一般式［Z-III］、および一般式［Z-IV］について詳説する。

[In the general formula [Z-IV], x is an integer of 0 or 1 or more,
R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group;
R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ]
General formula [ZI], general formula [Z-II], general formula [Z-III], and general formula [Z-IV] are described in detail below.

<<General formula [ZI]>>
In formula [ZI], u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. When w is 1, the ring represented by w is a 6-membered ring, and when w is 0, the ring is a 5-membered ring.

R ⁶¹ to R ⁷⁸ , R ^a1 and R ^b1 may be the same or different and each is a hydrogen atom, a halogen atom or a hydrocarbon group.
Here, a halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl. 20 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as vinyl, allyl and isopropenyl; carbon atoms such as ethynyl and propargyl 2 to 30, preferably 2 to 20 linear or branched alkynyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, norbornyl, tetracyclododecyl, etc., having 3 to 3 carbon atoms 30, preferably 3 to 20 cycloalkyl groups; cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as; .

Hydrogen atoms in the above hydrocarbon groups may be substituted with halogens, and examples thereof include monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, chlorophenyl, and the like. 1 to 30, preferably 1 to 20 halogenated alkyl or halogenated aryl groups.

In addition, the above hydrocarbon group may be substituted with other hydrocarbon groups, such as aryl-substituted alkyl groups such as benzyl and cumyl.
Furthermore, the above hydrocarbon group is a heterocyclic compound residue; Containing group; amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group and ammonium salt boron-containing groups such as boranediyl, boranetriyl, diboranyl; mercapto, thioester, dithioester, alkylthio, arylthio, thioacyl, thioether, thiocyanate, Sulfur-containing groups such as isocyanate group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, sulfenyl group; phosphide group, phosphoryl group, thiophosphoryl group, phosphato may have phosphorus-containing groups such as groups, silicon-containing groups; germanium-containing groups; or tin-containing groups.

The above hydrocarbon groups are particularly those having 1 to 30 carbon atoms, preferably 1, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl and n-hexyl. cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, tetracyclododecyl, etc., having 3 to 30 carbon atoms, preferably 3 to 20 cyclo Alkyl groups; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl; these aryl groups have halogen atoms, preferably 1 to 30 carbon atoms, A substituted aryl group substituted with 1 to 5 substituents such as an alkyl group or alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, or an aryloxy group is preferred.

Furthermore, in the above general formula [ZI], R ⁷⁵ and R ⁷⁶ , R ⁷⁷ and R ⁷⁸ , R ⁷⁵ and R ⁷⁷ , R ⁷⁶ and R ⁷⁸ , R ⁷⁵ and R ⁷⁸ , or Each of R ⁷⁶ and R ⁷⁷ may be combined (together with each other) to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group thus formed may be a double bond may have Specific examples of the monocyclic or polycyclic ring formed here include the following.

なお、上記例示において、１または２の番号を付した炭素原子は、上記一般式（Ｉ）においてそれぞれＲ⁷⁵（Ｒ⁷⁶）またはＲ⁷⁷（Ｒ⁷⁸）が結合している炭素原子を表す。

In the above examples, the carbon atoms numbered 1 or 2 represent the carbon atoms to which R ⁷⁵ (R ⁷⁶ ) or R ⁷⁷ (R ⁷⁸ ) is bonded in the general formula (I).

Also, R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include ethylidene, propylidene, isopropylidene and the like.

《General formula [Z-II]》
In formula [Z-II], x and d are 0 or positive integers; y and z are 0, 1 or 2;

Also, R ⁸¹ to R ⁹⁹ may be the same or different, and are a hydrogen atom, a halogen atom, or a hydrocarbon group.
As the halogen atom and hydrocarbon group, the same halogen atom and hydrocarbon group in the above formula [ZI] can be exemplified.

Here, the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms may be connected via That is, when the above two carbon atoms are bonded through an alkylene group, R ⁸⁹ and R ⁹³ or R ⁹⁰ and R ⁹¹ jointly form a methylene group (--CH ₂ --), an ethylene group (--CH ₂ CH ₂ --) or a propylene group (--CH ₂ CH ₂ CH ₂ --).

Furthermore, when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. Specifically, when y=z=0, the following aromatic rings formed by R ⁹⁵ and R ⁹² are exemplified.

ここで、ｌは上記一般式［Z-II］におけるｄと同じである。

Here, l is the same as d in the general formula [Z-II].

<<General formula [Z-III]>>
In formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ , which may be the same or different, are a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≤ f ≤ 18. .

The hydrocarbon group having 1 to 5 carbon atoms is preferably an alkyl group, a halogenated alkyl group or a cycloalkyl group. Specific examples thereof are the same as the specific examples of R ⁶¹ to R ⁷⁸ in formula [ZI] above.

<<General formula [Z-IV]>>
In general formula [Z-IV], x is 0 or an integer of 1 or more.
R ¹¹¹ to R ¹¹⁸ and R ¹²¹ to R ¹²⁴ are selected from hydrogen atoms, halogen atoms and hydrocarbon groups, and may be the same or different.

As the halogen atom and hydrocarbon group, the same halogen atom and hydrocarbon group in the above formula [ZI] can be exemplified.
Adjacent two groups of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Among these, specific examples of the cyclic olefin in which R ¹²¹ and R ¹²² combine to form an aromatic ring include the following structures.

また、Ｒ¹²²とＲ¹²³が結合して芳香族環が形成される環状オレフィンとして具体的には、以下のような構造が挙げられる。

Specific examples of the cyclic olefin in which R ¹²² and R ¹²³ combine to form an aromatic ring include the following structures.

また、Ｒ¹²¹とＲ¹²²、Ｒ¹²³とＲ¹²⁴が結合して芳香族環が形成される環状オレフィンとして具体的には、以下のような構造が挙げられる。

Specific examples of cyclic olefins in which R ¹²¹ and R ¹²² and R ¹²³ and R ¹²⁴ combine to form an aromatic ring include the following structures.

これらの芳香族環上にハロゲン原子、アルキル基、およびアリール基から選ばれる置換基が置換された環状オレフィンも例として挙げられる。

Cyclic olefins in which substituents selected from halogen atoms, alkyl groups and aryl groups are substituted on these aromatic rings are also exemplified.

Specific examples of the cyclic olefin represented by the general formula [ZI], [Z-II], [Z-III] or [Z-IV] include:
Bicyclo-2-heptene and its derivatives (bicyclohept-2-ene and its derivatives), tricyclo-3-decene and its derivatives, tricyclo-3-undecene and its derivatives, tetracyclo-3-dodecene and its derivatives, pentacyclo-4- pentadecene and its derivatives, pentacyclopentadecadiene and its derivatives, pentacyclo-3-pentadecadiene and its derivatives, pentacyclo-4-hexadecene and its derivatives, pentacyclo-3-hexadecene and its derivatives, hexacyclo-4-heptadecene and its derivatives, Heptacyclo-5-eicosene and its derivatives, heptacyclo-4-eicosene and its derivatives, heptacyclo-5-heneicosene and its derivatives, octacyclo-5-docosene and its derivatives, nonacyclo-5-pentacosene and its derivatives, nonacyclo-6-hexacosene and derivatives thereof, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a,9a-tetrahydrofluorene and its derivatives, 1,4-methano-1,4,4a,5,10,10a-hexa Hydroanthracene and its derivatives, cycloalkylene having 3 to 20 carbon atoms and its derivatives, benzonorbornadiene and its derivatives, 1,4-dihydro-1,4-methanoanthracene and its derivatives and the like.

More specific examples of the cyclic olefins represented by the general formulas [Z-I], [Z-II], [Z-III] and [Z-IV] are shown below.

cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, cycloeicosene and the like.
Benzonorbornadiene and its derivatives

１，４－ジヒドロ－１，４－メタノアントラセンおよびその誘導体

1,4-dihydro-1,4-methanoanthracene and its derivatives

これらの中では、ビシクロ［２．２．１］－２－ヘプテンおよびその誘導体、テトラシクロ［４．４．０．1^2,5．１^7,10］－３－ドデセンおよびその誘導体、ベンゾノルボルナジエンおよびその誘導体、１，４－ジヒドロ－１，４－メタノアントラセンおよびその誘導体、ならびにペンタシクロ［７．４．０．１^2,5．１^9,12．０^8,13］－３－ペンタデセンおよびその誘導体が好ましく、特にビシクロ［２．２．１］－２－ヘプテン、テトラシクロ［４．４．０．１^2,5．１^7,10］－３－ドデセン、ベンゾノルボルナジエン、１，４－ジヒドロ－１，４－メタノアントラセン、および１，４－メタノ－１，４，４ａ，９ａ－テトラヒドロフルオレンが好ましい。

Among these are bicyclo[2.2.1]-2-heptene and its derivatives, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene and its derivatives, benzonorbornadiene and its derivatives, 1,4-dihydro-1,4-methanoanthracene and its derivatives, and pentacyclo[7.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ]-3-pentadecenes and their derivatives are preferred, especially bicyclo[2.2.1]-2-heptene, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, benzonorbornadiene, 1,4-dihydro-1,4-methanoanthracene, and 1,4-methano-1,4,4a,9a-tetrahydrofluorene are preferred.

Cyclic olefins (Z-2) represented by these general formulas [ZI], [Z-II], [Z-III] or [Z-IV] may be used singly or in combination of two or more. They may be used together.
Further examples of olefins subjected to the polymerization reaction in the method for producing an olefin polymer of the present invention include conjugated/nonconjugated polyenes and vinylcyclohexane.

The conjugated/nonconjugated polyenes include cyclic or chain hydrocarbons having 4 to 30, preferably 4 to 20 carbon atoms and two or more double bonds. Specific examples include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene butadiene, isoprene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, etc. JP-A-2011-122146 and the compounds exemplified in [0211] of

In the method for producing an olefin polymer of the present invention, a polymerizable compound other than an olefin may be polymerized together with the olefin described above. Examples of such polymerizable compounds include a polar group and a polymerizable unsaturated bond. aromatic vinyl compounds, and functional group-containing styrene derivatives.

Specific examples of the compound having a polar group and a polymerizable unsaturated bond include compounds exemplified as unsaturated hydrocarbons having a polar group in [0208] to [0211] of JP-A-2011-122146.

Specific examples of aromatic vinyl compounds and functional group-containing styrene derivatives include compounds exemplified in [0211] of JP-A-2011-122146.
A preferred embodiment of the production method of the present invention includes an embodiment in which the α-olefin (Z-1) and the cyclic olefin (Z-2) are copolymerized. In this embodiment, the α-olefin (Z-1) is preferably ethylene, and the cyclic olefin (Z-2) is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene is preferred.

When the α-olefin (Z-1) and the cyclic olefin (Z-2) are copolymerized, the pressure of the α-olefin (Z-1) and the concentration of the cyclic olefin (Z-2) can be arbitrarily set. It can be set and is not particularly limited. The pressure of the α-olefin (Z-1) is preferably the above polymerization pressure, and the concentration of the cyclic olefin (Z-2) is 0.001 to 100M, preferably 0.01 to 10M, more preferably 0.1 to 1M.

[Second invention]
[Transition metal compound]
The transition metal compound according to the second aspect of the present invention (hereinafter also referred to as “transition metal compound (A-1′)”) is represented by the following general formula [A-1′-1] or [A-1′-2] expressed.

［遷移金属化合物（Ａ－１’－１）］
まず、式［A-1'-1］で表される遷移金属化合物（以下「遷移金属化合物（Ａ－１’－１）」ともいう。）について説明する。

[Transition metal compound (A-1'-1)]
First, the transition metal compound represented by the formula [A-1'-1] (hereinafter also referred to as "transition metal compound (A-1'-1)") will be described.

《M》
In formula [A-1], M represents a titanium atom, a zirconium atom, or a hafnium atom, preferably a titanium atom or a zirconium atom, more preferably a titanium atom.

<<R ¹ to R ⁵ and R ⁸ >>
In formula [A-1], R ¹ to R ⁵ and R ⁸ are each independently a hydrogen atom and have 1 to 2 carbon atoms.
0 hydrocarbon groups, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, or phosphorus-containing groups, and adjacent groups among R ¹ to R ⁵ are bonded to each other; may form a ring.

Specific embodiments of R ¹ to R ⁵ and R ⁸ are specific examples of R ¹ to R ⁸ in formula [A-1] representing the transition metal compound (A-1) that can be used in the first aspect of the present invention. Examples include those exemplified as specific embodiments.

As R ¹ ,
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-
linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as butyl, neopentyl, n-hexyl;
aryl groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl;
Hydrocarbon groups having 1 to 20 carbon atoms such as substituted aryl groups in which one or more hydrogen atoms of these aryl groups are substituted with halogen atoms, alkyl groups, alkoxy groups, aryl groups or aryloxy groups are preferred.
Hydrogen atoms are particularly preferred as R ² to R ⁵ .

<< ^R6 and ^R7 >>
In formula [A-1'-1], R ⁶ and R ⁷ are each independently a halogen atom or a halogen-containing group, preferably a halogen-containing group.

Preferred examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the halogen-containing group include trifluoromethyl, pentafluoroethyl, 1,1,1,3,3,3-hexafluoro-2-propyl, nonafluoro-tert-butyl, pentafluorophenyl, chlorophenyl, and the like. 1 to 20, preferably 1 to 10 halogenated hydrocarbon groups, more preferably a trifluoromethyl group.

《n》
In formula [A-1'-1], n is an integer of 1 to 4, and depending on the valence of M and the type of X, the transition metal compound (A-1'-1) as a whole is electrically neutral. selected to be sexual.

《X》
In formula [A-1'-1], each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, A boron-containing group, an aluminum-containing group, or a diene-based divalent derivative group.

Specific embodiments of X include those exemplified as specific embodiments of X in formula [A-1] representing the transition metal compound (A-1) that can be used in the first aspect of the present invention.
Specific examples of the transition metal compound (A-1'-1) include compounds represented by the following formula.

遷移金属化合物（Ａ－１’－１）の存在下でオレフィンを重合すると、高活性で、高分子量のオレフィン重合体を製造することができる。その理由としては、必ずしも定かではないが、ピラゾラト配位子に存在する電子吸引性のハロゲン原子またはハロゲン含有基によって、中心金属のカチオン性が高まり、結果、中心金属により強くオレフィンが配位することで重合が進行し易くなるからであると推測される。

Polymerizing an olefin in the presence of a transition metal compound (A-1'-1) can produce a highly active, high-molecular-weight olefin polymer. The reason for this is not entirely clear, but the electron-withdrawing halogen atom or halogen-containing group present in the pyrazolato ligand increases the cationicity of the central metal, resulting in stronger olefin coordination to the central metal. It is presumed that this is because the polymerization is likely to proceed at

[Transition metal compound (A-1′-2)]
Next, the transition metal compound represented by the formula [A-1'-2] (hereinafter also referred to as "transition metal compound (A-1'-2)") will be described.

《M》
In formula [A-1'-2], M represents a titanium atom, a zirconium atom, or a hafnium atom, preferably a titanium atom or a zirconium atom, more preferably a titanium atom.

《 ^R11 ～ ^R20 》
In formula [A-1'-2], R ¹¹ to R ²⁰ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, nitrogen It may be a containing group, a sulfur-containing group, or a phosphorus-containing group, and adjacent groups among these may be bonded to each other to form a ring.

Specific embodiments of R ¹¹ to R ²⁰ include specific embodiments of R ¹ to R ⁸ in formula [A-1] representing the transition metal compound (A-1) that can be used in the first aspect of the present invention. Examples are given.

Examples of the indenyl moiety having a ring formed by bonding adjacent groups among R ¹¹ to R ²⁰ include the following ring structures, and the ring structure may further have a substituent. good.

Ｒ¹¹～Ｒ¹⁷としては、特に、水素原子が好ましい。
Ｒ¹⁸およびＲ¹⁹としては、特に、炭素原子数１～２０の炭化水素基が好ましい。

Hydrogen atoms are particularly preferred as R ¹¹ to R ¹⁷ .
Hydrocarbon groups having 1 to 20 carbon atoms are particularly preferred as R ¹⁸ and R ¹⁹ .

《n》
In formula [A-1'-2], n is an integer of 1 to 4, and depending on the valence of M and the type of X, the transition metal compound (A-1'-2) as a whole is electrically neutral. selected to be sexual.

《X》
In formula [A-1'-2], each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, A boron-containing group, an aluminum-containing group, or a diene-based divalent derivative group.

Specific embodiments of X are exemplified as specific embodiments of X in formula [A-1] in formula [A-1] representing the transition metal compound (A-1) that can be used in the first invention described above. The following are listed.
Specific examples of the transition metal compound (A-1'-2) include compounds represented by the following formula.

By polymerizing an α-olefin and a cyclic olefin in the presence of a transition metal compound (A-1′-2), an α-olefin/cyclic olefin copolymer can be produced with high copolymerizability (i.e., copolymer Many structural units derived from cyclic olefins are contained in the polymer.). The reason for this is not necessarily clear, but it is thought that the planarity of the indenyl ligand is involved, and a moderate steric effect to maintain ion separation with the co-catalyst so that the polymerization reaction can continue. It is presumed that the cyclic olefins can be polymerized more efficiently because the steric barrier is low against the cyclic olefins that coordinatively insert.

[Method for producing transition metal compound (A-1′)]
The transition metal compound (A-1′) according to the second invention can be produced by the above-described method for producing the transition metal compound (A-1) that can be used in the first invention.

[Catalyst for olefin polymerization]
The polymerization catalyst according to the second aspect of the present invention is
(A-1′) the transition metal compound according to the second aspect of the present invention described above;
(B) (B-1) an organometallic compound,
(B-2) an organoaluminumoxy compound, and (B-3) at least one compound selected from the group consisting of compounds that form an ion pair by reacting with the transition metal compound (A-1′) is characterized by
The olefin polymerization catalyst of the present invention may further contain (D) a carrier and may further contain (E) an organic compound, if necessary.

<Compound (B)>
The details of the compound (B) are as explained in the column of the explanation of the compound (B) contained in the catalyst for olefin polymerization according to the first aspect of the present invention.

<Carrier (D)>
The details of the carrier (D) are as explained in the column for explaining the carrier (D) contained in the catalyst for olefin polymerization according to the first aspect of the present invention.

<Organic compound component (E)>
The organic compound component (E) is used for the purpose of improving polymerization performance and physical properties of the produced polymer. Examples of the organic compound component (E) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers and sulfonates.

[Method for producing olefin polymer]
A method for producing an olefin polymer according to the second aspect of the present invention is characterized by polymerizing an olefin in the presence of the catalyst for olefin polymerization according to the second aspect of the present invention.

In the method for producing an olefin polymer according to the second aspect of the present invention, an olefin homopolymer may be produced by polymerizing one kind of olefin, or two or more kinds of olefins may be copolymerized to produce an olefin copolymer. may be manufactured. In the present specification, polymerization and copolymerization are also referred to as "polymerization" without particular distinction, and olefin homopolymers and olefin copolymers are also referred to as "olefin polymers" without particular distinction.

In polymerization, the method of using each component constituting the catalyst for olefin polymerization of the present invention and the order of addition to the polymerization vessel are arbitrarily selected, but the following methods are exemplified. Hereinafter, the transition metal complex (A-1'), compound (B), carrier (D) and organic compound component (E) are also referred to as "components (A-1') to (E)" respectively.
(1) A method of adding component (A-1') alone to a polymerization vessel.
(2) A method of adding component (A-1') and component (B) in any order to a polymerization vessel.
(3) A method of adding the catalyst component in which the component (A-1') is supported on the component (D) and the component (B) in any order to the polymerization vessel.
(4) A method of adding the catalyst component in which the component (B) is supported on the component (D) and the component (A-1') in an arbitrary order to the polymerization vessel.
(5) A method of adding a catalyst component in which component (A-1') and component (B) are supported on component (D) to a polymerization vessel.

In each of the above methods, component (E) may be added at any stage.
In each of the above methods, at least two of each catalyst component may be pre-contacted.
In the above methods (4) and (5) in which component (B) is supported, component (B) that is not supported may be added in any order, if desired. In this case, the components (B) may be the same or different. Further, the solid catalyst component in which the component (A-1′) is supported on the component (D) and the solid catalyst component in which the component (A-1′) and the component (B) are supported on the component (D) are It may be prepolymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

Olefin polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Examples of inert hydrocarbon media 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. aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. The inert hydrocarbon medium may be used singly or in combination of two or more.

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, the transition metal compound (A-1') is generally 10 ^-12 to 10 ^-2 mol, preferably 10 ^-2 mol, per liter of reaction volume. It is used in an amount such that it is ¹⁰ to 10 ^-3 mol.

The organometallic compound (B-1) is the molar ratio [(B-1)/M ] is usually 0.01 to 50,000, preferably 0.05 to 10,000.

The organoaluminumoxy compound (B-2) has a molar ratio of the aluminum atoms in the organoaluminumoxy compound (B-2) to the total transition metal (M) in the transition metal compound (A-1′) [(B -2)/M] is usually used in an amount of 10 to 5,000, preferably 20 to 2,000.

The ionized ionic compound (B-3) has a molar ratio of the ionized ionic compound (B-3) and the transition metal atom (M) in the transition metal compound (A-1′) [(B-3)/ M] is generally used in an amount of 1 to 10,000, preferably 1 to 5,000.

When the carrier (D) is used, the weight ratio [(A-1')/(D)] between the transition metal compound (A-1') and the carrier (D) is preferably 0.0001 to 1, more preferably is used in an amount of 0.0005 to 0.5, more preferably 0.001 to 0.1.

In the production method of the present invention, the polymerization temperature in the polymerization step is usually −50 to +200° C., preferably 0 to 180° C.; 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 in any of a batch system, a semi-continuous system and a continuous system. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen to exist in the polymerization system, by changing the polymerization temperature, or by adjusting the amount of compound (B) used. When hydrogen is added, the appropriate amount thereof is about 0.001 to 5,000 NL per 1 kg of the olefin polymer produced.

Examples of olefins to be subjected to the polymerization reaction in the method for producing an olefin polymer according to the second invention include linear or branched α-olefins and cyclic olefins. These details are as described in the description of the method for producing an olefin polymer according to the first aspect of the present invention.

[Third invention]
[Cyclic olefin copolymer]
The cyclic olefin copolymer according to the third aspect of the present invention is a copolymer of linear α-olefins such as ethylene, propylene, butene, hexene, octene, and decene, particularly ethylene, and a cyclic olefin, and has a specific It is characterized by having a chain structure. That is, the cyclic olefin copolymer according to the third aspect of the present invention is
Structural unit (z-1') represented by the following general formula [Z'], and the following general formula [Z-I'], general formula [Z-II'], general formula [Z-III'] or general Structural unit (z-2') represented by formula [Z-IV']
It is a cyclic olefin copolymer that contains and satisfies the following requirements [I].

〔式［Ｚ'］中、Ｒ³⁰⁰は水素原子又は炭素原子数１～２９の直鎖状または分岐状の炭化水素基を示す。〕

[In the formula [Z′], R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. ]

〔式［Z-I'］中、ｕは０または１であり、
ｖは０または正の整数であり、
ｕ＋ｖ≧１を満たし、
ｗは０または１であり、
Ｒ⁶¹～Ｒ⁷⁸ならびにＲ^a1およびＲ^b1は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁷⁵～Ｒ⁷⁸は、互いに結合して単環または、多環を形成していてもよく、かつ該単環または多環が二重結合を有していてもよく、またＲ⁷⁵とＲ⁷⁶とで、またはＲ⁷⁷とＲ⁷⁸とでアルキリデン基を形成していてもよい。〕

[In the formula [Z-I'], u is 0 or 1,
v is 0 or a positive integer;
satisfies u+v≧1,
w is 0 or 1;
R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and R ⁷⁵ to R ⁷⁸ are bonded together to form a monocyclic or polycyclic ring; and the monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. . ]

〔式［Z-II'］中、ｘおよびｄは０または１以上の整数であり、
ｙおよびｚは０、１または２であり、
Ｒ⁸¹～Ｒ⁹⁹は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁸⁹およびＲ⁹⁰が結合している炭素原子と、Ｒ⁹³が結合している炭素原子またはＲ⁹¹が結合している炭素原子とは、直接あるいは炭素原子数１～３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ⁹⁵とＲ⁹²またはＲ⁹⁵とＲ⁹⁹とは互いに結合して単環または多環の芳香族環を形成していてもよい。〕

[In the formula [Z-II'], x and d are 0 or an integer of 1 or more,
y and z are 0, 1 or 2;
R ⁸¹ to R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, the carbon atom to which R ⁹³ is bonded, or R ⁹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ]

〔式［Z-III'］中、Ｒ¹⁰⁰およびＲ¹⁰¹は、それぞれ独立に水素原子または炭素原子数１～５の炭化水素基であり、ｆは１≦ｆ≦１８である。〕

[In the formula [Z-III′], R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18. ]

〔一般式［Z-IV'］中、ｘは０または１以上の整数であり、
Ｒ¹¹¹～Ｒ¹¹⁸は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、
Ｒ¹²¹～Ｒ¹²⁴は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、隣接する２つの基は互いに結合し単環または複環の芳香族環を形成していてもよい。〕
要件［I］：前記構造単位（ｚ－２'）（以下「［ＣＯ］」とも記載する。）の二連子連鎖構造（以下「［ＣＯ］－［ＣＯ］構造」とも記載する。）の割合が０．５～３０モル％である。
〔ただし、前記構造単位（ｚ－１’）（以下「［Ｅ］」とも記載する。）の二連子連鎖構造（［以下「［Ｅ］－［Ｅ］構造」とも記載する。）の割合、前記構造単位（ｚ－１’）と前記構造単位（ｚ－２’）との連結構造（以下「［Ｅ］－［ＣＯ］構造」とも記載する。）の割合、および前記構造単位（ｚ－２’）の二連子連鎖構造（［ＣＯ］-［ＣＯ］構造）の割合の合計を１００モル％とする。〕

[In the general formula [Z-IV'], x is an integer of 0 or 1 or more,
R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group;
R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ]
Requirement [I]: The structure of the structural unit (z-2′) (hereinafter also referred to as “[CO]”) of the double chain structure (hereinafter also referred to as “[CO]-[CO] structure”) The proportion is 0.5 to 30 mol %.
[However, the ratio of the biad chain structure ([hereinafter also referred to as “[E]-[E] structure”) of the structural unit (z-1′) (hereinafter also referred to as “[E]”) , the ratio of the structural unit (z-1′) and the structural unit (z-2′) connected structure (hereinafter also referred to as “[E]-[CO] structure”), and the structural unit (z -2′), the total ratio of the biad chain structure ([CO]—[CO] structure) is 100 mol %. ]

The cyclic olefin copolymer according to the present invention can be produced, for example, by the following method.

(Method 1): In the method for producing an olefin polymer according to the first aspect of the present invention, the transition metal compound (A-1) is used as the transition metal compound (A), and the The above-described linear or branched α-olefin (Z-1) having 2 to 30 carbon atoms corresponding to the structural unit (z-1′), and the above general formula [Z-I′], The above general formula [Z-I] corresponding to the structural unit (z-2') represented by general formula [Z-II'], general formula [Z-III'] or general formula [Z-IV'] (However, u + v ≥ 1.) Addition polymerization with cyclic olefin (Z-2) represented by general formula [Z-II], general formula [Z-III] or general formula [Z-IV] .

(Method 2): In Method 1, at least one compound (C) selected from the group consisting of the alcohol compound (C-1) and the phenol compound (C-2) is added to the olefin polymerization catalyst. Polymerization is carried out without inclusions.

(Method 3): In the method for producing an olefin polymer according to the second aspect of the present invention, the above-mentioned number of carbon atoms corresponding to the structural unit (z−1′) represented by the general formula [Z′] 2 to 30 linear or branched α-olefins (Z-1) and the above general formula [Z-I'], general formula [Z-II'], general formula [Z-III'] or general The above-mentioned general formula [Z-I] (where u + v ≥ 1), general formula [Z-II], which corresponds to the structural unit (z-2') represented by formula [Z-IV'], It is subjected to addition polymerization with a cyclic olefin (Z-2) represented by general formula [Z-III] or general formula [Z-IV].

Ethylene is preferable as the α-olefin (Z-1).
Regarding the cyclic olefin (Z-2), a polycyclic structure having a substituent such as norbornene has an endo form and an exo form. In the present invention, the range of endo/exo ratio is not particularly limited.

The cyclic olefin copolymer of the present invention may contain structures other than the above-described structural units within a range that does not impair the object of the present invention. For example, structural units of known compounds such as structural units derived from diene compounds and structural units derived from aromatic vinyl compounds exemplified in the first invention may be included. The content of other structural units is preferably 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less.

<Requirement [I]>
The ratio of the biad chain structure ([CO]-[CO] structure) of the structural unit (z-2′) (that is, the structural unit derived from the cyclic olefin (Z-2)) is 0.5 to 30. in the mole % range. However, this value is the ratio of the double chain structure ([E]-[E] structure) of the structural unit (z-1 '), the structural unit (z-1 ') and the structural unit (z- 2′) and the ratio of the linked structure ([E]-[CO] structure) and the ratio of the double chain structure ([CO]-[CO] structure) of the structural unit (z-2′). is 100 mol %.

The lower limit of the ratio of the biad chain structure ([CO]-[CO] structure) of the structural unit (z-2′) is preferably 0.7 mol%, more preferably 1.0 mol%, and further It is preferably 2.0 mol %, particularly preferably 5.0 mol %, particularly preferably 7.0 mol %. On the other hand, the upper limit is preferably 28 mol%, more preferably 26 mol%, still more preferably 25 mol%, particularly preferably 23 mol%, and most preferably 21 mol%.

As far as the present inventors have investigated, (substances having a considerable amount of a chain structure of a norbornene skeleton (outside the scope of the claims of the present invention) and a structure derived from an olefin are known as cyclic olefins, but conventional olefins and a cyclic olefin copolymer, a cyclic olefin copolymer in which the [CO]-[CO] structure is observed in a considerable amount has not been reported, and the report of the glass transition temperature is also unknown.

Regarding copolymers of ethylene and norbornene, conventionally, there have been reported copolymers having a composition in which structural units derived from norbornene exceed 50 mol %. has a very high glass transition temperature. In addition, as can be seen from the results of Examples and Comparative Examples described later, the cyclic olefin copolymer of the present invention is considered to have a very high effect of improving the glass transition temperature, which is considered to be due to the [CO]-[CO] structure. have a tendency to be For example, as shown in Examples and Comparative Examples of the present invention, the ethylene-tetracyclododecene copolymer according to the present invention has a temperature of 210° C. even when the content of [CO] slightly exceeds 50 mol %. It can exhibit a glass transition temperature above. Further, the copolymer according to the present invention has a high glass transition of around 190 ° C. even if the [CO] (the content of the structural unit (z-2′)) is about 40 mol% to 50 mol%. temperature, ie even this degree of [CO] content exhibits a high glass transition temperature which may have been influenced by the [CO]--[CO] structure. These glass transition temperatures can be considered to be values that cannot be predicted from conventional knowledge.

The cyclic olefin copolymer of the present invention contains a chain structure of a specific bulky and large cyclic olefin structure (that is, a [CO]-[CO] structure) in a specific ratio. Therefore, it is presumed that the cyclic olefin copolymer of the present invention exhibits an unprecedentedly high glass transition temperature because the movement of the polymer molecular chain is restricted more than expected due to its unique structure. .

The cyclic olefin copolymer of the present invention also preferably contains a relatively high proportion of [E]-[CO] structures. In the cyclic olefin copolymer of the present invention, the sum of the ratio of [E]-[CO] structure and the ratio of [CO]-[CO] structure is preferably 75 to 99 mol %. Its lower limit is more preferably 80 mol %, still more preferably 85 mol %. The upper limit is more preferably 98 mol %, more preferably 97 mol %.

Having such a structure is also considered preferable for the cyclic olefin copolymer according to the present invention to exhibit a high glass transition temperature and exhibit excellent transparency.
The above linkage structures can be identified using ¹³ C NMR methods. At this time, depending on the structure, it may be difficult to identify the signal of each carbon by the usual ¹³ C NMR method. In such a case, a method such as determining the assignment by the INADEQUATE method, which is one of the two-dimensional NMR methods, may be used. In the copolymer of ethylene and tetracyclododecene in the examples described later, a signal in the region of 50 to 56 ppm of carbon derived from the [CO]-[CO] structure was observed by the INADEQUATE method. was found. Signals of other [E]-[E] structures and [E]-[CO] structures can be identified by conventional methods such as past reports.

The values of the above-mentioned [CO]-[CO] structure ratio, [E]-[E] structure ratio, and [E]-[CO] structure ratio are as follows for the cyclic olefin copolymer of the present invention: It is a value determined by a conventional method based on the intensity of each corresponding signal obtained by performing NMR measurement under conditions or equivalent conditions.
Measurement device: Bruker Biospin AVANCE III cryo-500 type nuclear magnetic resonance device Measurement nucleus: ¹³ C (125 MHz)
Measurement mode: Single pulse proton decoupling Pulse width: 90° (10.0 μs)
Measurement range: -55 to 195ppm
Chemical shift standard: 1,1,2,2,tetrachloroethane-d2 (74.2ppm)
Repeat time: 12 seconds Accumulation times: 256 times or more (1024 times or more during INADEQUATE measurement)
Measurement solvent; 1,1,2,2,tetrachloroethane-d2
Sample concentration: 10%w/v
Measurement temperature: 120℃

In addition, in the cyclic olefin copolymer, the higher the molecular weight, the lower the glass transition temperature, but the cyclic olefin copolymer of the present invention tends to exhibit a high glass transition temperature even if the molecular weight is high. . The present inventors presume that this is also to satisfy the preferable definition of the above [CO]-[CO] structure and [E]-[CO] structure.

<Requirement [II]>
The weight average molecular weight of the cyclic olefin copolymer of the present invention is preferably 5×10 ⁴ or more and 10×10 ⁵ or less as determined by gel permeation chromatography (GPC). Its lower limit is more preferably 8×10 ⁴ , still more preferably 1×10 ⁵ . On the other hand, the upper limit is more preferably 8×10 ⁵ , still more preferably 7×10 ⁵ , particularly preferably 6×10 ⁵ . As specific measurement conditions for GPC, the conditions described in Examples below are employed.
If the weight-average molecular weight is within the above range, the cyclic olefin copolymer of the present invention has a good balance among moldability, strength, transparency, etc., and can be suitably used for various purposes.

<Glass-transition temperature>
As described above, the cyclic olefin copolymer according to the third invention exhibits a high glass transition temperature, eg, 180°C to 300°C. The lower limit is preferably 183°C, more preferably 185°C, even more preferably 190°C, and particularly preferably 200°C. On the other hand, the upper limit is more preferably 280°C, still more preferably 270°C, and particularly preferably 260°C, from the viewpoint of the heat resistance stability of the polymer during melt molding.

The value of the glass transition temperature is measured under the following conditions or equivalent conditions.
Measurement conditions: Using a differential scanning calorimeter (SII Nanotechnology Co., Ltd. DSC6220), about 5.0 mg of a sample (cyclic olefin copolymer) was heated from 30°C to 300°C at a rate of 10°C/min under a nitrogen atmosphere. and held at that temperature for 5 minutes. (However, in the case of a copolymer that decomposes in the temperature range of 250° C. or higher and 320° C. or lower, the temperature to be maintained may be appropriately adjusted to a lower temperature as usual.) Furthermore, the temperature is lowered to 0° C. at a rate of 10° C./min. and maintained at that temperature for 5 minutes, then heated up to 300°C at a heating rate of 20°C/min. During this second temperature increase, the DSC curve bends due to the change in specific heat, and the baseline is sensed as a parallel shift. The temperature at the intersection of the tangent line of the baseline at a temperature lower than the bend and the tangent line of the point where the inclination is maximum at the bend is defined as the glass transition temperature (Tg).

If the Tg is unclear under the above conditions (for example, in the case of a polymer having a Tg of around 300°C), raise the upper limit of measurement temperature from 300°C by 10°C and measure again. If the condition is unclear, raise the upper limit temperature of measurement by 10° C. and measure again.

From the viewpoint of protecting the measuring device, the measurement above the upper limit temperature of 350° C. is not performed.
The cyclic olefin copolymer of the present invention has a high glass transition temperature and can be expected to have high transparency as well. It can be suitably used in applications where conventional cyclic olefin copolymers are employed, such as applications (containers for medical liquids such as intravenous drips). It is also expected to be used as an alternative material to glass in image pickup lenses used in automotive sensors, for which demand is expected to increase in the future.

EXAMPLES The present invention will be described in more detail based on examples below, but the present invention is not limited to these.
[Measuring method]
[Structure of Transition Metal Compound]
The structure of the transition metal compound is ¹ H-NMR spectrum (270 MHz, JEOL GSH-
270).

[Polymer Weight Average Molecular Weight (Mw), Molecular Weight Distribution (Mw/Mn)]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained by Waters "Alliance GPC 2000" gel permeation chromatograph (high temperature size exclusion chromatograph), the operating conditions are as follows:
<Apparatus used and conditions>
Measuring device; gel permeation chromatograph alliance GPC2000 type (Waters)
Analysis software; chromatography data system Empower (trademark, Waters)
Column; TSKgel GMH6-HT × 2 + TSKgel GMH6-HT × 2 (inner diameter 7.5 mm × length 30 cm, Tosoh Corporation)
Mobile phase; o-dichlorobenzene [= ODCB] (Wako Pure Chemical special grade reagent)
Detector: Differential refractometer (built-in)
Column temperature; 140°C
Flow rate; 1.0 mL/min
Injection volume: 400 μL
Sampling time interval; 1 second Sample concentration; 0.15% (w/v)
Molecular weight calibration; monodisperse polystyrene (Tosoh Corporation) / molecular weight from 495 to 20,600,000

[Polymer comonomer (cyclic olefin) content]
The comonomer (cyclic olefin) content of the polymer was determined by ¹³ C-NMR spectrum according to [0216] to [0219] of JP-A-2011-122146.

[Tg of polymer]
DSC measurement was performed under the following conditions to determine the Tg (glass transition temperature) of the polymer.
Apparatus: DSC6220 from SII Nano Technology Co., Ltd.
Measurement conditions: A sample held at 300° C. for 5 minutes was rapidly cooled to 0° C. and then heated to 250° C. at a heating rate of 20° C./min to determine Tg.

[Structure of polymer]
NMR measurement was performed under the following conditions, and the ratio of the structural units contained in the cyclic olefin copolymer, the ratio of the [CO]-[CO] structure, the [E]-[CO] structure (the [CO]- The sum of the [CO] structure, the [E]-[CO] structure and the [E]-[E] structure is defined as 100 mol %).

< ^13C NMR>
Apparatus: Bruker Biospin AVANCE IIIcryo-500 type nuclear magnetic resonance apparatus Measurement nuclei: 13C (125 MHz)
Measurement mode: single pulse proton (with reverse gate) decoupling Pulse width: 90 degrees Number of points: 64k
Observation range: 250 ppm (-55 to 195 ppm)
Repeat time: 12 seconds Accumulation times: 256 times Solvent: 1,1,2,2 tetrachloroethane-d2
Concentration: 10% (w/v)
Temperature: 120℃
Chemical shift standard: Tetramethylsilane standard (1,1,2,2-tetrachloroethane-d2: 74.2ppm)

< ¹³ C NMR (two-dimensional method - INADEQUATE measurement) >
Apparatus: Bruker Biospin AVANCE IIIcryo-500 type nuclear magnetic resonance apparatus Measurement nuclei: 13C (125 MHz)
Pulse program: inadqf
Number of points (tetracyclododecene-derived skeleton) F2: 4096 × F1: 256 (NUS 50%)
Observation range: 60ppm
Repeat time: 12 seconds Accumulation times: 1024 times Solvent: 1,1,2,2 tetrachloroethane-d2
Concentration: 10% (w/v)
Temperature: 120℃
Chemical shift standard: Tetramethylsilane standard (1,1,2,2-tetrachloroethane-d2: 74.2ppm)
Chemical shifts of peaks derived from TD-TD linkages, E-TD linkages, etc. ⁽ * ⁾ were assigned by the INADEQUATE method described above. The composition of each structural unit was obtained from the intensity of those peaks.
(*) TD: Tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene E: Ethylene

[Embodiment etc. of the first invention]
<(1) Synthesis of transition metal compound>
[Synthesis Example 1-1]
Titanium compound (1) is described in Macromolcules 2011, 44, 1986. Synthesized by the method described.

[Synthesis Example 1-2]
3.06 g (20.0 mmol) of 3,5-diisopropylpyrazole and 20 mL of n-hexane were charged into a 100 mL glass reactor which had been sufficiently dried and purged with nitrogen, and stirred. After adding 12.2 mL of n-butyllithium solution (hexane solution, 1.64 M, 20.0 mmol) to this solution at 0° C., stirring was continued at room temperature for 4 hours. The solvent of the reaction solution was distilled off to obtain 3.08 g of a colorless solid.

0.27 g (1.0 mmol) of indenyl titanium (IV) trichloride and 8 mL of diethyl ether were charged into another 30 mL glass reactor which was sufficiently dried and purged with nitrogen, and stirred. To this solution, a solution prepared from 0.16 g (1.0 mmol) of the previously obtained colorless solid and 2 mL of diethyl ether was added at -78°C, and stirring was continued at room temperature for 18 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting brown solid to prepare a suspension, and insoluble matter was removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, n-hexane was added, filtered, washed and dried to obtain 66.7 mg (yield 17%) of titanium compound (2) represented by the following formula (2). rice field.
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.48-7.41 (2H, m, Ar-H), 7.19-7.10 (5H, m, Ar-H), 6.44 (1H, s, CH), 2.84 (2H, sept, J=6.9 Hz, CH (CH3)2), 1.25 (12H, d, J=6.9 Hz, CH( CH3 )2) ppm

[Synthesis Example 1-3]
0.96 g (4.7 mmol) of 3,5-bis(trifluoromethyl)-1H-pyrazole, 5 mL of n-hexane and 5 mL of toluene were charged into a 30 mL reactor which was sufficiently dried and purged with nitrogen, and stirred. After adding 2.9 mL of n-butyllithium solution (hexane solution, 1.64 M, 4.7 mmol) to this solution at 0° C., stirring was continued at room temperature for 4 hours. After distilling off the solvent of the reaction solution, the dried solid obtained was washed with 5 mL of n-hexane, recovered, and dried under reduced pressure to obtain 0.80 g of a colorless solid.

0.29 g (1.0 mmol) of tert-butylcyclopentadienyltrichlorotitanium and 5 mL of diethyl ether were charged into another 30 mL reactor which was sufficiently dried and purged with nitrogen, and stirred. To this solution, a solution prepared from 0.21 g (1.0 mmol) of the previously obtained colorless solid and 5 mL of diethyl ether was added at -78°C, and stirring was continued at room temperature for 24 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the resulting oil to prepare a suspension, and insoluble matter was removed with a membrane syringe filter. After concentrating the resulting solution under reduced pressure, n-hexane is added and the yellow-orange crystals obtained by standing at -30 ° C. are collected and dried under reduced pressure to obtain titanium represented by the following formula (1). 38 mg of compound (1) was obtained (8% yield). ¹ H-NMR (270 MHz, CDCl ₃ ) δ 7.33 (1H, s, CH), 6.84 (2H, t, J = 2.8 Hz, Cp-H), 6.69 (2H, t, J = 2.8 Hz, Cp-H), 1.30 (9H, s, C( _CH3 ) ₃ ) ppm

〔式中、ｔＢｕはｔｅｒｔ－ブチル基である。〕

[In the formula, tBu is a tert-butyl group. ]

<(2) Olefin polymerization>
[Example 1-1]
In a glass reactor with an internal volume of 500 mL that has been sufficiently purged with nitrogen, 250 mL of a cyclohexane/hexane (9/1) mixed solution and tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene ( Hereinafter, also simply referred to as “tetracyclododecene”) and 82.6 mg (0.375 mmol) of BHT (dibutylhydroxytoluene (also known as 2,6-di-tert-butyl-4-methylphenol)). The liquid phase and gas phase were saturated with 50 liters/hr of ethylene. Thereafter, 0.75 mmol of methylaluminoxane in terms of aluminum atom and 0.0015 mmol of titanium compound (1) obtained in Synthesis Example 1-1 were added to initiate polymerization. Ethylene was continuously supplied at a rate of 50 liters/hr, and polymerization was carried out at 50° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reactant was added to 1 liter of acetone/methanol (3/1) mixed solvent containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 130° C. for 10 hours to obtain 0.730 g of an ethylene/tetracyclododecene copolymer. The polymerization activity was 2.92 kg/mmol-Ti·hr, and the weight average molecular weight Mw of the obtained ethylene/tetracyclododecene copolymer was 348 kg/mol. The glass transition temperature measured by DSC was 190° C., and the tetracyclododecene content in the polymer estimated by ¹³ C NMR was 44.9 mol %. Table 1 shows the results.

[Example 1-2]
250 mL of a cyclohexane/hexane (9/1) mixed solution, 5 g of tetracyclododecene, and 331 mg (1.50 mmol) of BHT were charged into a glass reactor having an internal volume of 500 mL that was sufficiently purged with nitrogen, and 50 liters/hr of ethylene was added. to saturate the liquid and gas phases. Thereafter, 1.5 mmol of methylaluminoxane in terms of aluminum atom and 0.0030 mmol of titanium compound (1) obtained in Synthesis Example 1-1 were added to initiate polymerization. Ethylene was continuously supplied at a rate of 50 liters/hr, and polymerization was carried out at 50° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reactant was added to 1 liter of acetone/methanol (3/1) mixed solvent containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 130° C. for 10 hours to obtain 1.292 g of an ethylene/tetracyclododecene copolymer. The polymerization activity was 2.58 kg/mmol-Ti·hr, and the weight average molecular weight Mw of the obtained ethylene/tetracyclododecene copolymer was 320 kg/mol. The glass transition temperature measured by DSC was 188° C., and the tetracyclododecene content in the polymer estimated by ¹³ C NMR was 44.6 mol %. Table 1 shows the results.

[Example 1-3]
The procedure of Example 1-2 was repeated except that 661 mg (3.00 mmol) of BHT was charged, and 1.081 g of an ethylene/tetracyclododecene copolymer was obtained. The polymerization activity was 2.16 kg/mmol-Ti·hr, and the weight average molecular weight Mw of the obtained ethylene/tetracyclododecene copolymer was 295 kg/mol. The glass transition temperature measured by DSC was 189° C., and the tetracyclododecene content in the polymer estimated by ¹³ C NMR was 44.8 mol %. Table 1 shows the results.

[Example 1-4]
A 500-mL glass reactor fully purged with nitrogen was charged with 250 mL of a cyclohexane/hexane (9/1) mixed solution, 26 g of tetracyclododecene, and 82.6 mg (0.375 mmol) of BHT, and 50 liters of ethylene. /hr to saturate the liquid and gas phases. Then, 1.5 mmol of methylaluminoxane in terms of aluminum atom and 0.0030 mmol of titanium compound (2) obtained in Synthesis Example 1-2 were added to initiate polymerization. Ethylene was continuously supplied at a rate of 50 liters/hr, and polymerization was carried out at 50° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reactant was added to 1 liter of acetone/methanol (3/1) mixed solvent containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 130° C. for 10 hours to obtain 1.269 g of an ethylene/tetracyclododecene copolymer. The polymerization activity was 2.54 kg/mmol-Ti·hr, and the weight average molecular weight Mw of the obtained ethylene/tetracyclododecene copolymer was 751 kg/mol. The glass transition temperature measured by DSC was 250° C., and the tetracyclododecene content in the polymer estimated by ¹³ C NMR was 57.1 mol %. Table 1 shows the results.

[Example 1-5]
The procedure of Example 1-4 was repeated except that 165 mg (0.750 mmol) of BHT was charged, and 0.830 g of an ethylene/tetracyclododecene copolymer was obtained. The polymerization activity was 1.66 g/mmol-Ti·hr, and the weight average molecular weight Mw of the obtained ethylene/tetracyclododecene copolymer was 579 kg/mol. The glass transition temperature measured by DSC was 251° C., and the tetracyclododecene content in the polymer estimated by ¹³ C NMR was 57.4 mol %. Table 1 shows the results.

[Comparative Example 1-1]
0.303 g of an ethylene/tetracyclododecene copolymer was obtained in the same manner as in Example 1-1 except that BHT was not charged. The polymerization activity was 1.21 kg/mmol-Ti·hr, and the weight average molecular weight Mw of the obtained ethylene/tetracyclododecene copolymer was 262 kg/mol. The glass transition temperature measured by DSC was 195° C., and the tetracyclododecene content in the polymer estimated by ¹³ C NMR was 45.9 mol %. Table 1 shows the results.

[Comparative Example 1-2]
250 mL of a cyclohexane/hexane (9/1) mixed solution and 10 g of tetracyclododecene were charged into a glass reactor having an internal volume of 500 mL which was sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with 50 L/hr of ethylene. let me Then, 1.5 mmol of methylaluminoxane in terms of aluminum atom and 0.0030 mmol of titanium compound (2) obtained in Synthesis Example 1-2 were added to initiate polymerization. Ethylene was continuously supplied at a rate of 50 liters/hr, and polymerization was carried out at 50° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reactant was added to 1 liter of acetone/methanol (3/1) mixed solvent containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 130° C. for 10 hours to obtain 0.201 g of an ethylene/tetracyclododecene copolymer. The polymerization activity was 0.40 kg/mmol-Ti·hr, and the weight average molecular weight Mw of the obtained ethylene/tetracyclododecene copolymer was 113 kg/mol. The glass transition temperature measured by DSC was 217° C., and the tetracyclododecene content in the polymer estimated by ¹³ C NMR was 52.7 mol %. Table 1 shows the results.

[Comparative Example 1-3]
0.066 g of an ethylene/tetracyclododecene copolymer was obtained in the same manner as in Example 1-4 except that BHT was not added. The polymerization activity was 0.13 kg/mmol-Ti·hr. The glass transition temperature measured by DSC was 241° C., and the tetracyclododecene content in the polymer estimated by ¹³ C NMR was 55.4 mol %. No further analysis could be performed due to the low polymer yield. Table 1 shows the results.

[Comparative Example 1-4]
0.403 g of an ethylene/tetracyclododecene copolymer was obtained in the same manner as in Comparative Example 1-1 except that 2.5 g of tetracyclododecene was used. The polymerization activity was 0.81 kg/mmol-Ti·hr, and the weight average molecular weight Mw of the obtained ethylene/tetracyclododecene copolymer was 195 kg/mol. The glass transition temperature measured by DSC was 171° C., and the tetracyclododecene content in the polymer estimated by ¹³ C NMR was 41.1 mol %. Table 1 shows the results.

First, in Comparative Examples 1-1 to 1-3, the polymerization activity and weight average molecular weight decreased as the tetracyclododecene content increased. On the other hand, in Examples 1-1 to 1-5, the addition of BHT greatly increased the polymerization activity and the weight average molecular weight, showing an effect opposite to the tendency seen in the comparative examples. It is presumed that this is because the added BHT deactivated the trialkylaluminum species serving as a polymerization inhibitor and a chain transfer agent.

[Embodiment etc. of the second invention]
<(1) Production of titanium compound>
[Example 2-A1]
Synthesis Example 1-3 described above is used as Example 2-A1.
[Example 2-A2]
Synthesis Example 1-2 described above is used as Example 2-A2.

<(2) Production of olefin polymer>
[Example 2-B1]
250 mL of a cyclohexane/hexane (9/1) mixed solution and 10 g of tetracyclododecene (equivalent to 0.250 mol/L) were charged into a glass reactor having an internal volume of 500 mL that was sufficiently purged with nitrogen, and 50 liters/hr of ethylene was added. to saturate the liquid and gas phases. Thereafter, 0.75 mmol of methylaluminoxane in terms of aluminum atom and 0.0015 mmol of titanium compound (3) obtained in Example 2-A1 were added to initiate polymerization. Ethylene was continuously supplied at a rate of 50 liters/hr, and polymerization was carried out at 50° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reactant was added to 1 liter of acetone/methanol (3/1) mixed solvent containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 130° C. for 10 hours to obtain an ethylene/tetracyclododecene copolymer. Table 2 shows the physical properties of the ethylene/tetracyclododecene copolymer.

[Example 2-B2]
The same operation as in Example 2-B1 except that the titanium compound was changed to 0.0030 mmol of the titanium compound (2) obtained in Example 2-A2, and the amount of methylaluminoxane was changed to 1.50 mmol in terms of aluminum atoms. was performed to obtain an ethylene/tetracyclododecene copolymer. Table 2 shows the physical properties of the ethylene/tetracyclododecene copolymer.

[Comparative Example 2-B1]
An ethylene/tetracyclododecene copolymer was obtained in the same manner as in Example 2-B1, except that the titanium compound was changed to 0.0015 mmol of the titanium compound (1) obtained in Synthesis Example 1-1. rice field. Table 2 shows the physical properties of the ethylene/tetracyclododecene copolymer.

[Embodiment etc. of the third invention]
<Production of cyclic olefin copolymer>
[Example 3-1]
As Example 3-1, Example 1-2 described above is used.
The proportion of tetracyclododecene chain units (TD-TD chain units) and the proportion of ethylene and tetracyclododecene chain units (E-TD chain units) contained in the obtained cyclic olefin copolymer were specified. . Table 3 shows the results.

[Example 3-2]
As Example 3-2, Example 1-4 described above is used.
The ratio of the tetracyclododecene biad chain structure (TD-TD chain) and the ratio of the linking structure (E-TD chain) between ethylene and tetracyclododecene contained in the obtained cyclic olefin copolymer were measured. identified. Table 3 shows the results.

[Comparative Example 3-1]
A copolymer of ethylene and tetracyclododecene was prepared according to Example 1 of JP-A-62-215611 to obtain a copolymer. The proportion of tetracyclododecene double chain structure (TD-TD chain) and the proportion of linking structure (E-TD chain unit) between ethylene and tetracyclododecene contained in the obtained cyclic olefin copolymer. identified. Table 3 shows the results.

From the above results, it can be seen that the cyclic olefin copolymer according to the third aspect of the present invention has a unique structure not found in the prior art and exhibits a high Tg.
FIG. 1 shows the polymers obtained in Examples 1-1 to 1-5 including Example 3-1 and Example 3-2, and Comparative Examples 1-1, 1-3, and 1-4 (the above are It corresponds to (or may correspond to) the cyclic olefin copolymer according to the third aspect of the present invention), Comparative Example 3-1, and the composition of ethylene, norbornene, and the copolymer described in Non-Patent Document 1. It is the figure which showed the relationship with Tg.
It can also be recognized from FIG. 1 that the cyclic olefin copolymer according to the third aspect of the present invention has a unique structure and thus tends to exhibit a higher Tg than conventional ones.

Claims (12)

(A) a transition metal compound;
(B) (B-1) an organometallic compound (B-2) an organoaluminum oxy compound, and (B-3) at least one selected from the group consisting of a compound that forms an ion pair by reacting with the transition metal compound (A) a compound;
(C) (C-1) an alcohol compound, and (C-2) at least one compound selected from a phenol compound,
A catalyst for olefin polymerization, wherein the transition metal compound (A) is a compound represented by the following general formula [A-1].

[In formula [A-1],
M is a titanium atom, a zirconium atom, or a hafnium atom;
n is an integer from 1 to 4,
Each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene is a divalent derivative group,
R ¹ to R ⁸ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group; and adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring. ] In the general formula [A-1],
M is a titanium atom or a zirconium atom,
each X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group;
R ¹ to R ⁵ and R ⁸ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a halogen-containing group, or a silicon-containing group, and adjacent groups among R ¹ to R ⁵ may be bonded to each other to form a ring,
2. The olefin polymerization catalyst according to claim 1, wherein R ⁶ and R ⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms. In the general formula [A-1],
M is a titanium atom,
R ¹ to R ⁵ and R ⁸ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and adjacent groups among R ¹ to R ⁵ are bonded to each other to form a ring. may be
3. The olefin polymerization catalyst according to claim 2, wherein R ⁶ and R ⁷ are each independently a hydrocarbon group having 1 to 20 carbon atoms. The olefin polymerization catalyst according to any one of claims 1 to 3, wherein the compound (C) contains the alcohol compound (C-1) having 1 to 20 carbon atoms. The olefin polymerization catalyst according to any one of claims 1 to 4, wherein the compound (C) contains the phenol compound (C-2) having 6 to 20 carbon atoms. The alcohol compound (C-1) is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol. 5. The olefin polymerization catalyst according to claim 4, which is one or two or more. The phenol compound (C-2) is 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 4-nonylphenol, 4-hexylphenol, 4-isopropylphenol, 3, 5-dimethylphenol, 2,3,6-trimethylphenol, 2,3,5-trimethylphenol, 2,4-di-tert-butylphenol, 2-isopropylphenol, 2-tert-butylphenol, p-dodecylphenol, 2 6. The olefin polymerization catalyst according to claim 5, which is one or more selected from the group consisting of -phenylphenol and p-phenylphenol. (Z-1) a linear or branched α-olefin having 2 to 30 carbon atoms;
(Z-2) Claims used for copolymerization with cyclic olefins represented by the following general formula [ZI], general formula [Z-II], general formula [Z-III] or general formula [Z-IV] Item 8. The olefin polymerization catalyst according to any one of Items 1 to 7.

[In the formula [ZI], u is 0 or 1,
v is 0 or a positive integer;
w is 0 or 1;
R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and R ⁷⁵ to R ⁷⁸ are bonded together to form a monocyclic or polycyclic ring; and the monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. . ]

[In the formula [Z-II], x and d are 0 or an integer of 1 or more,
y and z are 0, 1 or 2;
R ⁸¹ to R ⁹⁹ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded, the carbon atom to which R ⁹³ is bonded, or R ⁹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ]

[In formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18. ]

[In the general formula [Z-IV], x is an integer of 0 or 1 or more,
R ¹¹¹ to R ¹¹⁸ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group;
R ¹²¹ to R ¹²⁴ are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring.
] The α-olefin (Z-1) is ethylene, and the cyclic olefin (Z-2) is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, the olefin polymerization catalyst according to claim 8. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 9. The olefin according to claim 10, wherein the olefin polymerization catalyst is the olefin polymerization catalyst according to claim 8, and the olefin comprises the α-olefin (Z-1) and the cyclic olefin (Z-2). A method for producing a polymer. The α-olefin (Z-1) is ethylene, and the cyclic olefin (Z-2) is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, the method for producing an olefin polymer according to claim 11.

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