JP7660391B2 - Method for producing ethylene-α-olefin-non-conjugated polyene copolymer - Google Patents

Description

The present invention relates to a method for producing an ethylene-α-olefin-non-conjugated polyene copolymer using an olefin polymerization catalyst containing a transition metal compound having a specific ligand structure.

Ethylene-α-olefin rubber, typified by ethylene-propylene-non-conjugated diene copolymer (EPDM), has no unsaturated bonds in the main chain of its molecular structure, and therefore has superior heat resistance and weather resistance compared to commonly used conjugated diene rubber. It is therefore widely used in a variety of applications, including automotive parts, electrical wire materials, construction and civil engineering materials, industrial parts, and as a modifier for various resins.

Conventionally, ethylene-α-olefin-non-conjugated polyene copolymers such as EPDM have been produced using a catalyst system (so-called Ziegler-Natta catalyst system) that generally consists of a combination of a titanium-based catalyst or a vanadium-based catalyst and an organoaluminum compound. The biggest drawback of this catalyst system is its productivity. The catalyst has low polymerization activity and a short catalyst life, so it is necessary to carry out the polymerization at a low temperature of around 0 to 50°C. When polymerization is carried out at such low temperatures, the viscosity generally increases as the temperature decreases, so the product concentration in the polymerization system is limited due to the viscosity bottleneck of the polymerization solution, and a process for decatalyzing and deashing the product is essential. Furthermore, it is difficult to control the polymerization heat due to the low-temperature polymerization. Due to the above problems, improvements were desired in terms of production and cost.

On the other hand, metallocene catalyst systems, which have been the subject of active research since the 1980s, exhibit superior polymerization activity and α-olefin copolymerization ability compared to Ziegler-Natta catalyst systems, and because they are single-site catalysts, they make it possible to produce new olefin copolymers with narrow molecular weight and composition distributions. There have also been reports on new production methods for ethylene-α-olefin-non-conjugated polyene copolymers.

However, even with such metallocene catalyst systems, there are many issues that prevent commercial practical use. Examples of issues related to the production of ethylene-α-olefin-non-conjugated polyene copolymers include issues in terms of production, cost, and physical properties, such as polymerization activity that can be adapted to a non-decalcifying process, high molecular weight that can withstand high-temperature polymerization, non-conjugated polyene copolymerization ability that does not place a burden on the monomer recovery process, and high monomer alternating copolymerization ability to exhibit good low-temperature properties in terms of physical properties.

For example, Patent Documents 1, 2, 3, and 4 disclose manufacturing methods using geometrically constrained catalysts. These geometrically constrained catalysts have excellent copolymerizability with α-olefins and produce high molecular weight products, but because of low alternating copolymerizability of monomers, the average ethylene chain length in the ethylene-α-olefin-non-conjugated polyene copolymer is long, and as a result, there remains the issue of insufficient low-temperature properties, which are one of the important physical properties. In addition, manufacturing methods using geometrically constrained catalysts often show high polymerization activity in the early stages of polymerization, making it difficult to control the polymerization heat.

In addition, Patent Documents 5, 6, 7, etc. disclose bridged metallocene catalysts having biscyclopentadienyl groups or bisindenyl groups in the ligand, and although the alternating copolymerization of monomers is relatively high, all of them have problems such as low polymerization activity and low molecular weight of the obtained ethylene-α-olefin-non-conjugated polyene copolymer.

Therefore, there is a need for a manufacturing method for more efficiently and cheaply producing ethylene-α-olefin-non-conjugated polyene copolymers with excellent heat resistance, weather resistance, and low-temperature properties. In particular, if a catalyst system with higher copolymerization ability for non-conjugated polyenes could be developed, it would be possible to reduce the amount of non-conjugated polyene fed, reducing the load on the monomer recovery process and providing a more efficient and cost-effective manufacturing method.

More recently, in response to increasing legal regulations regarding chemical safety, it is expected that the amount of non-conjugated polyene residues in ethylene-α-olefin-non-conjugated polyene copolymer products will be reduced, and polymerization catalysts are now required to have even higher non-conjugated polyene copolymerization ability. However, with conventional metallocene catalysts, when attempting to increase the non-conjugated polyene copolymerization ability above a certain level, the α-olefin copolymerization ability is impaired, making it difficult to reduce the amount of non-conjugated polyene residues in the resin while maintaining product quality.

European Patent Application Publication No. 416815 WO 95/00526 WO 98/27103 Special Publication No. 2001-522398 JP 2005-344101 A Japanese Patent Application Publication No. 9-151205 Special Publication No. 2000-507635

In view of these problems, the present invention aims to provide a method for producing an ethylene-α-olefin-non-conjugated polyene copolymer using a polymerization catalyst that has a higher copolymerization ability for non-conjugated polyenes while maintaining the copolymerization ability of α-olefins.

As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by copolymerizing ethylene, an α-olefin, and a non-conjugated polyene in a specific monomer charging ratio using an olefin polymerization catalyst comprising a transition metal compound having a bidentate ligand of a specific structure, and have thus completed the present invention.
The gist of the present invention is as follows.
[1]
[A] a transition metal compound represented by the following general formula (I), and [B] [B-1] an organometallic compound,
A method for producing an ethylene-α-olefin-non-conjugated polyene copolymer, comprising a step [P] of polymerizing ethylene-α-olefin-non-conjugated polyene in the presence of an olefin polymerization catalyst comprising at least one compound selected from the group consisting of [B-2] an organoaluminum oxy compound, and [B-3] a compound that reacts with the transition metal compound [A] to form an ion pair.

（式（Ｉ）において、
Ｍは周期律表第３～１１族の遷移金属原子を示し、
ｍは、１～６の整数を示し、
Ｒ¹～Ｒ³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、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、
Ｒ⁴，Ｒ⁵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、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、互いに結合して炭素原子－窒素原子間に二重結合を構成してもよく、
Ｚは、下記式（ＩＩ）で表される構造を示し

(In formula (I),
M represents a transition metal atom of Groups 3 to 11 of the periodic table;
m represents an integer from 1 to 6;
R ¹ to R ³ may be the same or different and each represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a 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 to each other to form a ring;
R ⁴ and R ⁵ may be the same or different and each represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and may be bonded to each other to form a double bond between a carbon atom and a nitrogen atom,
Z represents a structure represented by the following formula (II):

（式（ＩＩ）において、複数個あるＲ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、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、隣接するＲ同士が結合して二重結合を構成してもよく、●は、炭素原子（Ｃ）との結合点を示し、○は、窒素原子（Ｎ）との結合点を示し、ｐは、１～６の整数を示す。）
また、ｍが２以上の場合には各々に存在するＲ¹～Ｒ³およびＲで示される基のうち２個の基が連結されていてもよく、
ｎは、Ｍの価数を満たす数であり、
Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の場合は、Ｘで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよく、
Ｒ¹⁰～Ｒ¹⁴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、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよい。〕
［２］
前記一般式（Ｉ）のＲ⁴とＲ⁵が互いに結合して、炭素原子－窒素原子間が二重結合を構成する、項［１］に記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。
［３］
前記一般式（Ｉ）のＺが下記式（ＩＩＩ）で表される、項［１］または［２］に記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法；

(In formula (II), the multiple R's may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a 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 bonded to each other to form a ring, adjacent R's may be bonded to each other to form a double bond, ● represents a bonding point with a carbon atom (C), ○ represents a bonding point with a nitrogen atom (N), and p represents an integer from 1 to 6.)
When m is 2 or more, two of the groups represented by R ¹ to R ³ and R may be linked to each other.
n is a number that satisfies the valence of M;
X represents 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 compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different from one another, and the multiple groups represented by X may be bonded to one another to form a ring;
R ¹⁰ to R ¹⁴ may be the same or different and each represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring.
[2]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to item [1], wherein R ⁴ and R ⁵ in the general formula (I) are bonded to each other to form a double bond between the carbon atom and the nitrogen atom.
[3]
The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to item [1] or [2], wherein Z in the general formula (I) is represented by the following formula (III):

〔式中、Ｒ⁶～Ｒ⁹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、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、●は、炭素原子（Ｃ）との結合点を示し、○は、窒素原子（Ｎ）との結合点を示す〕。
［４］
前記一般式（Ｉ）のＲ¹～Ｒ³が、炭素原子数１～１０の直鎖状または分岐状のアルキル基、炭素原子数３～１０の環状飽和炭化水素基、または、炭素原子数６～１０のアリール基である、項［１］～［３］のいずれかに記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。
［５］
前記一般式（Ｉ）のＲ¹～Ｒ³が、水素、メチル基、フェニル基のいずれかである、項［１］～［３］のいずれかに記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。
［６］
前記一般式（Ｉ）のＭが、周期律表第４または５族の遷移金属原子である、項［１］～［５］のいずれかに記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。
［７］
前記一般式（Ｉ）のＭが、周期律表第４族の遷移金属原子である、項［１］～［５］のいずれかに記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。
［８］
非共役ポリエンが下記一般式（ＩＶ）で表される、項［１］～［７］のいずれかに記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。

[In the formula, R ⁶ to R ⁹ may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring, and ● represents a bonding point to a carbon atom (C), and ○ represents a bonding point to a nitrogen atom (N)].
[4]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of items [1] to [3], wherein R ¹ to R ³ in the general formula (I) are a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
[5]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of items [1] to [3], wherein R ¹ to R ³ in the general formula (I) are hydrogen, a methyl group, or a phenyl group.
[6]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of items [1] to [5], wherein M in the general formula (I) is a transition metal atom of Group 4 or 5 of the periodic table.
[7]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of items [1] to [5], wherein M in the general formula (I) is a transition metal atom of Group 4 of the periodic table.
[8]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of items [1] to [7], wherein the non-conjugated polyene is represented by the following general formula (IV):

〔式中、ｍは０から２の整数であり、
Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷およびＲ¹⁸は、それぞれ独立に、水素原子、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、該炭化水素基は二重結合を有していてもよく、
Ｒ¹⁵からＲ¹⁸までのうちの任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹⁵とＲ¹⁶とで、またはＲ¹⁷とＲ¹⁸とでアルキリデン基を形成していてもよく、Ｒ¹⁵とＲ¹⁷とが、またはＲ¹⁶とＲ¹⁸とが互いに結合して二重結合を形成していてもよく、
以下の（i）から（iv）の要件の少なくとも一つが満たされる。
（i）Ｒ¹⁵からＲ¹⁸までの少なくとも一つは、二重結合を一つ以上有する炭化水素基であ
る。
（ii）Ｒ¹⁵からＲ¹⁸までの任意の二つの置換基は互いに結合して環を形成し、該環は二重結合を含んでいる。
（iii）Ｒ¹⁵とＲ¹⁶とで、またはＲ¹⁷とＲ¹⁸とでアルキリデン基を形成している。
（iv）Ｒ¹⁵とＲ¹⁷とが、またはＲ¹⁶とＲ¹⁸とが互いに結合して二重結合を形成している。〕
［９］
前記非共役ポリエンが、５－エチリデン－２－ノルボルネン（ＥＮＢ）または５－ビニル－２－ノルボルネン（ＶＮＢ）であることを特徴とする、項［８］に記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。
［１０］
前記工程［Ｐ］がエチレンと炭素数が３から１０のα－オレフィンと非共役ポリエンとを共重合する工程である項［８］または［９］に記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。
［１１］
前記α－オレフィンがプロピレンである、項［１０］に記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。
［１２］
前記工程［Ｐ］の重合温度が８０℃以上である、項［１］～［１１］のいずれかに記載のエチレン・α－オレフィン・非共役ポリエン共重合体の製造方法。

[In the formula, m is an integer from 0 to 2,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, the hydrocarbon group optionally having a double bond;
any two of the substituents R ¹⁵ to R ¹⁸ may be bonded to each other to form a ring, the ring may contain a double bond, R ¹⁵ and R ¹⁶ , or R 17 and R ¹⁸ may be bonded to each other to form an alkylidene group, or R ¹⁵ and R ^{17 , or R 16 and} R ¹⁸ may be bonded to each other to form a double bond;
At least one of the following requirements (i) to (iv) is met:
(i) At least one of R ¹⁵ to R ¹⁸ is a hydrocarbon group having one or more double bonds.
(ii) any two of the substituents R ¹⁵ to R ¹⁸ are bonded to each other to form a ring, and the ring contains a double bond.
(iii) R ¹⁵ and R ¹⁶ together, or R ¹⁷ and R ¹⁸ together form an alkylidene group.
(iv) R ¹⁵ and R ¹⁷ , or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond.
[9]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to item [8], characterized in that the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB).
[10]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to item [8] or [9], wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, and a non-conjugated polyene.
[11]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to item [10], wherein the α-olefin is propylene.
[12]
The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of items [1] to [11], wherein the polymerization temperature in the step [P] is 80° C. or higher.

According to the present invention, it is possible to produce an ethylene-α-olefin-non-conjugated polyene copolymer with higher non-conjugated polyene copolymerizability while maintaining the copolymerizability of the α-olefin, so that an ethylene-α-olefin-non-conjugated polyene copolymer of the same composition can be produced using a smaller amount of non-conjugated polyene. This not only enables process streamlining in the production process of the ethylene-α-olefin-non-conjugated polyene copolymer, such as reducing the load of the demonomerization step, but is also expected to improve quality and safety, such as reducing the amount of non-conjugated polyene remaining in the product.

The olefin polymerization catalyst and the method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention are described in detail below.

[Olefin Polymerization Catalyst]
The olefin polymerization catalyst according to the present invention has, as essential components, a transition metal compound [A] and at least one compound selected from [B], [B-1] an organometallic compound, [B-2] an organoaluminum oxy compound, and [B-3] a compound that reacts with the transition metal compound [A] to form an ion pair.
The above-mentioned components [A] and [B], which are the constituent elements of the olefin polymerization catalyst of the present invention, as well as other components that can be used as necessary, will now be described in detail.

[Transition metal compound [A]]
In the present invention, the transition metal compound [A] is represented by the following general formula (I).

上記一般式（Ｉ）において、Ｍは周期律表第３～１１族の遷移金属原子（３族にはランタノイドも含まれる）を示し、好ましくは３～９族の金属原子であり、より好ましくは３～５族から選ばれる遷移金属原子であり、さらに好ましくは４族または５族から選ばれる遷移金属原子であり、特に好ましくは４族の遷移金属原子である。具体的には、スカンジウム、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタル、コバルト、ロジウム、イットリウム、クロム、モリブデン、タングステン、マンガン、レニウム、鉄、ルテニウムなどであり、好ましくはスカンジウム、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタル、コバルト、ロジウムなどであり、より好ましくは、チタン、ジルコニウム、ハフニウム、コバルト、ロジウム、バナジウム、ニオブ、タンタルなどであり、より好ましくはチタン、ジルコニウム、ハフニウムであり、特に好ましくはジルコニウムおよびハフニウムである。

In the above general formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably a metal atom of Groups 3 to 9, more preferably a transition metal atom selected from Groups 3 to 5, further preferably a transition metal atom selected from Group 4 or Group 5, and particularly preferably a transition metal atom of Group 4. Specifically, M is scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, etc., preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, etc., more preferably titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum, etc., more preferably titanium, zirconium, hafnium, and particularly preferably zirconium and hafnium.

In general formula (I), the dotted line connecting N and M generally indicates that N is coordinated to M, but in the present invention, it does not matter whether N is coordinated or not.

In the above general formula (I), m is an integer from 1 to 6, preferably an integer from 1 to 4, and more preferably 1.

In the above general formula (I), R ¹ to R ³ may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ¹ to R ³ may be linked to each other to form a ring.
The halogen atom includes fluorine, chlorine, bromine, and iodine.

Examples of the hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic hydrocarbon groups having 3 to 30 carbon atoms, and aromatic hydrocarbon groups having 6 to 30 carbon atoms. Specific examples include linear or branched alkyl groups having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group;
linear or branched alkenyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group;
Straight-chain or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20, and more preferably 2 to 10 carbon atoms, such as an ethynyl group or a propargyl group; cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20, and more preferably 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or an adamantyl group;
cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as a cyclopentadienyl group, an indenyl group, or a fluorenyl group;
aryl groups having 6 to 30, preferably 6 to 20, and more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group;
Alkyl-substituted aryl groups such as a tolyl group, an iso-propylphenyl group, a t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group;
etc.

The above-mentioned hydrocarbon groups may have hydrogen atoms substituted with halogens. Examples of such hydrocarbon groups in which hydrogen atoms are substituted with halogens include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as trifluoromethyl groups, pentafluorophenyl groups, and chlorophenyl groups.

The above-mentioned hydrocarbon groups may be substituted with other hydrocarbon groups. Examples of such substituted hydrocarbon groups include aryl-substituted alkyl groups such as benzyl and cumyl groups.

Furthermore, the hydrocarbon group may be a heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, and carboxylic anhydride groups;
nitrogen-containing groups such as amino groups, imino groups, amido groups, imido groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups in the form of ammonium salts;
boron-containing groups such as a boranediyl group, a boranetriyl group, and a diboranyl group;
Sulfur-containing groups such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group;
Phosphorus-containing groups such as phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups;
It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

The 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, as well as groups in which these heterocyclic compound residues are further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

The silicon-containing group may be a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, or a hydrocarbon-substituted siloxy group, and more specifically may be a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, a dimethyl-t-butylsilyl group, or a dimethyl(pentafluorophenyl)silyl group. Of these, the methylsilyl group, the dimethylsilyl group, the trimethylsilyl group, the ethylsilyl group, the diethylsilyl group, the triethylsilyl group, the dimethylphenylsilyl group, or the triphenylsilyl group is preferred, and the trimethylsilyl group, the triethylsilyl group, the triphenylsilyl group, or the dimethylphenylsilyl group is particularly preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

The germanium-containing group or the tin-containing group may be a group in which the silicon of the silicon-containing group is replaced with germanium or tin.

Among the groups exemplified as the groups that the hydrocarbon group may have,
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group.
Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.
Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.
Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group.
Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group.
Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group.
Specific examples of the imide group include an acetimide group and a benzimide group.
Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
Specific examples of the alkylthio group include a methylthio group and an ethylthio group.
Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group.
Specific examples of the sulfonate group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.
Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group;
aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group;
Preferred are substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents such as a halogen atom, an alkyl group or alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms, or an aryl group or aryloxy group having 6 to 30, preferably 6 to 20, carbon atoms.

As described above, R ¹ to R ³ can be a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and examples of these include the same as those exemplified in the explanation of the hydrocarbon group above.

As described above, two or more groups among R ¹ to R ³ in the above general formula (I) may be linked to each other to form a ring. More specifically, two or more groups among R ¹ to R ³ , preferably adjacent groups, may be linked to each other to form a ring such as an aliphatic ring, an aromatic ring, or a heterocycle containing a heteroatom such as a nitrogen atom, and these rings may further have a substituent.

From the viewpoint of activity, R ¹ among R ¹ to R ³ in the above general formula (I) is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and among these, a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a methyl group is more preferable.

In the above general formula (I), R ⁴ and R ⁵ may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and may be bonded to each other to form a double bond between a carbon atom and a nitrogen atom.

Examples of the halogen atoms, 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 the same groups as those exemplified in the description of R ¹ to R ³ above.

From the viewpoint of the structural stability of the resulting compound, it is particularly preferred that ^R4 and ^R5 are bonded to each other to form a double bond between the carbon atom to which ^R4 is bonded and the nitrogen atom to which ^R5 is bonded.

In the general formula (I), Z represents a structure represented by the following formula (II):

上記式（ＩＩ）中、●は、炭素原子（Ｃ）との結合点を示し、○は、窒素原子（Ｎ）との結合点を示す。

In the above formula (II), a black circle indicates a point of attachment to a carbon atom (C), and a white circle indicates a point of attachment to a nitrogen atom (N).

In the above formula (II), p is an integer from 1 to 6, preferably an integer from 1 to 4, and more preferably 2.

In the above formula (II), a plurality of R may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring.
The halogen atom includes fluorine, chlorine, bromine, and iodine.

The hydrocarbon group may be a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.

Specifically, linear or branched alkyl groups having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, or an n-hexyl group;
linear or branched alkenyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group;
linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, and more preferably 2 to 10 carbon atoms, such as an ethynyl group or a propargyl group;
cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, and more preferably 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or an adamantyl group;
cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as a cyclopentadienyl group, an indenyl group, or a fluorenyl group;
aryl groups having 6 to 30, preferably 6 to 20, and more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group;
Alkyl-substituted aryl groups such as a tolyl group, an iso-propylphenyl group, a t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group;
etc.

The above-mentioned hydrocarbon groups may have hydrogen atoms substituted with halogens. Examples of such hydrocarbon groups in which hydrogen atoms are substituted with halogens include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as trifluoromethyl groups, pentafluorophenyl groups, and chlorophenyl groups.

The above-mentioned hydrocarbon groups may be substituted with other hydrocarbon groups. Examples of such substituted hydrocarbon groups include aryl-substituted alkyl groups such as benzyl and cumyl groups.

Furthermore, the hydrocarbon group may be a heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, and carboxylic anhydride groups;
nitrogen-containing groups such as amino groups, imino groups, amido groups, imido groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups in the form of ammonium salts;
boron-containing groups such as a boranediyl group, a boranetriyl group, and a diboranyl group;
Sulfur-containing groups such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group;
Phosphorus-containing groups such as phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups;
It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

The 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, as well as groups in which these heterocyclic compound residues are further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

The silicon-containing group may be a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, or a hydrocarbon-substituted siloxy group, and more specifically may be a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, a dimethyl-t-butylsilyl group, or a dimethyl(pentafluorophenyl)silyl group. Of these, the methylsilyl group, the dimethylsilyl group, the trimethylsilyl group, the ethylsilyl group, the diethylsilyl group, the triethylsilyl group, the dimethylphenylsilyl group, or the triphenylsilyl group is preferred, and the trimethylsilyl group, the triethylsilyl group, the triphenylsilyl group, or the dimethylphenylsilyl group is particularly preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

The germanium-containing group or the tin-containing group may be a group in which the silicon of the silicon-containing group is replaced with germanium or tin.

Among the groups exemplified as the groups that the hydrocarbon group may have,
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group.
Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.
Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.
Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group.
Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group.
Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group.
Specific examples of the imide group include an acetimide group and a benzimide group.
Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
Specific examples of the alkylthio group include a methylthio group and an ethylthio group.
Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group.
Specific examples of the sulfonate group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.
Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group;
aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group;
Preferred are substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents such as a halogen atom, an alkyl group or alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms, or an aryl group or aryloxy group having 6 to 30, preferably 6 to 20, carbon atoms.

As described above, R can be a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and examples of these include the same as those exemplified in the description of the hydrocarbon group above.

In addition, adjacent R in the formula (II) may be bonded to each other to form a double bond. When adjacent R in Z are bonded to each other to form a double bond, specific examples of the structure represented by Z and the structure including the carbon atom and nitrogen atom to which Z is bonded include a pyrrole skeleton, a pyridine skeleton, an azepine skeleton, an azocine skeleton, an azonine skeleton, and an azecine skeleton. Of these, the pyrrole skeleton and the pyridine skeleton are preferred, and the pyridine skeleton is more preferred.

It is particularly preferable that Z has a structure represented by the following formula (III) (i.e., a pyridine skeleton).

上記式（ＩＩＩ）中、●は、炭素原子（Ｃ）との結合点を示し、○は、窒素原子（Ｎ）との結合点を示す。

In the above formula (III), a black circle indicates a point of attachment to a carbon atom (C), and a white circle indicates a point of attachment to a nitrogen atom (N).

In the above formula (III), R ⁶ to R ⁹ may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ⁶ to R ⁹ may be linked to each other to form a ring.
The halogen atom includes fluorine, chlorine, bromine, and iodine.

Examples of the hydrocarbon group include linear or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic hydrocarbon groups having 3 to 30 carbon atoms, and aromatic hydrocarbon groups having 6 to 30 carbon atoms. Specific examples include linear or branched alkyl groups having 1 to 30, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group;
linear or branched alkenyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group;
Straight-chain or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20, and more preferably 2 to 10 carbon atoms, such as an ethynyl group or a propargyl group; cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20, and more preferably 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or an adamantyl group;
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms, such as a cyclopentadienyl group, an indenyl group, or a fluorenyl group;
aryl groups having 6 to 30, preferably 6 to 20, and more preferably 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group;
Alkyl-substituted aryl groups such as a tolyl group, an iso-propylphenyl group, a t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group;
etc.

The above-mentioned hydrocarbon groups may have hydrogen atoms substituted with halogens. Examples of such hydrocarbon groups in which hydrogen atoms are substituted with halogens include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as trifluoromethyl groups, pentafluorophenyl groups, and chlorophenyl groups.

The above-mentioned hydrocarbon groups may be substituted with other hydrocarbon groups. Examples of such substituted hydrocarbon groups include aryl-substituted alkyl groups such as benzyl and cumyl groups.

Furthermore, the hydrocarbon group may be a heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, and carboxylic anhydride groups;
nitrogen-containing groups such as amino groups, imino groups, amido groups, imido groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups in the form of ammonium salts;
boron-containing groups such as a boranediyl group, a boranetriyl group, and a diboranyl group;
Sulfur-containing groups such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group;
Phosphorus-containing groups such as phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups;
It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

The 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, as well as groups in which these heterocyclic compound residues are further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. More specific examples include a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, a dimethyl-t-butylsilyl group, and a dimethyl(pentafluorophenyl)silyl group.
Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, triphenylsilyl group, etc. are preferred, and trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and dimethylphenylsilyl group are particularly preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy group.

The germanium-containing group or the tin-containing group may be a group in which the silicon of the silicon-containing group is replaced with germanium or tin.

Among the groups exemplified as the groups that the hydrocarbon group may have,
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group.
Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.
Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.
Specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group.
Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group.
Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group.
Specific examples of the imide group include an acetimide group and a benzimide group.
Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
Specific examples of the alkylthio group include a methylthio group and an ethylthio group.
Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group.
Specific examples of the sulfonate group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.
Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group;
aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group;
Preferred are substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents such as a halogen atom, an alkyl group or alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms, or an aryl group or aryloxy group having 6 to 30, preferably 6 to 20, carbon atoms.

As described above, ^R6 to ^R9 can be a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and examples of these include the same as those exemplified in the explanation of the hydrocarbon group above.

As described above, two or more groups among R ⁶ to R ⁹ in the above general formula (III) may be linked together to form a ring. More specifically, two or more groups among R ⁶ to R ⁹ , preferably adjacent groups, may be linked together to form a ring such as an aliphatic ring, an aromatic ring, or a heterocycle containing a heteroatom such as a nitrogen atom, and these rings may further have a substituent.

In the above general formula (I), when m is 2 or more, two of the groups represented by R ¹ to R ³ and R (including R ⁶ to R ⁹ when Z is a structure represented by general formula (III)) may be linked together. More specifically, R ¹ 's, R ² 's, R ³ 's, R ⁴ 's, R ⁵ 's, or R's (R ⁶ 's, R ⁷ 's, R ⁸ 's, R ⁹ 's) may be linked together, and, regardless of the above, substituents present at other positions may be linked together.

Furthermore, when m is 2 or more, ^R1 's, ^R2 's, ^R3 's, ^R4 's, ^R5 's, and R's ( ^R6 's, ^R7 's, ^R8 's, and ^R9 's) may be the same or different.

In the above general formula (I), X represents 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 compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group.
The halogen atom includes fluorine, chlorine, bromine, and iodine.

Examples of the hydrocarbon group include the same groups as those exemplified in the above description of R ¹ to R ^3. Specific examples include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a nonyl group, a dodecyl group, and an eicosyl group;
cycloalkyl groups having 3 to 30 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group;
Alkenyl groups such as a vinyl group, a propenyl group, or a cyclohexenyl group;
Arylalkyl groups such as a benzyl group, a phenylethyl group, and a phenylpropyl group;
Examples of the aryl groups include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, and a phenanthryl group.

However, the hydrocarbon groups are not limited to these. These hydrocarbon groups also include halogenated hydrocarbon groups, specifically groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is replaced with a halogen. Of these, halogenated hydrocarbon groups having 1 to 10 carbon atoms are preferred.

The oxygen-containing group may be a hydroxy group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; an aryloxy group such as a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, or a naphthoxy group; an arylalkoxy group such as a phenylmethoxy group or a phenylethoxy group; an acetoxy group; or a carbonyl group. However, the oxygen-containing group is not limited to these.

Examples of the sulfur-containing group include the same groups as those exemplified in the description of R ¹ to R ³ above. Specific examples of the sulfonate group include sulfonate groups such as a methylsulfonate group, a trifluoromethanesulfonate group, a phenylsulfonate group, a benzylsulfonate group, a p-toluenesulfonate group, a trimethylbenzenesulfonate group, a triisobutylbenzenesulfonate group, a p-chlorobenzenesulfonate group, and a pentafluorobenzenesulfonate group;
Examples of the sulfinate group include a methylsulfinate group, a phenylsulfinate group, a benzylsulfinate group, a p-toluenesulfinate group, a trimethylbenzenesulfinate group, a pentafluorobenzenesulfinate group, and the like; an alkylthio group; and an arylthio group. However, the sulfur-containing group is not limited to these.

Specific examples of the nitrogen-containing group include the same as those exemplified in the description of R ¹ to R ³ above, specifically, an amino group;
Alkylamino groups such as a methylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, or a dicyclohexylamino group;
Examples of the nitrogen-containing group include arylamino groups or alkylarylamino groups such as a phenylamino group, a diphenylamino group, a ditolylamino group, a dinaphthylamino group, and a methylphenylamino group, although the nitrogen-containing group is not limited to these.

Specific examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

Specific examples of the aluminum-containing group include AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.), but are not limited thereto.

Specific examples of the phosphorus-containing group include trialkylphosphine groups such as a trimethylphosphine group, a tributylphosphine group, and a tricyclohexylphosphine group;
triarylphosphine groups such as a triphenylphosphine group and a tritolylphosphine group;
Phosphite groups (phosphido groups) such as methyl phosphite groups, ethyl phosphite groups, and phenyl phosphite groups;
Examples of the aryl group include, but are not limited to, a phosphonic acid group; a phosphinic acid group; and the like.

Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl ₆ , and iodine-containing groups such as IO ₄ , but are not limited thereto.

Examples of the heterocyclic compound residue include the same ones as those exemplified in the explanation of R ¹ to R ³ above.

Specific examples of the silicon-containing group include the same groups as those exemplified in the description of R ¹ to R ³ above. Specific examples include hydrocarbon-substituted silyl groups such as a phenylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tricyclohexylsilyl group, a triphenylsilyl group, a methyldiphenylsilyl group, a tritolylsilyl group, and a trinaphthylsilyl group;
Hydrocarbon-substituted silyl ether groups, such as trimethylsilyl ether groups;
silicon-substituted alkyl groups such as trimethylsilylmethyl groups;
Examples of the aryl group include silicon-substituted aryl groups such as trimethylsilylphenyl group.

Specific examples of the germanium-containing group include those exemplified in the above description of R ¹ to R ³ , and specific examples include groups in which the silicon of the silicon-containing group is substituted with germanium.

Specific examples of the tin-containing group include those exemplified in the above description of R ¹ to R ³ , and more specific examples include groups in which the silicon of the above silicon-containing group is substituted with tin.

In the above general formula (I), n is a number that satisfies the valence of M, and is usually an integer from 0 to 5, preferably an integer from 1 to 4, more preferably an integer from 1 to 3, and particularly preferably 1. When n is 2 or more, the multiple Xs may be the same or different. Furthermore, the multiple groups represented by X may be bonded to each other to form a ring.

In the above general formula (I), R ¹⁰ to R ¹⁴ may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of R ¹⁰ to R ¹⁴ may be linked together to form a ring. For the halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, the same substituents as those for R ¹ to R ³ described above can be exemplified.

As an embodiment in which two or more groups among R ^{to R} are linked to each other to form a ring, preferably adjacent groups are linked to each other to form one ring or two rings, and the ring formed may form a ring such as an aromatic ring, an aliphatic ring, or a heterocycle containing a heteroatom such as a nitrogen atom, and these rings may further have a substituent.

Specific examples of the cyclopentadienyl group having R to ^R include ^alkyl -substituted cyclopentadienyl groups such as a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an ethylcyclopentadienyl group, a methylethylcyclopentadienyl group, a propylcyclopentadienyl group, a methylpropylcyclopentadienyl group, a butylcyclopentadienyl group, a methylbutylcyclopentadienyl group, and a hexylcyclopentadienyl group, as well as an indenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, etc. The hydrogen atoms in these groups may be substituted with a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom, etc.

R ¹⁰ to R ¹⁴ in the above general formula (I) are preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, from the viewpoint of protecting the central metal with a planar and sterically bulky ligand structure formed by introducing a substituent onto the cyclopentadienyl group, and two or more of R ¹⁰ to R ¹⁴ may be linked together to form a ring. However, from the viewpoint of imparting high copolymerizability to non-conjugated polyenes, it is preferable that three or more of R ¹⁰ to R ¹⁴ are hydrogen.

Specific examples of the transition metal compound [A] represented by the above general formula (I) are shown below, but the transition metal compound [A] is not limited to these.

なお、上記例示中、Ｍｅはメチル基を、Ｐｈはフェニル基を示す。また上記例示において、金属上の２個のメチル基のうち少なくとも１個を、一般式（Ｉ）におけるＸとして例示した置換基に置き換えた遷移金属化合物も、遷移金属化合物［Ａ］の例として挙げることができる。

In the above examples, Me represents a methyl group and Ph represents a phenyl group. In addition, examples of the transition metal compound [A] include transition metal compounds in which at least one of the two methyl groups on the metal is replaced with a substituent exemplified as X in general formula (I).

The method for producing such a transition metal compound [A] is not particularly limited, and it can be produced, for example, as follows.

First, the ligand can be synthesized by a previously reported method (Organic Letters, 2002, 4, 435.). Next, the obtained ligand can be reacted with a compound containing a transition metal atom M to synthesize the corresponding transition metal compound. The compound containing a transition metal atom M can be synthesized by a previously reported method (Organometallics, 1982, 1, 793. J. Am. Chem. Soc. 1988, 110, 7701.). Specifically, the ligand is dissolved in a solvent, and mixed with a compound having a transition metal atom M, such as a metal alkylate, a metal arylate, or a metal aryl alkylate, at a temperature range of -78°C to room temperature, and stirred at a temperature range of -78°C to room temperature or under reflux conditions for about 10 minutes to 48 hours. As the solvent, a solvent generally used for such reactions can be used, but among them, polar solvents such as ether and tetrahydrofuran (THF), and hydrocarbon solvents such as toluene are preferably used.

In addition, the transition metal compound obtained by this production method can be used directly in the polymerization of olefins as a reaction solution of the ligand and the metal compound without isolation.

[Compound [B] Group]
The following describes the compounds selected as components of the olefin polymerization catalyst of the present invention, which react with the organometallic compound [B-1], the organoaluminum oxy compound [B-2], and the transition metal compound [A] to form ion pairs.

[[B-1] Organometallic compound]
Specific examples of the organometallic compound [B-1] used in the present invention include organoaluminum compounds represented by the following general formula (B-1a), complex alkyl compounds of a metal in Group 1 of the periodic table and aluminum represented by the following general formula (B-1b), and dialkyl compounds of a metal in Group 2 or Group 12 of the periodic table represented by the following general formula (B-1c). Note that the organometallic compound [B-1] does not include the organoaluminum oxy compound [B-2] described below.

R ^a _p Al (OR ^b ) _q H _r Y _s ...(B-1a)
(In general formula (B-1a), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; Y represents a halogen atom; p represents a number satisfying 0<p≦3, q represents a number satisfying 0≦q<3, r represents a number satisfying 0≦r<3, s represents a number satisfying 0≦s<3, and m+n+p+q=3.)
M ³ AlR ^c ₄ ...(B-1b)
(In general formula (B-1b), ^M3 represents Li, Na or K, and ^Rc represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
R ^d R ^e M ⁴ ...(B-1c)
(In general formula (B-1c), R ^d and R ^e may be the same or different and each represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and M ⁴ represents Mg, Zn, or Cd.)
Examples of the organoaluminum compound represented by the general formula (B-1a) include the following compounds.
R ^ap _Al (OR ^b ) _3-p
(wherein R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and p is preferably a number satisfying 1.5≦p≦3),
R ^a _p AlY _3-p
(wherein R ^a represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, Y represents a halogen atom, and p is preferably a number satisfying 0<p<3),
R ^a _p AlH _3-p
(wherein R ^a represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and p is preferably a number satisfying 2≦p<3),
R ^a _p Al(OR ^b ) _q Y _s
(wherein R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; Y represents a halogen atom; p represents a number satisfying 0<p≦3, q represents a number satisfying 0≦q<3, s represents a number satisfying 0≦s<3, and p+q+s=3).

More specific examples of the organoaluminum compound belonging to the general formula (B-1a) include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum;
tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum;
Triarylaluminum such as triphenylaluminum and tritolylaluminum;
dialkylaluminum hydrides such as diisobutylaluminum hydride; trialkenylaluminums such as triisoprenylaluminum represented by (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers and z≧2x);
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, and isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide;
Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide;
partially alkoxylated alkylaluminum having an average composition represented by R ^a _2.5 Al(OR ^b ) _0.5 (wherein R ^a and R ^b may be the same or different and each represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms);
dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide;
partially halogenated alkylaluminums, such as alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, and the like;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums, such as alkylaluminum dihydrides, such as ethylaluminum dihydride, propylaluminum dihydride, etc.;
Examples of the aluminum compounds include partially alkoxylated and halogenated alkylaluminum compounds such as ethylaluminum ethoxy chloride, butylaluminum butoxy chloride, and ethylaluminum ethoxy bromide.

Compounds similar to (B-1a) can also be used in the present invention, such as organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms, such as (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the general formula (B-1b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

Examples of compounds that belong to the general formula (B-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, bis(pentafluorophenyl)zinc, dimethylcadmium, and diethylcadmium.

Other examples of the (B-1) organometallic compound that can be used include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, butyl magnesium bromide, and butyl magnesium chloride.

Furthermore, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium, can also be used as the organometallic compound (B-1).
The organometallic compounds [B-1] as described above may be used singly or in combination of two or more kinds.

[B-2] Organoaluminum oxy compound
The organoaluminum oxy compound [B-2] used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A-2-78687. Specific examples of the organoaluminum oxy compound [B-2] include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the like.

Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent.
(1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc., to react the adsorbed water or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or water vapor is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, tetrahydrofuran, etc.
(3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the resulting aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of organoaluminum compounds used in preparing aluminoxanes include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the general formula (B-1a) above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, with trimethylaluminum being particularly preferred.
The above organoaluminum compounds may be used singly or in combination of two or more.

Examples of solvents that can be used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and halides of the above aromatic, aliphatic, and alicyclic hydrocarbons, particularly chlorides and bromides. Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy-compound used in the present invention is preferably one in which the amount of Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less, calculated as Al atoms, i.e., it is preferably insoluble or poorly soluble in benzene.

The organoaluminum oxy compound [B-2] used in the present invention can also be, for example, an organoaluminum oxy compound containing boron represented by the following general formula (V):

（一般式（Ｖ）中、Ｒ¹¹は炭素原子数が１～１０の炭化水素基を示し、４つのＲ¹²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、炭素原子数が１～１０の炭化水素基を示す。）
前記一般式（Ｖ）で表されるボロンを含んだ有機アルミニウムオキシ化合物は、下記一般式（ＶＩ）で表されるアルキルボロン酸と、有機アルミニウム化合物とを、不活性ガス雰囲気下に不活性溶媒中で、－８０℃～室温の温度で１分～２４時間反応させることにより製造できる。

(In general formula (V), R ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms, and the four R ¹² may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.)
The boron-containing organoaluminum oxy compound represented by the general formula (V) can be produced by reacting an alkylboronic acid represented by the following general formula (VI) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

R ¹² -B(OH) ₂ ...(VI)
(In formula (VI), R ¹² represents the same group as R ¹² in formula (V).)
Specific examples of the alkylboronic acid represented by the general formula (V) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid, etc. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the general formula (B-1a) above. As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferred. These may be used alone or in combination of two or more.
The organoaluminum oxy compounds (B-2) as described above may be used singly or in combination of two or more kinds.

[B-3] Compound that reacts with transition metal compound [A] to form an ion pair]
Examples of the compound (hereinafter sometimes referred to as "ionizing ionic compound [B-3]") used in the present invention that reacts with the transition metal compound [A] [B-3] to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds.

Specifically, the Lewis acid includes compounds represented by _BR3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.
The ionic compound may, for example, be a compound represented by the following general formula (VII).

（一般式（ＶＩＩ）中、Ｒ¹³はＨ⁺、カルボニウムカチオン、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または遷移金属を有するフェロセニウムカチオンであり、Ｒ¹⁴～Ｒ¹⁷は、互いに同一でも異なっていてもよく、炭素原子数が１～１０の炭化水素基、好ましくは炭素原子数６～１０のアリール基または置換アリール基である。）。

(In general formula (VII), R ¹³ is H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a ferrocenium cation having a transition metal, and R ¹⁴ to R ¹⁷ may be the same or different and are a hydrocarbon group having 1 to 10 carbon atoms, preferably an aryl group or a substituted aryl group having 6 to 10 carbon atoms.)

Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

As R ¹³⁺ , a carbonium cation or an ammonium cation is preferable, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation or an N,N-diethylanilinium cation is particularly preferable.

Each of ^R to ^R is a hydrocarbon group having 1 to 10 carbon atoms, preferably an aryl group or a substituted aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a dimethylphenyl group, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, a pentafluorophenyl group, and a tolylpentafluorophenyl group. Of these, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, and a pentafluorophenyl group are preferred, and a pentafluorophenyl group is particularly preferred.

Other examples of ionic compounds include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

Specific examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

Specific examples of the dialkylammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

Further examples of ionic compounds include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula (VIII) or (IX).

（式（ＶＩＩＩ）中、Ｅｔはエチル基を示す。）

(In formula (VIII), Et represents an ethyl group.)

（式（ＩＸ）中、Ｅｔはエチル基を示す。）
イオン化イオン性化合物（化合物［Ｂ－３］）の例であるボラン化合物として具体的には、例えば、デカボラン；
ビス〔トリ（ｎ－ブチル）アンモニウム〕ノナボレート、ビス〔トリ（ｎ－ブチル）アンモニウム〕デカボレート、ビス〔トリ（ｎ－ブチル）アンモニウム〕ウンデカボレート、ビス〔トリ（ｎ－ブチル）アンモニウム〕ドデカボレート、ビス〔トリ（ｎ－ブチル）アンモニウム〕デカクロロデカボレート、ビス〔トリ（ｎ－ブチル）アンモニウム〕ドデカクロロドデカボレートなどのアニオンの塩；
トリ（ｎ－ブチル）アンモニウムビス（ドデカハイドライドドデカボレート）コバルト酸塩（ＩＩＩ）、ビス〔トリ（ｎ－ブチル）アンモニウム〕ビス（ドデカハイドライドドデカボレート）ニッケル酸塩（ＩＩＩ）などの金属ボランアニオンの塩などが挙げられる。

(In formula (IX), Et represents an ethyl group.)
Specific examples of the borane compound, which is an example of the ionizing ionic compound (compound [B-3]), include decaborane;
Salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate;
Examples of the salt include salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate) cobaltate (III) and bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate) nickelate (III).

Specific examples of carborane compounds, which are examples of ionized ionic compounds, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl-1,3-dicarbanonaborane. 1-methyl-7,8-dicarboxylic acid borane, dodecahydride-11-methyl-2,7-dicarboxylic acid borane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7-carboundecaborate, tri(n-butyl)ammonium 7,8-dicarboxaundecaborate, tri(n-butyl)ammonium 2,9-dicarboxaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarboxaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarboxaundecaborate Salts of anions such as carboundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate;
Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxecaporate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxecaporate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)nickelate (IV).

Heteropoly compounds, which are examples of ionized ionic compounds, are compounds containing atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specific examples of the acid include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids. Examples of the salt include salts of the acid with metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

Isopoly compounds, which are examples of ionized ionic compounds, are compounds composed of metal ions of one type of atom selected from vanadium, niobium, molybdenum and tungsten, and can be considered to be molecular ion species of metal oxides.Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids.Furthermore, examples of the salts include salts of the acids with metals of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.
The above-mentioned ionizing ionic compounds (compounds [B-3] that react with the transition metal compound [A] to form an ion pair) may be used singly or in combination of two or more kinds.

The above-described compounds that react with the organometallic compound [B-1], the organoaluminum oxy compound [B-2], and the transition metal compound [A] to form an ion pair can be used in combination. In particular, when the transition metal compound [A] of the present invention is used, it has been revealed that high polymerization activity and high copolymerizability are exhibited when the organometallic compound [B-1] and the compound that reacts with the transition metal compound [A] to form an ion pair are used in combination. Up until now, examples have been reported in which high polymerization activity is exhibited by using the organoaluminum oxy compound [B-2] such as methylaluminoxane as a cocatalyst component in combination with a known transition metal compound, but the organoaluminum oxy compound (B-2) such as methylaluminoxane is generally expensive, and depending on the amount used, this leads to high costs for the resulting olefin polymer.

On the other hand, as described above, the transition metal compound [A] in the present invention exhibits high polymerization activity and high copolymerizability even when used in combination with the cocatalyst components [B-1] organometallic compound and [B-3] a compound that reacts with the transition metal compound [A] to form an ion pair, and these cocatalyst components are very inexpensively available, which has the advantage that it is possible to produce olefin polymers at low cost.

The olefin polymerization catalyst according to the present invention may contain the above-mentioned transition metal compound [A], at least one compound [B] selected from the group consisting of [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and [B-3] ionizing ionic compounds, and may also contain the following carrier [C] as necessary.

[Carrier [C]]
The olefin polymerization catalyst according to the present invention may use a carrier [C], if necessary.
The carrier [C] that can be used in the present invention is an inorganic or organic compound, and is a granular or fine particle solid. By supporting the transition metal compound [A] and the compound [B] on the carrier [C], a polymer with good morphology can be obtained.
The inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral, or an ion-exchangeable layered compound.

Specifically, the porous oxide may be SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a composite or mixture containing these, and may further be, for example, natural or synthetic zeolite, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, etc. Among these, the porous oxide is preferably one containing SiO ₂ and/or Al ₂ O ₃ as the main component.

In addition, the above-mentioned porous oxide may contain small amounts of carbonates _{, sulfates ,} nitrates, and oxide components such as _Na2CO3 , _K2CO3 , _CaCO3 , _MgCO3 , _Na2SO4 , _Al2 ( _SO4 ) ₃ , _BaSO4 , _KNO3 , Mg( _NO3 ) ₂ , Al( _NO3 ) _{3 ,} Na2O, _K2O , and _Li2O .

The properties of such porous oxides vary depending on the type and production method, but the porous oxides preferably used in the present invention have a particle size of 10 to 300 μm, preferably 20 to 200 μm, a specific surface area of 50 to 1000 ^{m 2} /g, preferably 100 to 700 ^{m 2} /g, and a pore volume of 0.3 to 3.0 cm ³ /g. Such porous oxides are calcined at 100 to 1000° C., preferably 150 to 700° C., as necessary, before use.

As the inorganic halide, _MgCl2 , _MgBr2 , _MnCl2 , _MnBr2 , etc. can be used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. In addition, the inorganic halide may be dissolved in a solvent such as alcohol, and then precipitated into fine particles by a precipitating agent.

The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compounds are compounds with a crystal structure in which planes formed by ionic bonds are stacked in parallel with each other with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and artificially synthesized products can also be used.

Examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl ₂ type, and CdI ₂ type.

Further, examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, and halloysite, and examples of ion-exchangeable layered compounds include α-Zr(HAsO ₄ ) _{2.H 2 O} , α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) _{2.3H 2} O, α-Ti(HPO ₄ ) ₂ , α-Ti(HAsO ₄ ) _{2.H 2} O, α-Sn(HPO ₄ ) _{2.H 2} O, γ-Zr(HPO ₄ ) ₂ , and γ-Ti(HPO ₄ ) _2. and crystalline acid salts of polyvalent metals such as γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ O.

Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc/g or more, particularly preferably 0.3 to 5 cc/g, having a radius of 20 Å or more, as measured by mercury intrusion porosimetry, where the pore volume is measured for a pore radius range of 20 to 30,000 Å by mercury intrusion porosimetry using a mercury porosimeter.
When a carrier having a pore volume of less than 0.1 cc/g and a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

It is also preferable to subject the clay and clay minerals used in the present invention to chemical treatment. Any of the following chemical treatments can be used: surface treatment to remove impurities adhering to the surface, and treatment to affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment removes surface impurities and increases the surface area by dissolving cations such as Al, Fe, and Mg in the crystalline structure. Alkaline treatment destroys the crystalline structure of the clay, resulting in a change in the structure of the clay. Salt treatment and organic treatment also form ionic complexes, molecular complexes, and organic derivatives, which can change the surface area and interlayer distance.

The ion-exchangeable layered compound used in the present invention may be a layered compound in which the space between layers is expanded by utilizing the ion exchangeability and exchanging the exchangeable ions between layers with other large bulky ions. Such bulky ions play a role of supporting the layered structure and are usually called pillars. The introduction of another substance between layers of a layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ (R is a hydrocarbon group, etc.), and metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ and [Fe ₃ O(OCOCH ₃ ) ₆ ] ⁺ . These compounds may be used alone or in combination of two or more. In addition, when intercalating these compounds, polymers obtained by hydrolysis of metal alkoxides (R represents a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ , and Ge(OR) ₄ , and colloidal inorganic compounds such as SiO ₂ can be coexisted. Examples of pillars include oxides generated by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as is, or may be used after treatment such as ball milling or sieving. They may also be used after newly adding and adsorbing water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more kinds.
Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica are particularly preferred.

As mentioned above, the carrier [C] is an inorganic or organic compound, and examples of organic compounds include granular or fine particle solids with particle sizes in the range of 10 to 300 μm. Specific examples include (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane and styrene, and their modified products.

The olefin polymerization catalyst according to the present invention contains the above-mentioned transition metal compound [A], preferably the above-mentioned compound [B], and, if necessary, the carrier [C]. In addition to these, if necessary, it can also contain the following specific organic compound component [D].

[Organic compound component [D]]
In the present invention, the organic compound component [D] is used, if necessary, for the purpose of improving the polymerization performance (e.g., catalytic activity) of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (e.g., increasing the molecular weight of the produced polymer). Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

The alcohols and phenolic compounds typically used are those represented by ^R18 -OH, where ^R18 represents a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, the number of carbon atoms is 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, the number of carbon atoms is 6 to 50).

As the alcohols, those in which R ¹⁸ is a halogenated hydrocarbon group are preferred, and as the phenolic compounds, those in which the α,α'-positions of the hydroxyl group are substituted with a hydrocarbon having 1 to 20 carbon atoms are preferred.

The carboxylic acid is usually represented by R ¹⁹ -COOH, where R ¹⁹ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and is particularly preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms.

As the phosphorus compound, phosphoric acids having a P--O--H bond, phosphates having a P--OR or P=O bond, and phosphine oxide compounds are preferably used.
The sulfonate may be represented by the following general formula (X).

（一般式（Ｘ）中、Ｍ⁵は周期律表第１～１４族の元素であり、Ｒ²⁰は水素、炭素原子数１～２０の炭化水素基または炭素原子数１～２０のハロゲン化炭化水素基であり、Ｚは水素原子、ハロゲン原子、炭素原子数が１～２０の炭化水素基または炭素原子数が１～２０のハロゲン化炭化水素基であり、ｔは１～７の整数であり、ｕは１≦ｕ≦７となる整数である。また、ｔ－ｕはｔ－ｕ≧１となる整数である。）

(In general formula (X), ^M5 is an element of Groups 1 to 14 of the periodic table; ^R20 is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; t is an integer from 1 to 7; u is an integer that satisfies 1≦u≦7; and t-u is an integer that satisfies t-u≧1.)

[Method for producing ethylene-α-olefin-non-conjugated polyene copolymer]
In the process for producing an ethylene-α-olefin-non-conjugated polyene polymer of the present invention, an ethylene-α-olefin-non-conjugated polyene polymer can be obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the presence of the above-mentioned olefin polymerization catalyst.
In the present invention, when ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene are copolymerized, the method of using and the order of adding each component constituting the above-mentioned olefin polymerization catalyst may be arbitrarily selected, and the following method may be exemplified.

(1) A method in which the transition metal compound [A] is added alone to a polymerization reactor.
(2) A method of adding the transition metal compound [A] and the compound [B] to a polymerization reactor in any order, (3) A method of adding the catalyst component in which the transition metal compound [A] is supported on the carrier [C], and the compound [B] to a polymerization reactor in any order.
(4) A method in which a catalyst component in which the compound [B] is supported on a carrier [C] and a transition metal compound [A] are added to a polymerization reactor in any order.
(5) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C] is added to a polymerization vessel.
(6) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C], and the compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different.
(7) A method in which a catalyst component in which the compound [B] is supported on the carrier [C], and a transition metal compound [A] are added to a polymerization vessel in any order.
(8) A method in which a catalyst component in which the compound [B] is supported on a carrier [C], a transition metal compound [A], and a compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different.
(9) A method in which a component in which the transition metal compound [A] is supported on a carrier [C] and a component in which the compound [B] is supported on a carrier [C] are added to a polymerization vessel in any order.
(10) A method in which a component in which a transition metal compound [A] is supported on a carrier [C], a component in which a compound [B] is supported on a carrier [C], and a compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different.
(11) A method in which the transition metal compound [A], the compound [B], and the organic compound component [D] are added to a polymerization reactor in any order.
(12) A method in which the compound [B] and the organic compound component [D], which have been contacted in advance, and the transition metal compound [A] are added to a polymerization reactor in any order.
(13) A method in which the compound [B], the organic compound component [D] supported on the carrier [C], and the transition metal compound [A] are added to a polymerization reactor in any order.
(14) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] have been contacted in advance, and an organic compound component [D] are added to a polymerization reactor in any order.
(15) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] have been contacted in advance, the compound [B], and an organic compound component [D] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different.
(16) A method of adding a catalyst component in which a transition metal compound [A] is contacted with a compound [B] in advance, and a component in which a compound [B] is contacted with an organic compound component [D] in advance, to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different.
(17) A method in which a transition metal compound [A] supported on a carrier [C], a compound [B], and an organic compound component [D] are added to a polymerization reactor in any order.
(18) A method in which a component in which a transition metal compound [A] is supported on a carrier [C], and a component in which a compound [B] is contacted with an organic compound component [D] in advance are added to a polymerization reactor in any order.
(19) A method in which a catalyst component obtained by previously contacting a transition metal compound [A], a compound [B] and an organic compound component [D] in any order is added to a polymerization vessel.
(20) A method in which a catalyst component obtained by contacting a transition metal compound [A], a compound [B] and an organic compound component [D] in any order in advance, and compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different.
(21) A method in which a catalyst comprising a transition metal compound [A], a compound [B] and an organic compound component [D] supported on a carrier [C] is added to a polymerization reactor.
(22) A method in which a catalyst component comprising a transition metal compound [A], a compound [B] and an organic compound component [D] supported on a carrier [C], and a compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] may be the same or different.

In the solid catalyst component in which the transition metal compound [A] is supported on the support [C], and in the solid catalyst component in which the transition metal compound [A] and the compound [B] are supported on the support [C], an olefin may be prepolymerized, or the transition metal compound [A] and/or the compound [B] may be further supported on the prepolymerized solid catalyst component.
In each of the above methods (2) to (5), at least two of the transition metal compound [A], the compound [B] and the support [C] may be previously contacted with each other.

In the above methods (4) and (5) in which the compound [B] is supported, the unsupported compound [B] may be added in any order, if necessary. In this case, the compound [B] may be the same as or different from the compound [B] supported on the carrier [C].

In addition, the solid catalyst component in which the transition metal compound [A] is supported on the above-mentioned carrier [C], and the solid catalyst component in which the transition metal compound [A] and the compound [B] are supported on the carrier [C] may be prepolymerized with an olefin, or a further catalyst component may be supported on the prepolymerized solid catalyst component.

The prepolymerization is preferably a substantially homopolymerization of 95 mol% or more of olefin. The olefin used in the prepolymerization is preferably the same as that used in the main polymerization. Specifically, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene, cyclopentene, and vinylcyclohexane are particularly preferred, and ethylene, propylene, 1-butene, 1-heptene, 3-methyl-1-butene, 1-hexene, and 4-methyl-1-pentene are particularly preferred.

The amount of olefin polymerized in the prepolymerization is in the range of 0.1 to 1000 g, preferably 1 to 50 g, per gram of the solid catalyst component.
The above prepolymerization is usually preferably carried out by slurry polymerization, and as a solvent, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, or toluene can be used alone or in combination.

The prepolymerization temperature is preferably in the range of -50 to +100°C, particularly -20 to +80°C, and more preferably 0 to +40°C. The prepolymerization time may be appropriately determined depending on the prepolymerization temperature and the amount of polymerization in the prepolymerization, and the pressure in the prepolymerization is not limited, but in the case of slurry polymerization, it is generally about normal pressure to 50 kg/ ^cm2 . Each prepolymerization may be carried out in any of batch, semi-batch, and continuous manners. After the completion of each prepolymerization, it is preferable to wash with saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene, either alone or with a mixed solvent of these, and the number of washings is usually preferably 5 to 6 times.

In the present invention, an ethylene-α-olefin-non-conjugated polyene copolymer can be suitably obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the presence of the above-mentioned olefin polymerization catalyst.

When olefin polymerization is carried out using the above catalyst, the transition metal compound [A] is used in an amount of usually 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 to 10 ^-8 mol, per liter of reaction volume.

The organometallic compound [B-1] is used in an amount such that the molar ratio [[B-1]/[M]] of the organometallic compound [B-1] to the total transition metal atoms [M] in the transition metal compound [A] is usually 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound [B-2] is used in an amount such that the molar ratio [[B-2]/[M]] of the aluminum atoms in the organoaluminum oxy compound [B-2] to the total transition metals [M] in the transition metal compound [A] is usually 10 to 500,000, preferably 20 to 100,000. The ionized ionic compound [B-3] is used in an amount such that the molar ratio [[B-3]/[M]] of the ionized ionic compound [B-3] to the transition metal atoms [M] in the transition metal compound [A] is usually 1 to 10, preferably 1 to 5.

When compound [B] is an organometallic compound [B-1], the organic compound component [D] is used in an amount such that the molar ratio [[D]/[B-1]] is usually 0.01 to 10, preferably 0.1 to 5. When compound [B] is an organoaluminum oxy compound [B-2], the organic compound component [D] is used in an amount such that the molar ratio [[D]/[B-2]] is usually 0.01 to 2, preferably 0.005 to 1. When compound [B] is an ionized ionic compound [B-3], the organic compound component [D] is used in an amount such that the molar ratio [[D]/[B-3]] is usually 0.01 to 10, preferably 0.1 to 5.

In the present invention, the method for producing the ethylene-α-olefin-non-conjugated polyene copolymer is not particularly limited and can be carried out by any of liquid phase polymerization methods such as solution (dissolution) polymerization and suspension polymerization, or gas phase polymerization, but it is preferable to have a step of obtaining the following polymerization reaction liquid.

The process for obtaining a polymerization reaction liquid is a process for copolymerizing ethylene, the α-olefin, and the non-conjugated polyene in the presence of an olefin polymerization catalyst medium containing the transition metal compound [A] according to the present invention using an aliphatic hydrocarbon as a polymerization solvent, thereby obtaining a polymerization reaction liquid of an ethylene-α-olefin-non-conjugated polyene copolymer.

If the concentration of the ethylene-α-olefin-non-conjugated polyene copolymer in the polymerization solvent exceeds the above range, the viscosity of the polymerization solution will be too high, and the solution will not be stirred uniformly, which may make the polymerization reaction difficult.

Examples of polymerization solvents include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These can be used alone or in combination of two or more. Olefin itself can also be used as the solvent. Of these, hexane is preferred from the viewpoint of separation and purification from the resulting ethylene-α-olefin-non-conjugated polyene copolymer.

The polymerization temperature is usually -50 to +200°C, preferably 0 to +200°C, and more preferably +80 to +200°C. Although it depends on the molecular weight and polymerization activity of the metallocene catalyst system used, a higher temperature (+80°C or higher) is desirable from the standpoint of catalyst activity, copolymerizability, and productivity.

The polymerization pressure is usually between normal pressure and 10 MPa gauge pressure, preferably between normal pressure and 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous, and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

The reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

The molecular weight of the resulting ethylene-α-olefin-non-conjugated polyene copolymer can be adjusted by making hydrogen present in the polymerization system or by changing the polymerization temperature. It can also be adjusted by the amount of compound [B] used. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the appropriate amount is about 0.001 to 100 NL per kg of olefin.

The molar ratio of ethylene to the above α-olefin (ethylene/α-olefin) is preferably 25/75 to 80/20, more preferably 30/70 to 70/30.
The molar ratio of the ethylene to the non-conjugated polyene (ethylene/non-conjugated polyene) is preferably 70/30 to 99/1, more preferably 80/20 to 98/2.

[Ethylene-α-olefin-non-conjugated polyene copolymer]
The ethylene/α-olefin/non-conjugated polyene copolymer obtained by the production method of the present invention will be described below.

[α-Olefin]
The α-olefin constituting the ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention is usually an α-olefin having 3 to 20 carbon atoms, and examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferred, and propylene is particularly preferred. Such α-olefins are preferred because the raw material cost is relatively low, the ethylene-α-olefin-non-conjugated polyene copolymer exhibits excellent mechanical properties, and a molded article having rubber elasticity can be obtained. These α-olefins may be used alone or in combination.

The ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention contains structural units derived from at least one type of α-olefin having 3 to 20 carbon atoms, and may contain structural units derived from two or more types of α-olefins having 3 to 20 carbon atoms.

[Non-conjugated polyenes]
Specific examples of the non-conjugated polyene constituting the ethylene/α-olefin/non-conjugated polyene copolymer according to the present invention include cyclic dienes such as 5-ethylidene-2-norbornene (ENB), 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene (VNB), 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, and norbornadiene; chain non-conjugated dienes such as 2,3-diisopropylidene-5-norbornene, 4-ethylidene-8-methyl-1,7-nonadiene, etc. Among these, 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), 5-methylene-2-norbornene, 7-methyl-1,6-octadiene, 1,4-hexadiene, and dicyclopentadiene are preferred. Among these, 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), and 7-methyl-1,6-octadiene are particularly preferred. When a composition containing an ethylene-α-olefin-non-conjugated polyene copolymer is crosslinked with sulfur, ENB, 1,4-hexadiene, and dicyclopentadiene, which have excellent mechanical strength, are preferred as such non-conjugated polyenes, and when a composition containing an ethylene-α-olefin-non-conjugated polyene copolymer is crosslinked with an organic peroxide, VNB and 5-methylene-2-norbornene, which have excellent crosslinking efficiency and heat aging resistance, are preferred. These non-conjugated polyenes may be used alone or in combination of two or more.

The ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention usually has a content of constitutional units derived from non-conjugated polyene of 0.1 to 5 mol %, preferably 2.5 to 4 mol %. The total of the constitutional units derived from ethylene, the constitutional units derived from α-olefin, and the constitutional units derived from non-conjugated polyene is 100 mol %. Within the above range, the strength, rubber elasticity, compression set, etc. of a molded article obtained from a composition containing the ethylene-α-olefin-non-conjugated polyene copolymer are excellent, and when the composition containing the ethylene-α-olefin-non-conjugated polyene copolymer contains a crosslinking agent and a foaming agent, it is preferable because it has excellent foamability, dimensional stability, etc.
The content of the structural units derived from ethylene can be determined by ¹³ C NMR.

The ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention typically has an intrinsic viscosity [η] measured in decalin at 135°C of 0.1 to 1.0 dL/g, preferably 0.2 to 0.5 dL/g.

The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
The structure of the transition metal compound [A] was determined by measuring the ¹ H NMR spectrum (270 MHz, GSH-270 manufactured by JEOL Ltd.), FD-mass (hereinafter FD-MS) spectrum (SX-102A manufactured by JEOL Ltd.), and the like.
The physical properties of the ethylene-α-olefin-non-conjugated polyene copolymer were measured by the following methods.

[Ethylene content, propylene content, 5-ethylidene-2-norbornene (ENB) content]
13C NMR spectra were measured using o-dichlorobenzene/benzene- _d6 (4/1 {vol/vol%}) as the measurement solvent under the following measurement conditions (100 MHz, JEOL ECX400P): measurement temperature 120°C, spectrum width 250 ppm, pulse repetition time 5.5 seconds, pulse width 4.7 μsec (45° pulse), or under the following measurement conditions (125 MHz, Bruker Biospin AVANCEIII cryo-500): measurement temperature 120°C, spectrum width 250 ppm, pulse repetition time 5.5 seconds, pulse width ^5.0 μsec (45° pulse), and calculations were performed.

[Intrinsic viscosity ([η])]
The measurement was performed at 135°C using decalin solvent. Approximately 20 mg of the polymer was dissolved in 15 mL of decalin, and the specific viscosity η _sp was measured in an oil bath at 135°C. After diluting the decalin solution by adding 5 mL of decalin solvent, the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated two more times, and the value of η _sp /C when the concentration (C) was extrapolated to 0 was adopted as the limiting viscosity.
[η]=lim(η _sp /C) (C→0)

[Synthesis of transition metal compound [A]]
[Synthesis Example 1]
In a 50 mL eggplant flask that had been thoroughly dried and substituted with nitrogen, 575 mg (2.62 mmol) of trichloro(η5-cyclopentadienyl)titanium and 20 mL of ether were placed and cooled in a methanol-dry ice bath at about -30°C. To this suspension, 6.8 mL (7.89 mmol) of a 1.16 M ether solution of methyllithium was added. To the resulting gray-green suspension, a toluene solution (20 mL) of 440 mg (2.55 mmol) of 2-(2-pyridyl)-3,5-dimethylpyrrole was dropped, and the mixture was stirred overnight while slowly warming to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrate of the filtrate was azeotroped with a hexane-ether mixture, and the obtained solid was washed with hexane and then pentane, to obtain 500 mg of the target product shown below (hereinafter referred to as transition metal compound [A-1]) (dark red powder, 64% yield).
^1H NMR ( _CDCl3 ): δ=7.56-7.44 (3H, m, Ar-H), 6.70-6.65 (1H, m, Ar-H), 6.50 (5H, s, Cp-H), 5.85 (1H, s, Ar-H), 2. 41 (3H, s, Ar-Me), 2.00 (3H, s, Ar-Me), 0.96 (3H, d, Ti-Me, J = 0.9 Hz), 0.80 (3H, d, Ti-Me, J = 0.9 Hz)
FD-MS (m/z): 314.1

[Synthesis Example 2]
In a 50 mL eggplant flask that had been thoroughly dried and substituted with nitrogen, 480 mg (2.14 mmol) of trichloro(η5-cyclopentadienyl)titanium and 20 mL of ether were placed and cooled in a methanol-dry ice bath at about -30°C. 5.5 mL (6.38 mmol) of a 1.16 M ether solution of methyllithium was added to this suspension. A toluene solution (20 mL) of 630 mg (2.13 mmol) of 2-(2-pyridyl)-3,5-diphenylpyrrole was added dropwise to the resulting gray-green suspension, and the mixture was stirred overnight while slowly warming to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrated filtrate was washed with hexane and then pentane to obtain 512 mg (dark red powder, 50% yield) of the target product shown below (hereinafter referred to as transition metal compound [A-2]).
¹ H NMR (CDCl ₃ ): δ = 7.67-7.23 (13H, m, Ar-H), 6.79-6.74 (1H, m, Ar-H), 6.45 (5H, s, Cp-H), 6.35 (1H, s, Ar-H), 0.75 (3H, broad s, Ti-Me), 0.50 (3H, broad s, Ti-Me) FD-MS (m/z): 438.2

[Synthesis Example 3]
In a 50 mL eggplant flask that had been thoroughly dried and substituted with nitrogen, 732 mg (2.60 mmol) of trichloro(tert-butyl-η5-cyclopentadienyl)titanium and 30 mL of ether were placed and cooled in a methanol-dry ice bath at about -30°C. To this suspension, 6.9 mL (8.00 mmol) of a 1.16 M ether solution of methyllithium was added. To the resulting gray-green suspension, a toluene solution (30 mL) of 460 mg (2.67 mmol) of 2-(2-pyridyl)-3,5-dimethylpyrrole was dropped, and the mixture was stirred overnight while slowly warming to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrated filtrate was dissolved in a small amount of pentane and left to stand overnight in a refrigerator, and the precipitated solid was filtered off, to obtain 499 mg (dark red powder, 50% yield) of the target product shown below (hereinafter referred to as transition metal compound [A-3]).
^1H NMR ( _CDCl3 ): δ = 7.57-7.45 (3H, m, Ar-H), 7.11-7.02 (1H, m, Ar-H), 6.67-6.62 (1H, m, Ar-H), 6.14-6.11 (1H, m, Cp-H ), 6.00-5.97 (1H, m, Cp-H), 5.83 (1H, s, Ar-H), 2.39 (3H, s, Ar-Me), 1.99 (3H, s, Ar-Me), 0.99 (3H, broad s, Ti-Me), 0.81 (3H, broad s, Ti-Me), 0.80 (9H, s, Cp-C(CH ₃ ) ₃ ) FD-MS (m/z): 370.2

[Synthesis Example 4]
In a 50 mL eggplant flask that had been thoroughly dried and substituted with nitrogen, 770 mg (2.80 mmol) of trichloro(η5-indenyl)titanium and 30 mL of ether were placed and cooled in a methanol-dry ice bath at about -78°C. To this suspension, 7.25 mL (8.41 mmol) of a 1.16 M ether solution of methyllithium was added. After the obtained brown suspension was heated to -30°C, a toluene solution (30 mL) of 479 mg (2.78 mmol) of 2-(2-pyridyl)-3,5-dimethylpyrrole was added dropwise, and the mixture was stirred overnight while slowly heating to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrated filtrate was washed with pentane to obtain 567 mg (red powder, 64% yield) of the target product shown below (hereinafter referred to as transition metal compound [A-4]).
^1H NMR ( _CDCl3 ): δ = 7.94-7.90 (1H, m, Ar-H), 7.58-7.52 (1H, m, Ar-H), 7.43-7.39 (2H, m, Ar -H), 7.36-7.25 (2H, m, Ar-H), 6.70-6.64 (1H, m, Ar-H), 6.21 (1H, t, Ar-H, J= 3.5Hz), 6.05-6.03 (1H, m, Ar-H), 5.83 (1H, s, Ar-H), 2.38 (3H, s, Ar-Me), 2. 13 (3H, s, Ar-Me), 0.89 (3H, d, Ti-Me, J = 1.0 Hz), 0.71 (3H, d, Ti-Me, J = 1.0 Hz)
FD-MS (m/z): 364.1

[Synthesis Example 5]
In a 50 mL eggplant flask that had been thoroughly dried and substituted with nitrogen, 285 mg (1.27 mmol) of trichloro(η5-cyclopentadienyl)titanium and 20 mL of toluene were placed and cooled in a methanol-dry ice bath at about -78°C. 3.60 mL (3.92 mmol) of a 1.09 M ether solution of methyllithium was added to this suspension. The resulting ocher suspension was stirred at -78°C for 75 minutes, and then 182 mg (1.26 mmol) of 2-(2-pyridyl)-pyrrole in toluene (20 mL) was added dropwise, and the mixture was stirred overnight while slowly warming to room temperature. The reaction solution was concentrated using a vacuum pump, and the residue was extracted with toluene and filtered through Celite. The concentrated filtrate was extracted and concentrated with methylcyclohexane, and the oily product obtained was washed with hexane to obtain 38.9 mg (dark red oily product, 11% yield) of the target product shown below (hereinafter referred to as transition metal compound [A-5]).
^1H NMR _{( C7D8} ): δ=7.13-7.09 (1H, m, Ar-H), 6.86-6.73 (3H, m, Ar-H), 6.65-6.64 (1H, m, Ar-H), 6. 39-6.37 (1H, m, Ar-H), 6.11-6.06 (1H, m, Ar-H), 5.97 (5H, s, Cp-H), 1.22 (6H, broad s, Ti-Me)
FD-MS (m/z): 286.1

[Synthesis Example 6]
According to the description in JP-A-2007-529584, the transition metal compound [A-6] shown below was synthesized.

[Production of ethylene-propylene-ENB copolymer]
[Example 1-1]
1030 mL of hexane and 12 mL of ethylidenenorbornene (ENB) were charged into a stainless steel autoclave with a capacity of 2 L, which had been thoroughly substituted with nitrogen. The temperature in the system was then raised to 95° C., and 0.90 MPa of propylene was charged at a partial pressure. Ethylene was then fed to the autoclave, and the total pressure was adjusted to 1.6 MPa-G. Next, 0.3 mmol of triisobutylaluminum, 0.005 mmol of the transition metal compound [A-1], and 0.02 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were fed with nitrogen, and polymerization was initiated by setting the stirring speed to 250 rpm. Then, only ethylene was continuously fed to maintain the total pressure at 1.6 MPa-G, and polymerization was carried out at 95° C. for 15 minutes. A small amount of ethanol was added to the system to terminate the polymerization, and unreacted ethylene was purged. The obtained polymer solution was poured into a large excess of a mixed solution of methanol/acetone and air-dried overnight. The obtained polymer was recovered by filtration and dried overnight at 120° C. under reduced pressure.
As a result, 0.79 g of an ethylene-propylene-ENB copolymer having an ethylene content of 63.2 mol % and an ENB content of 12.7 mass % was obtained. The polymerization activity was 0.6 kg/mmol-Ti/h.

[Comparative Example 1-2]
The same procedure as in Example 1-1 was carried out, except that 0.005 mmol of the transition metal compound [A-1] was changed to 0.001 mmol of the transition metal compound [A-5].
As a result, 0.62 g of an ethylene/propylene/ENB copolymer having an ethylene content of 60.2 mol % and an ENB content of 7.4 mass % was obtained. The polymerization activity was 2.5 kg/mmol-Ti/h.

[Example 2-1]
1030 mL of hexane and 4 mL of ethylidenenorbornene (ENB) were charged into a stainless steel autoclave with a capacity of 2 L, which had been thoroughly substituted with nitrogen. After raising the temperature in the system to 95° C., 0.45 MPa of propylene was charged at a partial pressure, and ethylene was supplied to adjust the total pressure to 1.6 MPa-G. Next, 0.3 mmol of triisobutylaluminum, 0.0025 mmol of the transition metal compound [A-1], and 0.01 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were pressed in with nitrogen, and polymerization was initiated by setting the stirring speed to 250 rpm. Thereafter, polymerization was carried out at 95° C. for 15 minutes while maintaining the total pressure at 1.6 MPa-G by continuously supplying only ethylene. A small amount of ethanol was added to the system to terminate the polymerization, and unreacted ethylene was purged. The obtained polymer solution was poured into a large excess of a mixed solution of methanol/acetone and air-dried overnight. The obtained polymer was recovered by filtration and dried overnight at 120° C. under reduced pressure.
As a result, 1.51 g of an ethylene-propylene-ENB copolymer having an ethylene content of 79.0 mol % and an ENB content of 13.1 mass % was obtained. The polymerization activity was 2.4 kg/mmol-Ti/h.

[Example 2-2]
The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-2].
As a result, 0.90 g of an ethylene/propylene/ENB copolymer having an ethylene content of 80.2 mol % and an ENB content of 11.9 mass % was obtained. The polymerization activity was 1.4 kg/mmol-Ti/h.

[Example 2-3]
The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-3].
As a result, 1.05 g of an ethylene-propylene-ENB copolymer having an ethylene content of 77.0 mol % and an ENB content of 10.2 mass % was obtained. The polymerization activity was 1.7 kg/mmol-Ti/h.

[Example 2-4]
The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-4].
As a result, 3.05 g of an ethylene-propylene-ENB copolymer having an ethylene content of 79.0 mol % and an ENB content of 9.5 mass % was obtained. The polymerization activity was 4.9 kg/mmol-Ti/h.

[ Comparative Example 2-5]
The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-5].
As a result, 3.63 g of an ethylene-propylene-ENB copolymer having an ethylene content of 72.3 mol % and an ENB content of 6.7 mass % was obtained. The polymerization activity was 5.8 kg/mmol-Ti/h.

[Comparative Example 2-6]
The same procedure as in Example 2-1 was carried out, except that the transition metal compound [A-1] used in Example 2-1 was changed to the transition metal compound [A-6].
As a result, 9.06 g of an ethylene-propylene-ENB copolymer having an ethylene content of 88.5 mol % and an ENB content of 2.4 mass % was obtained. The polymerization activity was 72.5 kg/mmol-Ti/h.

Claims (9)

[A] a transition metal compound represented by the following general formula (I), and [B] [B-1] an organometallic compound,
A method for producing an ethylene-α-olefin-non-conjugated polyene copolymer, comprising a step [P] of polymerizing ethylene, an α-olefin, and a non-conjugated polyene in the presence of an olefin polymerization catalyst comprising at least one compound selected from the group consisting of [B-2] an organoaluminum oxy compound, and [B-3] a compound that reacts with the transition metal compound [A] to form an ion pair.
[In the formula (I),
M represents a titanium atom;
m represents an integer from 1 to 6;
R1 is a methyl group or a phenyl group ^;
R2 ^{and R3} may be the same or different and each represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen - containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group , and may be linked to each other to form a ring;
R ⁴ and R ⁵ may be the same or different and each represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and may be bonded to each other to form a double bond between a carbon atom and a nitrogen atom,
Z represents a structure represented by the following formula (III) :
(In formula (III), R ⁶ to R ⁹ may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring, and ● represents a bonding point with a carbon atom (C), and ○ represents a bonding point with a nitrogen atom (N).)
When m is 2 or more, two of the groups represented by R ¹ to R ³ and R may be linked to each other.
n is a number that satisfies the valence of M;
X represents 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 compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different from one another, and the multiple groups represented by X may be bonded to one another to form a ring;
R ¹⁰ to R ¹⁴ may be the same or different and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a 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 to each other to form a ring, and three or more of R ¹⁰ to R ¹⁴ are hydrogen. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 1, wherein R ⁴ and R ⁵ in the general formula (I) are bonded to each other to form a double bond between the carbon atom and the nitrogen atom. The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to claim 1 or 2, wherein R ² and R ³ in the general formula (I) are a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 3. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 1 , wherein R ² and R ³ in the general formula (I) are any of hydrogen, a methyl group, and a phenyl group. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of claims 1 to 4 , wherein the non-conjugated polyene is represented by the following general formula (IV):
[In the formula, m is an integer from 0 to 2,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, the hydrocarbon group optionally having a double bond;
any two of the substituents R ¹⁵ to R ¹⁸ may be bonded to each other to form a ring, the ring may contain a double bond, R ¹⁵ and R ¹⁶ , or R 17 and R ¹⁸ may be bonded to each other to form an alkylidene group, or R ¹⁵ and R ^{17 , or R 16 and} R ¹⁸ may be bonded to each other to form a double bond;
At least one of the following requirements (i) to (iv) is met:
(i) At least one of R ¹⁵ to R ¹⁸ is a hydrocarbon group having one or more double bonds.
(ii) any two of the substituents R ¹⁵ to R ¹⁸ are bonded to each other to form a ring, and the ring contains a double bond.
(iii) R ¹⁵ and R ¹⁶ together, or R ¹⁷ and R ¹⁸ together form an alkylidene group.
(iv) R ¹⁵ and R ¹⁷ , or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 5 , wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB). The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to claim 5 or 6 , wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, and a non-conjugated polyene. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 7 , wherein the α-olefin is propylene. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of claims 1 to 8 , wherein the polymerization temperature in the step [P] is 80°C or higher.