JP2021073223A - Manufacturing method of transition metal compound, olefin polymerization catalyst, and olefin polymer - Google Patents

Abstract

To provide a novel transition metal compound, in particular, a novel transition metal compound capable of using in an olefin polymerization catalyst.SOLUTION: A transition metal compound expressed by the following general formula [A-2]. [In the formula [A-2], M expresses a titanium atom or the like, n is an integer of 1 to 4, X expresses a halogen atom or the like, R11 to R20 each expresses independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbons or the like.]SELECTED DRAWING: None

Description

The present invention relates to a novel transition metal compound, more specifically, a novel transition metal compound that can be used as a catalyst for olefin polymerization, a catalyst for olefin polymerization containing the compound, and a method for producing an olefin polymer using the catalyst. Regarding.

Conventionally, as a catalyst for producing an olefin polymer such as an ethylene / α-olefin copolymer, a catalyst composed of a metallocene compound and a cocatalyst such as an organic aluminum oxy compound is known.

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

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

(In the formula, M represents a transition metal of Group 4 of the periodic table such as Ti, L represents a monovalent anionic ligand in which an element of Group 15 of the periodic table serves as a coordination atom, and X represents a halogen or the like. , M represents an integer of 1 to 3, and R ^{1 to} R ⁵ represent hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, etc.), and are selected from organic aluminum oxy compounds and organic boron compounds. A cyclic olefin system that copolymerizes ethylene and / or an α-olefin having 3 to 20 carbon atoms with at least one cyclic olefin compound in the presence of a polymerization catalyst composed of one or more activators (B). A method for producing a polymer is described, and specific examples of the transition metal compound (A) include CpTi (t-Bu ₂ C = N) Cl ₂ and Cp ^* Ti (2,6- ⁱ Pr ₂ PhO) Cl _2. Is listed. (Cp represents a cyclopentadienyl group and Cp ^* represents a η ⁵ -pentamethylcyclopentadienyl group).

Further, Non-Patent Document 1 describes that copolymerization of ethylene and norbornene was carried out in the presence of a transition metal compound represented by the following formula and methylaluminoxane (MAO).

JP-A-2007-63409

Macromolecules 2011, 44, 1986-1998

However, when the transition metal compound described in Non-Patent Document 1 as a metallocene compound is used as a catalyst for olefin polymerization, there is room for further improvement in terms of catalytic activity, copolymerizability, and high molecular weight polymer. I understood.

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

Further, one aspect of the present invention includes a catalyst for olefin polymerization capable of producing a highly active and high molecular weight olefin polymer, a novel transition metal compound that can be used for such a catalyst for olefin polymerization, and the like. It is intended to be provided.

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

The present invention relates to the following [1] to [12].
[1]
A transition metal compound represented by the following general formula [A-1].

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

[In equation [A-1]
M is a titanium atom, a zirconium atom, or a hafnium atom,
n is an integer of 1 to 4
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene system. It is a divalent derivative group and
R ^{1 to} R ⁵ and R ⁸ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, or It is a phosphorus-containing group, and ^{adjacent groups of R 1 to} R ⁵ may be bonded to each other to form a ring.
R ⁶ and R ⁷ are independently halogen atoms or halogen-containing groups, respectively. ]

[2]
In the general formula [A-1], M is a titanium atom, which is the transition metal compound of the above [1].

[3]
In the general formula [A-1], R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ^{2 to} R ⁵ are hydrogen atoms. The transition metal compound of the above [2].

[4]
In the general formula [A-1], R ⁶ and R ⁷ are independent halogen-containing groups, respectively, which is the transition metal compound of the above [3].

[5]
A transition metal compound represented by the following general formula [A-2].

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

[In equation [A-2]
M is a titanium atom, a zirconium atom, or a hafnium atom,
n is an integer of 1 to 4
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene system. It is a divalent derivative group and
R ^{11 to} R ²⁰ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, or phosphorus-containing groups. Of these, adjacent groups may be bonded to each other to form a ring. ]

[6]
In the general formula [A-2], M is a titanium atom, which is the transition metal compound of the above [5].

[7]
In the general formula [A-2], R ^{11 to} R ¹⁷ are the transition metal compounds of the above [6] which are hydrogen atoms.

[8]
In the general formula [A-2], R ¹⁸ and R ¹⁹ are the transition metal compounds of the above [7], which are each independently a hydrocarbon group having 1 to 20 carbon atoms.

[9]
(A) The transition metal compound according to any one of [1] to [8] above,
(B) (B-1) Organometallic compound,
A catalyst for olefin polymerization containing (B-2) an organoaluminum oxy compound and (B-3) at least one compound selected from the group consisting of compounds that react with the transition metal compound to form an ion pair.

[10]
The method for producing an olefin polymer in which an olefin is polymerized in the presence of the catalyst for olefin polymerization according to the above [9].

[11]
The olefin is
(Z-1) Linear or branched α-olefin having 2 to 30 carbon atoms, and (Z-2) the following general formula [ZI], general formula [Z-II], general formula [Z-III] ] Or the method for producing the olefin polymer of the above [10], which contains a cyclic olefin represented by the general formula [Z-IV].

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

[In equation [ZI], u is 0 or 1,
v is 0 or a positive integer,
w is 0 or 1 and
R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and R ^{75 to} R ⁷⁸ are bonded to each other to form a monocyclic or polycyclic ring. The monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. .. ]

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

[In Equation [Z-II], x and d are integers greater than or equal to 0 or 1.
y and z are 0, 1 or 2,
R ^{81 to} R ⁹⁹ are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and ^{a carbon atom to which R 89} and R ⁹⁰ are bonded and a carbon atom to which R ⁹³ is bonded or R ^91. The carbon atom to which is bonded may be directly bonded or may be bonded via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R. ^{It may be bonded to 99} to form a monocyclic or polycyclic aromatic ring. ]

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

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

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

[In the general formula [Z-IV], x is an integer greater than or equal to 0 or 1, and
R ^{111 to} R ¹¹⁸ are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively.
R ^{121 to} R ¹²⁴ are independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or compound aromatic ring. ]

[12]
The α-olefin (Z-1) is ethylene, and the cyclic olefin (Z-2) is tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene The method for producing the olefin polymer of the above [11].

The present invention provides novel transition metal compounds.
The transition metal compound of the present invention can be used particularly as a catalyst for olefin polymerization.
Further, according to one aspect of the present invention, a catalyst for olefin polymerization capable of producing a highly active and high molecular weight olefin polymer, and a novel transition metal compound that can be used for such a catalyst for olefin polymerization. Etc. can be provided.

Further, according to one aspect of the present invention, an olefin polymerization catalyst capable of producing an α-olefin / cyclic olefin copolymer with high copolymerizability, and a novel catalyst capable of being used for such an olefin polymerization catalyst. Transitional metal compounds and the like can be provided.

Hereinafter, the transition metal compound and the like according to the present invention will be described in more detail.
[Transition metal compounds]
The transition metal compound of the present invention (hereinafter, also referred to as “transition metal compound (A)”) is represented by the following general formula [A-1] or [A-2].

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

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

<< M >>
In the formula [A-1], M represents a titanium atom, a zirconium atom, or a hafnium atom, preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

<< R ^{1 to R 5} and R ⁸ >>
In the formula [A-1], R ^{1 to} R ⁵ and R ⁸ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, and nitrogen. It is a containing group, a sulfur-containing group, or a phosphorus-containing group, and ^{adjacent groups of R 1 to} R ⁵ may be bonded to each other to form a ring.

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

Further, the hydrocarbon group may be one in which a hydrogen atom is substituted with another hydrocarbon group, and examples thereof include an aryl group-substituted alkyl group such as benzyl and cumyl.
Examples of the cyclopentadienyl moiety having a ring formed by bonding adjacent groups of R ^{1 to} R ⁵ to each other include the following ring structure, and the ring structure further has a substituent. You may be.

前記ハロゲン含有基の例としては、トリフルオロメチル、ペンタフルオロフェニル、クロロフェニルなどの炭素原子数１〜２０、好ましくは１〜１０のハロゲン化炭化水素基が挙げられる。

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

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Of these, the hydrocarbon-substituted silyl groups are specifically methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl (pentafluoro). Phenyl) Cyril and the like. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. In particular, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Examples of the oxygen-containing group include an alcohol group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic acid anhydride group, and a frill group.

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

Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyan acid ester group, an isothiocyanate group, a sulfone ester group, and a sulfonamide group. Examples thereof include a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group.

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

Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imide group, a pyrrolidino group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group and an amidino group. Examples thereof include a diazo group and an amino group in which an ammonium salt is used.

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

Examples of the phosphorus-containing group include a phosphido group, a phosphoryl group, a thiophosphoryl group, and a phosphato group.
As R ¹ , especially
Linear or branched with 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc. Alkyl group;
Aryl groups with 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracelyl;
A hydrocarbon group having 1 to 20 carbon atoms such as a substituted aryl group in which one or more hydrogen atoms of these aryl groups are substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or the like is preferable.
As R ^{2 to} R ⁵ , a hydrogen atom is particularly preferable.

《R ⁶ and R ⁷ 》
In the formula [A-1], R ⁶ and R ⁷ are independently halogen atoms or halogen-containing groups, preferably halogen-containing groups. As an example of the halogen atom, fluorine, chlorine, bromine and iodine are preferable. Examples of the halogen-containing group include trifluoromethyl, pentafluoroethyl, 1,1,1,3,3,3-hexafluoro-2-propyl, nonafluoro-tert-butyl, pentafluorophenyl, chlorophenyl and the like. Examples thereof include 1 to 20, preferably 1 to 10 halogenated hydrocarbon groups, and more preferably a trifluoromethyl group.

<< n >>
In the formula [A-1], n is an integer of 1 to 4, and is selected so as to be electrically neutral as a whole of the transition metal compound (A-1) according to the valence of M and the type of X. Will be done.

<< X >>
In the formula [A-1], X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, and a boron-containing group. , Aluminum-containing group, or diene-based divalent derivative group.

Specific embodiments of these halogen atoms, hydrocarbon groups, halogen-containing groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, and phosphorus-containing groups are described in R ^{1 to} R ⁵ and R ^{8 described above.} It is the same as the specific embodiment of the halogen atom, the hydrocarbon group, the halogen-containing group, the silicon-containing group, the oxygen-containing group, the sulfur-containing group, the nitrogen-containing group, and the phosphorus-containing group.

Examples of the boron-containing group include a bolangyl group, a bolantriyl group, a diboranyl group, and groups such as an alkyl group-substituted boron, an aryl group-substituted boron, a halogenated boron, and an alkyl group-substituted boron halide.

Examples of alkyl groups substituted _{boron, (Et) 2 B -,} (iPr) 2 B -, (iBu) 2 B -, table with _{(Et) 3 B, (iPr} ) 3 B or (iBu) ₃ B, The groups that are to be mentioned are listed
Examples of aryl group-substituted boron are (C ₆ H ₅ ) ₂ B-, (C ₆ H ₅ ) ₃ B, (C ₆ F ₅ ) ₃ B, or (3,5- (CF ₃ ) ₂ C ₆ H ₃₎ include groups represented by ₃ B,
Examples of boron halides include groups represented by _{BCl 2-} or BCl _3.
Examples of alkyl group-substituted boron halides include groups represented by (Et) BCl-, (iBu) BCl-, and (C ₆ H ₅ ) ₂ BCl. Of these, trisubstituted boron may be in a coordinated bond state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

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

Examples of alkyl group-substituted aluminum are represented by (Et) ₂ Al−, (iPr) ₂ Al−, (iBu) ₂ Al−, (Et) ₃ Al, (iPr) ₃ Al, or (iBu) ₃ Al. The group to be
Examples of aryl group-substituted aluminum include groups represented by _{(C 6} H ₅ ) _{2 Al−.}
Examples of aluminum halides include groups represented by _{AlCl 2-} or AlCl _3.
Examples of alkyl group-substituted aluminum halides include groups represented by (Et) AlCl- and (iBu) AlCl-. Of these, trisubstituted aluminum may be in a coordinated bond state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

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

Further, X has a structure in which the groups mentioned as specific examples of X are bonded to each other, and may form a ring together with M. For example, X is an alkylene group having a structure in which two alkyl groups are bonded, and this alkylene group may form a ring together with M.
Specific examples of the transition metal compound (A-1) include a compound represented by the following formula.

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

When the olefin is polymerized in the presence of the transition metal compound (A-1), a highly active, high molecular weight olefin polymer can be produced. The reason is not always clear, but the electron-withdrawing halogen atom or halogen-containing group present in the pyrazolate ligand enhances the cationic nature of the central metal, and as a result, the olefin is more strongly coordinated to the central metal. It is presumed that this is because the polymerization is likely to proceed.

[Transition metal compound (A-2)]
Next, a transition metal compound represented by the formula [A-2] (hereinafter, also referred to as “transition metal compound (A-2)”) will be described.

<< M >>
In the formula [A-2], M represents a titanium atom, a zirconium atom, or a hafnium atom, preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

《R ¹¹ ~ R ²⁰ 》
In the formula [A-2], R ^{11 to} R ²⁰ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, and nitrogen-containing groups. It is a sulfur-containing group or a phosphorus-containing group, and adjacent groups thereof may be bonded to each other to form a ring.

Specific embodiments of R ^{11 to} R ²⁰ include those exemplified as specific embodiments ^{of R 1 to} R ⁵ and R ^{8 in} the formula [A-1].
Examples of the indenyl moiety having a ring formed by bonding adjacent groups of R ^{11 to} R ²⁰ to each other include the following ring structures, even if the ring structure further has a substituent. Good.

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

As R ^{11 to} R ¹⁷ , a hydrogen atom is particularly preferable.
As R ¹⁸ and R ¹⁹ , hydrocarbon groups having 1 to 20 carbon atoms are particularly preferable.

<< n >>
In the formula [A-2], n is an integer of 1 to 4, and is selected so that the transition metal compound (A-2) as a whole is electrically neutral depending on the valence of M and the type of X. Will be done.

<< X >>
In the formula [A-2], X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, and a boron-containing group. , Aluminum-containing group, or diene-based divalent derivative group.

Specific embodiments of X include those exemplified as specific embodiments of X in the formula [A-1].
Specific examples of the transition metal compound (A-2) include a compound represented by the following formula.

遷移金属化合物（Ａ−２）の存在下でα−オレフィンと環状オレフィンとを重合すると、高い共重合性でα−オレフィン／環状オレフィン共重合体を製造することができる（すなわち、共重合体中に環状オレフィン由来の構造単位が多く含まれる。）。その理由としては、必ずしも定かではないが、インデニル配位子の平面性が関与していると考えられ、重合反応を継続できるように助触媒とのイオンセパレーションを保つ程度の適度な立体的効果を発揮しながら、配位挿入する環状オレフィンに対しては立体的な障壁が低いことから、より環状オレフィンが効率よく重合できると推測される。

By polymerizing an α-olefin and a cyclic olefin in the presence of the transition metal compound (A-2), an α-olefin / cyclic olefin copolymer can be produced with high copolymerizability (that is, in the copolymer). Contains many structural units derived from cyclic olefins.) The reason is not necessarily clear, but it is thought that the flatness of the indenyl ligand is involved, and it has an appropriate steric effect that maintains the ionic separation with the co-catalyst so that the polymerization reaction can be continued. Since the steric barrier is low for the cyclic olefin to be coordinated and inserted while exhibiting, it is presumed that the cyclic olefin can be polymerized more efficiently.

[Method for producing transition metal compounds]
The transition metal compound (A) of the present invention can be produced by combining known methods, and an example of a typical synthetic route is shown below, but the production method is not particularly limited. As a manufacturing method, for example
The anion compound of the pyrazolate compound represented by the following general formula [a-3] is obtained by reacting the pyrazolate compound (a-1) represented by the following general formula [a-1] with an alkyllithium (a-2). The step (1-1) for producing a-3) and the reaction of the anion body (a-3) with the compound (a-4) represented by the following general formula [a-4] are carried out to form the general formula. Examples thereof include a production method including a step (1-2) for producing the transition metal compound (A) represented by [A-1] or [A-2].

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

[Formula [a-1], the formula [a-3] and the formula [a-4] ^{in, R 1 ~R 8, M,} X and n are, R ¹ to R ⁸ each formula [A-1] , M, X and n. ]

First, various cyclopentadiene compounds can be produced by known methods, and the production method is not particularly limited. For example, JP-A-2000-136195, JP-A-2009-24019, Patent No. 3674509, WO1998 / 015510, WO2000 / 049029, "J. Organometallic Chem. 1999, 577, 211.", "J. Organometallic Chem. 2003, 677, 133.", "Organometallics 1988, 7, 1828.", "Organometallics 1996, 15, 4857.", "Organometallics 1997, 16, 2503." , 4693. "," J. Am. Chem. Soc. 2004, 126, 2089. "," Macromol. Chem. Phys. 2004, 205, 2275. "," Org. Lett. 2008, 10, 2545. ", Examples thereof include the production methods described in "Chem. Rev. 1992, 92, 965.", "Science 2012, 338, 504.", "Organometallics 2006, 25, 3824." And the like.

Methods for deriving compound (a-4) from various cyclopentadiene compounds are known, and the production method is not particularly limited. Known production methods include, for example, "Organometrics 2006, 25, 631.", "Macromolecules 2000, 33, 2796.", "J. Organomet. Chem. 1995, 489, 195.", "J. Am. Chem. Soc. 1996." , 118, 1906. ”,“ Organometrics 2006, 25, 3824. ”, And the like.

The pyrazolate compound (a-1) can be produced by a known method, and the production method is not particularly limited. Known production methods include, for example, "J. Org. Chem. 1985, 50, 4736.", "Inorgan. Chem. 2012, 51, 150.", and the production methods described in JP-A-2012-121875. Be done.

The anion compound (a-3) of the pyrazolate compound can be produced by a known method, and the production method is not particularly limited. As known production methods, for example, in addition to those mentioned as the production method of the pyrazolate compound, "Adv. Synth. Catal. 2005, 347, 463.", "Organometallics, 1997, 16, 2709.", "Organometallics, 2000, 19". , 2707. ”,“ Inorg. Chem. 2009, 48, 5011. ”, And the like.

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

[Catalyst for olefin polymerization]
The catalyst for olefin polymerization of the present invention includes (A) the transition metal compound according to the present invention described above, and (B) (B-1) an organometallic compound.
It is characterized by containing (B-2) an organoaluminum oxy compound and (B-3) at least one compound selected from the group consisting of a compound which reacts with a transition metal compound (A) to form an ion pair. There is.
The catalyst for olefin polymerization of the present invention may further contain (C) a carrier and may further contain (D) an organic compound, if necessary.

<Compound (B)>
《Organometallic compound (B-1》
Examples of the organometallic compound (B-1) (hereinafter, also referred to as “component (B-1)”) include an organoaluminum compound (B-1a) represented by the general formula (B-1a) and a general formula (B-1a). A complex alkylated product (B-1b) of a Group 1 metal represented by B-1b) and aluminum, and a dialkyl compound (B-) of a Group 2 or Group 12 metal represented by the general formula (B-1c). Examples thereof include organometallic compounds of Groups 1, 2 and 12 and 13 such as 1c).

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

(B-1b): M2AlRa ₄
In formula (B-1b), M2 is Li, Na or K, and Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkylated product (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

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

<< Organoaluminium oxy compound (B-2) >>
As the organoaluminum oxy compound (B-2) (hereinafter, also referred to as “component (B-2)”), conventionally known aluminoxane can be used as it is. Specifically, the following general formula [B2-1]

および／または下記一般式［B2-2］

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

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

(In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 2 or more), and benzene described in JP-A-2-78687 and JP-A-2-167305. Examples thereof include insoluble organic aluminum oxy compounds and aluminoxane having two or more types of alkyl groups described in JP-A-3-103407.

Further, examples of the organoaluminum oxy compound (B-2) include modified methylaluminoxane as represented by the following general formula [B2-3].

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

(In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, and m and n are independently integers of 2 or more.)

This modified methylaluminoxane is prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by the methods set forth in US Pat. No. 4,960,878 and US Pat. No. 5,041584.

Further, as the organoaluminum oxy compound (B-2), an organoaluminum oxy compound containing boron represented by the following general formula [B2-4] can also be mentioned.

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

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

As the organoaluminum oxy compound (B-2), methylaluminoxane, which is easily available as a commercially available product, and MMAO prepared by using trimethylaluminum and triisobutylaluminum are preferable. Of these, MMAO having improved solubility in various solvents and storage stability is particularly preferable.

<< Compound (B-3) that reacts with transition metal complex (A) to form an ion pair >>
The compound (B-3) that reacts with the transition metal complex (A) to form an ion pair (hereinafter, also referred to as “ionic compound (B-3)” or “component (B-3)”) is particularly specific. Kaihei 1-501950, JP 1-502036, JP 3-179005, JP 3-179006, JP 3-207703, JP 3-207704, USP 5321106, etc. Examples thereof include Lewis acid, an ionic compound, a borane compound and a carborane compound described in the above. Further, heteropoly compounds and isopoly compounds can also be mentioned. However, the above-mentioned (B-2) organoaluminum oxy compound is not included.

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

式中、Ｒ^e+としては、Ｈ⁺、カルベニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ^fからＲⁱは、互いに同一でも異なっていてもよく、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基であり、好ましくは置換アリール基である。

In the formula ^{, Examples of Re +} include H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptiltyrienyl cation, ferrosenium cation having a transition metal, and the like. R ^f to R ⁱ may be the same or different from each other, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups. Yes, preferably a substituted aryl group.

Examples of the boron compound represented by the general formula [B3-1] include those described in International Publication No. 2015/122414 [0133] to [0144].
The ionic compound (B-3) may be used alone or in combination of two or more.

(Carrier (C))
The carrier (C) is an inorganic or organic compound, which is a solid in the form of granules or fine particles, and is conventionally used in olefin polymerization using a transition metal complex and a carrier as catalyst components, for example, Japanese Patent Application Laid-Open No. Those described in [0110] to [0122] of the 2011-122146 publication can be used.

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

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

In the method for producing an olefin polymer of the present invention, one type of olefin may be polymerized to produce an olefin homopolymer, or two or more types of olefins may be copolymerized to produce an olefin copolymer. Good. In the present specification, polymerization and copolymer are also described as "polymerization" without particular distinction, and olefin homopolymer and olefin copolymer are also described as "olefin polymer" without particular distinction.

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

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

Polymerization of olefins can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization, or a gas phase polymerization method. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane and the like. Aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more.

When polymerizing an olefin using the above catalyst for olefin polymerization, the transition metal compound (A) is usually 10 ^-12 to ^10-2 mol, preferably 10 ^-10 to 10 mol, per liter of the reaction volume. It is used in an amount such that it becomes ^{-3 mol.}

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

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

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

When the carrier (C) is used, the weight ratio [(A) / (C)] of the transition metal compound (A) to the carrier (C) is preferably 0.0001 to 1, more preferably 0.0005 to 0. It is used in an amount of 5.5, more preferably 0.001 to 0.1.

In the production method of the present invention, the polymerization temperature in the polymerization step is usually −50 to + 200 ° C., preferably 0 to 180 ° C.; the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge. It's pressure. The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, the polymerization can be carried out in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system, changing the polymerization temperature, or adjusting the amount of compound (B) used. When hydrogen is added, the amount thereof is appropriately about 0.001 to 5,000 NL per 1 kg of the olefin polymer produced.
Examples of olefins subjected to the polymerization reaction in the method for producing an olefin polymer of the present invention include linear or branched α-olefins and cyclic olefins.

(Z-1) Linear or branched α-olefin having 2 to 30 carbon atoms The linear or branched α-olefin has a linear or branched carbon atom number of 2 to 30. Examples include α-olefins (Z-1).

The number of carbon atoms of the α-olefin (Z-1) is preferably 2 to 20.
Specific examples of the α-olefin (Z-1) include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 Included are -methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

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

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

[In equation [ZI], u is 0 or 1,
v is 0 or a positive integer,
w is 0 or 1 and
R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and R ^{75 to} R ⁷⁸ are bonded to each other to form a monocyclic or polycyclic ring. The monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. .. ]

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

[In Equation [Z-II], x and d are integers greater than or equal to 0 or 1.
y and z are 0, 1 or 2,
R ^{81 to} R ⁹⁹ are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and ^{a carbon atom to which R 89} and R ⁹⁰ are bonded and a carbon atom to which R ⁹³ is bonded or R ^91. The carbon atom to which is bonded may be directly bonded or may be bonded via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R. ^{It may be bonded to 99} to form a monocyclic or polycyclic aromatic ring. ]

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

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

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

[In the general formula [Z-IV], x is an integer greater than or equal to 0 or 1, and
R ^{111 to} R ¹¹⁸ are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively.
R ^{121 to} R ¹²⁴ are independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or compound aromatic ring. ]
Hereinafter, the general formula [ZI], the general formula [Z-II], the general formula [Z-III], and the general formula [Z-IV] will be described in detail.

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

R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other and are hydrogen atoms, halogen atoms or hydrocarbon groups.
Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 30, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl. 20 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20 carbon atoms such as vinyl, allyl, isopropenyl; carbon atoms such as ethynyl, propargyl Linear or branched alkynyl groups having a number of 2 to 30, preferably 2 to 20; having 3 to 3 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, norbonyl, tetracyclododecyl. 30, preferably 3 to 20 cycloalkyl groups; cyclic unsaturated hydrocarbon groups with 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl; phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl And the like, an aryl group having 6 to 30, preferably 6 to 20 carbon atoms; an alkyl-substituted aryl group such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl and the like can be mentioned. ..

The hydrocarbon group may have a hydrogen atom substituted with a halogen, for example, the number of carbon atoms of monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, chlorophenyl and the like. Examples thereof include 1 to 30, preferably 1 to 20 alkyl halide groups or aryl halide groups.

Further, the above-mentioned hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl-substituted alkyl groups such as benzyl and cumyl.
Further, the above hydrocarbon group is a heterocyclic compound residue; an oxygen such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group and a carboxylic acid anhydride group. Containing groups: Amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group as ammonium salt Nitrogen-containing groups such as those that have become; boron-containing groups such as bolangyl group, bolantriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanic acid ester group, Sulfur-containing groups such as isothian acid ester group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, sulfenyl group; phosphide group, phosphoryl group, thiophosphoryl group, phosphat It may have a phosphorus-containing group such as a group, a silicon-containing group; a germanium-containing group; or a tin-containing group.

Examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl and the like having 1 to 30 carbon atoms, preferably 1 Linear or branched alkyl groups of ~ 20; cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbonyl, tetracyclododecyl, etc., having 3 to 30 carbon atoms, preferably 3 to 20 cyclos. Alkyl group; aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc .; halogen atom, preferably 1 to 30 carbon atoms in these aryl groups. Substituent aryl groups in which 1 to 20 alkyl groups or alkoxy groups, 6 to 30 carbon atoms, preferably 6 to 20 aryl groups or aryloxy groups are substituted with 1 to 5 substituents are preferable.

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

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

In the above example, the carbon atoms numbered 1 or 2 represent the carbon atoms to which ^{R 75} (R ⁷⁶ ) or R ⁷⁷ (R ^{78) are bonded in the general formula (I), respectively.}

Further, an alkylidene group may be formed by ^{R 75} and R ⁷⁶ , or by R ⁷⁷ and R ^78. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include ethylidene, propylidene, isopropylidene and the like.

<< General formula [Z-II] >>
In formula [Z-II], x and d are 0 or positive integers, and y and z are 0, 1 or 2.

Further, R ^{81 to} R ⁹⁹ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, and a hydrocarbon group.
As the halogen atom and the hydrocarbon group, the same halogen atom and the hydrocarbon group in the above formula [ZI] can be exemplified.

Here, the ^{carbon atom to which R 89} and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are direct or alkylene groups having 1 to 3 carbon atoms. It may be connected via. That is, when the above two carbon atoms are bonded via an alkylene group, R ⁸⁹ and R ⁹³ or R ⁹⁰ and R ⁹¹ cooperate with each other to form a methylene group (-CH _2). -), An alkylene group of either an ethylene group (-CH ₂ CH _2- ) or a propylene group (-CH ₂ CH ₂ CH _{2-) is formed.}

Further, when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, when y = z = 0, the following aromatic rings formed by ^{R 95} and R ^{92 can be mentioned.}

ここで、ｌは上記一般式［Z-II］におけるｄと同じである。

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

<< General formula [Z-III] >>
In the formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, are hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. ..

Preferred examples of the hydrocarbon group having 1 to 5 carbon atoms include an alkyl group, an alkyl halide group and a cycloalkyl group. These specific examples are the same as the specific examples of R ^{61 to} R ⁷⁸ of the above formula [ZI].

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

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

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

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

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

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

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

Examples include cyclic olefins in which a substituent selected from a halogen atom, an alkyl group, and an aryl group is substituted on these aromatic rings.

Specific examples of the cyclic olefin represented by the above general formula [ZI], [Z-II], [Z-III] or [Z-IV] include tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene and the like, and examples thereof include the compounds exemplified in [0176] to [0207] of JP-A-2011-122146.

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

Examples of the conjugated / non-conjugated polyene include cyclic or chain hydrocarbons having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds. Specific examples thereof include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, and the like. 1,3-octadien, 1,4-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, ethylidene norbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadien, Japanese Patent Application Laid-Open No. 2011-122146 of 4-ethylidene-8-methyl-1,7-nonadien, 5,9-dimethyl-1,4,8-decatorien butadiene, isoprene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, etc. Examples of the compounds exemplified in [0211].

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

Specific examples of the compound having a polar group and a polymerizable unsaturated bond include compounds exemplified as unsaturated hydrocarbons having a polar group in [0208] to [0211] of JP2011-122146A.

Specific examples of the aromatic vinyl compound and the functional group-containing styrene derivative include the compounds exemplified in [0211] of JP2011-122146A.
A preferred embodiment of the production method of the present invention is an embodiment in which the α-olefin (Z-1) and the cyclic olefin (Z-2) are copolymerized. In this embodiment, the α-olefin (Z-1) is preferably ethylene, and the cyclic olefin (Z-2) is tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene is preferred.

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

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited thereto.
[Measuring method]
[Structure of transition metal compounds]
The structure of the transition metal compound ^{was determined by 1 1} H-NMR spectrum (270 MHz, JEOL GSH-270).

[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) of polymer]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained by the "Alliance GPC 2000" gel permeation chromatograph (high temperature size exclusion chromatograph) manufactured by Waters, and the operating conditions are as follows:

<Devices and conditions used>
Measuring device: Gel permeation chromatograph alliance GPC2000 type (Waters)
Analysis software; Chromatography data system Emper (trademark, Waters)
Column; TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2
(Inner diameter 7.5 mm x length 30 cm, Tosoh)
Mobile phase; o-dichlorobenzene [= ОDCB] (Wako Pure Chemicals Special Grade Reagent)
Detector; differential refractometer (built-in device)
Column temperature; 140 ° C
Flow velocity; 1.0 mL / min
Injection volume; 400 μL
Sampling time interval; 1 second Sample concentration: 0.15% (w / v)
Molecular Weight Calibration Monodisperse Polystyrene (Tosoh) / Molecular Weight 495 to Molecular Weight 20.6 Million

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

[Polymer Tg]
DSC measurement was performed under the following conditions to determine the Tg of the polymer.
Equipment: SII Nanotechnology, Inc. DSC6220
Measurement conditions: Tg was determined in the process of rapidly cooling the sample held at 300 ° C. for 5 minutes to 0 ° C. and then raising the temperature to 250 ° C. at a heating rate of 20 ° C./min.

[Manufacturing of titanium compounds]
[Reference example A1]
0.96 g (4.7 mmol) of 3,5-bis (trifluoromethyl) -1H-pyrazole, 5 mL of n-hexane, and 5 mL of toluene were charged into a 30 mL reactor that had been sufficiently dried and replaced with nitrogen, and the mixture was stirred. To this solution, 2.9 mL of an n-butyllithium solution (hexane solution, 1.64M, 4.7 mmol) was added at 0 ° C., and then stirring was continued at room temperature for 4 hours. After distilling off the solvent of the reaction solution, the obtained dry solid was washed with 5 mL of n-hexane, recovered, and dried under reduced pressure to obtain 0.80 g of a colorless solid.

0.29 g (1.0 mmol) of tert-butylcyclopentadienyl trichlorotitanium and 5 mL of diethyl ether were charged and stirred in another 30 mL reactor that had been sufficiently dried and replaced with nitrogen. To this solution, a solution prepared with 0.21 g (1.0 mmol) of the previously obtained colorless solid and 5 mL of diethyl ether was added at −78 ° C., and stirring was continued at room temperature for 24 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained oil to prepare a suspension, and the insoluble material was removed with a membrane syringe filter. After concentrating the obtained solution under reduced pressure, n-hexane was added, and the yellow-orange crystals obtained by allowing to stand at −30 ° C. were recovered and dried under reduced pressure to form titanium represented by the following formula (1). 38 mg (yield 8%) of compound (1) was obtained. ^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ 7.33 (1H, s, CH), 6.84 (2H, t, J = 2.8 Hz, Cp-H), 6.69 (2H, t, J) = 2.8 Hz, Cp-H), 1.30 (9H, s, C (CH ₃ ) ₃ ) ppm

〔式中、ｔＢｕはｔｅｒｔ−ブチル基である。〕

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

[Example A2]
0.27 g (1.0 mmol) of (indenyl) titanium (IV) trichloride and 8 mL of diethyl ether were charged into a 30 mL reactor that had been sufficiently dried and replaced with nitrogen, and the mixture was stirred. To this solution, Inorg. Chem. 2009, 48, 5011. A solution prepared from 0.16 g (1.0 mmol) of 3,5-diisopropylirazolatolith synthesized by the described method and 2 mL of diethyl ether was added at −78 ° C., and stirring was continued at room temperature for 17 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained dry matter to prepare a suspension, and the insoluble matter was removed by Celite filtration. After concentrating the obtained solution under reduced pressure, the dark red crystals obtained by adding n-hexane were recovered and dried under reduced pressure to obtain 67 mg (yield) of the titanium compound (2) represented by the following formula (2). 17%) Obtained.
^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ 7.48-7.42 (2H, m, Ar-H), 7.19-7.10 (5H, m, Ar-H), 6.44 (1H) , S, CH), 2.84 (2H, sept, J = 6.9Hz, Me ₂ CH), 1.25 (12H, d, J = 6.9Hz, CH ₃ ) ppm

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

[Example B2]
The same operation as in Reference Example B1 was carried out except that the titanium compound (1) was changed to 0.0030 mmol of the titanium compound (2) obtained in Example A2 and the amount of methylaluminoxane was changed to 1.50 mmol in terms of aluminum atoms. , Ethylene / tetracyclododecene copolymer was obtained. Table 1 shows the physical characteristics of the ethylene / tetracyclododecene copolymer.

[Comparative Example B1]
Similar to Reference Example B1 except that the titanium compound (1) was synthesized by the method described in Macromolcules 2011, 44, 1986-1998 and changed to 0.0015 mmol of the titanium compound (3) represented by the following formula (3). The operation was carried out to obtain an ethylene / tetracyclododecene copolymer. Table 1 shows the physical characteristics of the ethylene / tetracyclododecene copolymer.

〔式中、ｔＢｕはｔｅｒｔ−ブチル基であり、ｉＰｒはイソプロピル基である。〕

[In the formula, tBu is a tert-butyl group and iPr is an isopropyl group. ]

Claims (8)

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

[In equation [A-2]
M is a titanium atom, a zirconium atom, or a hafnium atom,
n is an integer of 1 to 4
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene system. It is a divalent derivative group and
R ^{11 to} R ²⁰ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, or phosphorus-containing groups. Of these, adjacent groups may be bonded to each other to form a ring. ] The transition metal compound according to claim 1, wherein M is a titanium atom in the general formula [A-2]. The transition metal compound according to claim 2, wherein in the general formula [A-2], R ^{11 to} R ^{17 are hydrogen atoms.} The transition metal compound according to claim 3, wherein in the general formula [A-2], R ¹⁸ and R ¹⁹ are each independently a hydrocarbon group having 1 to 20 carbon atoms. (A) The transition metal compound according to any one of claims 1 to 4,
(B) (B-1) Organometallic compound,
A catalyst for olefin polymerization containing (B-2) an organoaluminum oxy compound and (B-3) at least one compound selected from the group consisting of a compound that reacts with a transition metal compound (A) to form an ion pair. .. A method for producing an olefin polymer that polymerizes an olefin in the presence of the catalyst for olefin polymerization according to claim 5. The olefin is
(Z-1) Linear or branched α-olefin having 2 to 30 carbon atoms, and (Z-2) the following general formula [ZI], general formula [Z-II], general formula [Z-III] ] Or the method for producing an olefin polymer according to claim 10, which comprises a cyclic olefin represented by the general formula [Z-IV].

[In equation [ZI], u is 0 or 1,
v is 0 or a positive integer,
w is 0 or 1 and
R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and R ^{75 to} R ⁷⁸ are bonded to each other to form a monocyclic or polycyclic ring. The monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. .. ]

[In Equation [Z-II], x and d are integers greater than or equal to 0 or 1.
y and z are 0, 1 or 2,
R ^{81 to} R ⁹⁹ are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and ^{a carbon atom to which R 89} and R ⁹⁰ are bonded and a carbon atom to which R ⁹³ is bonded or R ^91. The carbon atom to which is bonded may be directly bonded or may be bonded via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R. ^{It may be bonded to 99} to form a monocyclic or polycyclic aromatic ring. ]

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

[In the general formula [Z-IV], x is an integer greater than or equal to 0 or 1, and
R ^{111 to} R ¹¹⁸ are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively.
R ^{121 to} R ¹²⁴ are independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or compound aromatic ring. ] The α-olefin (Z-1) is ethylene, and the cyclic olefin (Z-2) is tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] The method for producing an olefin polymer according to claim 7, which is -3-dodecene.