JP2005290245A - Method for manufacturing ethylene polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an economical method for manufacturing an ethylene polymer having an alkyl branching chain. <P>SOLUTION: This ethylene polymer is manufactured by supplying ethylene as a monomer component and performing polymerization using the following components (i)-(iii) as catalyst components: (i) a transition metal compound represented by formulae [1] or [2], wherein M is a group IV transition metal atom; Cp<SP>1</SP>and Cp<SP>2</SP>are each a group having a cyclopentadiene-type anion skeleton, X<SP>1</SP>-X<SP>4</SP>are each a hydrogen atom, halogen atom, hydrocarbon group, hydrocarbonoxy group, or the like, Z is a specific divalent group; Y is a divalent hydrocarbon group bonded to M by means of an oxygen atom, sulfur atom, nitrogen atom or phosphorus atom, and T is a hydrocarbonoxy group, disubstituted amino group, or the like; (ii) a chromium compound represented by formula 3 (CrJ<SB>j</SB>K<SB>k</SB>[3]), wherein j is an integer of 0-5, k is an integer of 0-6, 3≤j+k≤6, J is an oxygen atom, halogen atom, hydrocarbon group, hydrocarbonoxy group, or the like, and K is a group bonded to a chromium atom by means of a lone electron pair or π electron; or (iii) a specific aluminum compound and/or boron compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing an ethylene polymer having an alkyl side chain.

  An ethylene polymer having an alkyl side chain (ethyl group, butyl group, etc.) such as linear low density polyethylene is excellent in mechanical properties, chemical resistance, etc., and has an excellent balance between properties and economic efficiency. Therefore, it is used in many fields such as the packaging field. As a method for producing the polymer, a catalyst component composed of a metallocene complex such as dichloro [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy)] titanium, triisobutylaluminum, Copolymerizing α-olefins such as 1-butene and 1-hexene with ethylene using a so-called metallocene catalyst in contact with an activation co-catalyst component such as triphenylmethyltetrakis (pentafluorophenyl) borate There is a known method (for example, Patent Document 1).

JP-A-9-87313

However, in the conventional method for producing an ethylene polymer having an alkyl side chain, since polymerization is carried out by supplying ethylene and α-olefin as monomer components, the economical efficiency is not sufficiently satisfactory.
Under such circumstances, the problem to be solved by the present invention is to provide an economical method for producing an ethylene polymer having an alkyl side chain.

  In this invention, the economical manufacturing method of the ethylene-type polymer which has an alkyl side chain can be provided.

（一般式［１］においてそれぞれ、Ｍは元素の周期律表の第４族の遷移金属原子を示し、Ｃｐ¹はシクロペンタジエン型アニオン骨格を有する基を示す。Ｘ¹およびＸ²はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基または２置換アミノ基を示す。ＺはＳｉＲ^* ₂、ＣＲ^* ₂、ＳｉＲ^* ₂ＳｉＲ^* ₂、ＣＲ^* ₂ＣＲ^* ₂、ＣＲ^*＝ＣＲ^*、ＣＲ^* ₂ＳｉＲ^* ₂、ＧｅＲ^* ₂またはＢＲ^*（ここでＲ^*は、水素原子、炭化水素基、炭化水素オキシ基または２置換アミノ基を表し、Ｒ^*が複数ある場合、夫々のＲ^*は互いに同じであっても異なっていてもよく、複数あるＲ^*は結合して単環または多環を形成してもよい。）で示される２価の基を示す。Ｙは酸素原子、硫黄原子、窒素原子またはリン原子によりＭと結合するヘテロ原子含有の２価の炭化水素基を示す。）

（一般式［２］において、Ｍは元素の周期律表の第４族の遷移金属原子を示し、Ｃｐ²はシクロペンタジエン型アニオン骨格を有する基を示す。Ｘ³およびＸ⁴はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基または２置換アミノ基を示す。Ｔは炭化水素オキシ基、２置換アミノ基または３置換ホスフィノイミノ基を示す。）
（ii）下記一般式［２］で表されるクロム化合物
ＣｒＪ_ｊＫ_ｋ ［２］
（一般式［２］において、ｊは０〜５の整数を表し、ｋは０〜６の整数を表す。ただし、３≦ｊ＋ｋ≦６を充足する。Ｃｒはクロム原子を表す。Ｊは酸素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基または２置換アミノ基を表し、Ｊが複数ある場合、夫々のＪは互いに同じであっても異なっていてもよい。Ｋは孤立電子対もしくはπ電子によりクロム原子と結合する基を表し、Ｋが複数ある場合、夫々のＫは互いに同じであっても異なっていてもよい。）
（iii）下記成分（Ａ）および／または成分（Ｂ）
（Ａ）：下記（Ａ１）〜（Ａ３）から選ばれる１種以上のアルミニウム化合物
（Ａ１）一般式 Ｅ¹ _aＡｌＵ_3-aで示される有機アルミニウム化合物
（Ａ２）一般式 ｛−Ａｌ（Ｅ²）−Ｏ−｝_bで示される構造を有する環状のアルミノキサン
（Ａ３）一般式 Ｅ³｛−Ａｌ（Ｅ³）−Ｏ−｝_cＡｌＥ³ ₂で示される構造を有する線状のアルミノキサン
（上記（Ａ１）〜（Ａ３）において、ａは０＜ａ≦３を満足する数を表し、ｂは２以上の整数を表し、ｃは１以上の整数を表す。Ｅ¹、Ｅ²およびＥ³は炭化水素基を表し、Ｅ¹が複数ある場合は、夫々のＥ¹は互いに同じであっても異なっていてもよい。また、夫々のＥ²は互いに同じであっても異なっていてもよく、夫々のＥ³は互いに同じであっても異なっていてもよい。Ａｌはアルミニウム原子を表す。Ｕは水素原子またはハロゲン原子を表し、Ｕが複数ある場合は、夫々のＵは互いに同じであっても異なっていてもよい。）
（Ｂ）：下記（Ｂ１）〜（Ｂ３）から選ばれる１種以上のホウ素化合物
（Ｂ１）一般式 ＢＱ¹Ｑ²Ｑ³で表されるホウ素化合物
（Ｂ２）一般式 Ｇ⁺（ＢＱ⁴Ｑ⁵Ｑ⁶Ｑ⁷）^-で表されるホウ素化合物
（Ｂ３）一般式 （Ｌ−Ｈ）⁺（ＢＱ⁸Ｑ⁹Ｑ¹⁰Ｑ¹¹）^-で表されるホウ素化合物
（上記（Ｂ１）〜（Ｂ３）において、Ｂは３価のホウ素原子を表し、Ｑ¹〜Ｑ¹¹はハロゲン原子、炭化水素基、ハロゲン化炭化水素基、置換シリル基、アルコキシ基または２置換アミノ基を表し、Ｑ¹〜Ｑ¹¹は同じであっても異なっていてもよい。Ｇ⁺は無機または有機のカチオンを表し、Ｌは中性ルイス塩基を表し、（Ｌ−Ｈ）⁺はブレンステッド酸を表す。） The present invention is a method for producing an ethylene polymer having an alkyl side chain, wherein ethylene is supplied as a monomer component, and polymerization is carried out using the following components (i), (ii) and (iii) as catalyst components. The present invention relates to a method for producing an ethylene polymer.
(I) A transition metal compound represented by the following general formula [1] or [2].

(In the general formula [1], M represents a group 4 transition metal atom in the periodic table of elements, and Cp ¹ represents a group having a cyclopentadiene type anion skeleton. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, .Z indicating a hydrocarbon group or a disubstituted amino group is _{^{SiR * 2, CR * 2,}} SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = _{^{CR *, CR * 2 SiR *}} 2, GeR * 2 or BR ^* (wherein R ^* is a hydrogen atom, a hydrocarbon group, a hydrocarbon group or a disubstituted amino group, if R ^* is more, respectively R ^* in the formulas may be the same or different from each other, and a plurality of R ^* may combine to form a monocyclic or polycyclic group.) Y represents oxygen Hete bonded to M by an atom, sulfur atom, nitrogen atom or phosphorus atom A divalent hydrocarbon group containing a rho atom is shown.)

(In General Formula [2], M represents a transition metal atom of Group 4 of the periodic table of elements, and Cp ² represents a group having a cyclopentadiene type anion skeleton. X ³ and X ⁴ are each independently A hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbonoxy group or a disubstituted amino group, and T represents a hydrocarbonoxy group, a disubstituted amino group or a trisubstituted phosphinoimino group.
(Ii) Chromium compound represented by the following general formula [2] CrJ _j K _k [2]
(In General Formula [2], j represents an integer of 0 to 5, k represents an integer of 0 to 6. However, 3 ≦ j + k ≦ 6 is satisfied. Cr represents a chromium atom. J represents an oxygen atom. Represents a halogen atom, a hydrocarbon group, a hydrocarbon oxy group or a disubstituted amino group, and when there are a plurality of J, each J may be the same or different from each other, and K is a lone electron pair or a π electron. Represents a group bonded to a chromium atom, and when there are a plurality of K, each K may be the same as or different from each other.)
(Iii) The following component (A) and / or component (B)
(A): One or more aluminum compounds selected from the following (A1) to (A3) (A1) Organoaluminum compound represented by the general formula E ¹ _a AlU _3-a (A2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having the structure represented by _b (A3) linear aluminoxane having the structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ ₂ (the above ( In A1) to (A3), a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, c represents an integer of 1 or more, and E ¹ , E ^2, and E ³ represent carbonization. It represents a hydrogen group, if E ¹ is more, each E ¹ may be different be the same as each other. in addition, E ² each may be different, even the same as each other, respectively E ³ .al is optionally different from one another the same aluminum Hara .U representing a represents a hydrogen atom or a halogen atom, if U there are multiple, U of each may be different, even the same as each other.)
(B): One or more boron compounds selected from the following (B1) to (B3) (B1) Boron compounds represented by the general formula BQ ¹ Q ² Q ³ (B2) General formula G ⁺ (BQ ⁴ Q ⁵ Boron compound represented by Q ⁶ Q ⁷ ) ⁻ (B3) Boron compound represented by general formula (LH) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ⁻ (in the above (B1) to (B3) , B represents a trivalent boron atom, Q ^{1 to} Q ¹¹ represent a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, and Q ^{1 to} Q ¹¹ represent G ⁺ represents an inorganic or organic cation, L represents a neutral Lewis base, and (L—H) ⁺ represents a Bronsted acid.

（一般式［１］においてそれぞれ、Ｍは元素の周期律表の第４族の遷移金属原子を示し、Ｃｐ¹はシクロペンタジエン型アニオン骨格を有する基を示す。Ｘ¹およびＸ²はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基または２置換アミノ基を示す。ＺはＳｉＲ^* ₂、ＣＲ^* ₂、ＳｉＲ^* ₂ＳｉＲ^* ₂、ＣＲ^* ₂ＣＲ^* ₂、ＣＲ^*＝ＣＲ^*、ＣＲ^* ₂ＳｉＲ^* ₂、ＧｅＲ^* ₂またはＢＲ^*（ここでＲ^*は、水素原子、炭化水素基、炭化水素オキシ基または２置換アミノ基を表し、Ｒ^*が複数ある場合、夫々のＲ^*は互いに同じであっても異なっていてもよく、複数あるＲ^*は結合して単環または多環を形成してもよい。）で示される２価の基を示す。Ｙは酸素原子、硫黄原子、窒素原子またはリン原子によりＭと結合するヘテロ原子含有の２価の炭化水素基を示す。）

（一般式［２］において、Ｍは元素の周期律表の第４族の遷移金属原子を示し、Ｃｐ²はシクロペンタジエン型アニオン骨格を有する基を示す。Ｘ³およびＸ⁴はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基または２置換アミノ基を示す。Ｔは炭化水素オキシ基、２置換アミノ基または３置換ホスフィノイミノ基を示す。） Component (i) of the present invention is a transition metal compound represented by the following general formula [1] or [2].

(In the general formula [1], M represents a group 4 transition metal atom in the periodic table of elements, and Cp ¹ represents a group having a cyclopentadiene type anion skeleton. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, .Z indicating a hydrocarbon group or a disubstituted amino group is _{^{SiR * 2, CR * 2,}} SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = _{^{CR *, CR * 2 SiR *}} 2, GeR * 2 or BR ^* (wherein R ^* is a hydrogen atom, a hydrocarbon group, a hydrocarbon group or a disubstituted amino group, if R ^* is more, respectively R ^* in the formulas may be the same or different from each other, and a plurality of R ^* may combine to form a monocyclic or polycyclic group.) Y represents oxygen Hete bonded to M by an atom, sulfur atom, nitrogen atom or phosphorus atom A divalent hydrocarbon group containing a rho atom is shown.)

(In General Formula [2], M represents a transition metal atom of Group 4 of the periodic table of elements, and Cp ² represents a group having a cyclopentadiene type anion skeleton. X ³ and X ⁴ are each independently A hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbonoxy group or a disubstituted amino group, and T represents a hydrocarbonoxy group, a disubstituted amino group or a trisubstituted phosphinoimino group.

  In the above general formula [1] or [2], M is a transition metal atom of Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), for example, a titanium atom, a zirconium atom, a hafnium atom, etc. Preferably, it is a titanium atom.

In the general formulas [1] and [2], examples of the group having a cyclopentadiene type anion skeleton represented by Cp ¹ and Cp ² include η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ - dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, eta ⁵ - isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ^5-n-pentyl cycloalkyl Bae Ntajieniru group, eta ⁵ - neopentyl cycloalkyl Bae Ntajieniru group, eta ^{5-n-hexylcyclopentadienyl} Bae Ntaji Alkenyl group, eta ^5-n-octyl cyclopentane Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - Nafuchirushikuro Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ⁵ - triethylsilyl cycloalkyl Bae Ntajieniru group , eta ^{5-tert-butyldimethylsilyl} cycloalkyl Bae Ntajieniru group, eta ⁵ - indenyl group, eta ⁵ - methylindenyl group, eta ⁵ - dimethyl indenyl group, eta ⁵ - ethyl indenyl group, eta ^5-n-propyl indenyl group, eta ⁵ - isopropylindenyl group, eta ^5-n-butyl indenyl group, eta ^5-sec-butyl indenyl group, eta ^5-tert-butyl indenyl group, eta ^{5-n-pentyl-indenyl} group, eta ⁵ - neopentyl indenyl group, eta ^5-n-hexyl indenyl group, eta ^5-n-octyl indenyl group, eta ⁵ -n Deshiruindeniru group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group, eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - triethylsilyl indenyl group, eta ^5-tert- butyldimethylsilyl indenyl group, eta ⁵ - tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl fluorenyl group, eta ⁵ - ethyl fluorenyl group, eta ⁵ - diethyl fluorenyl group, eta ^{5-n-propyl-fluorenyl} group, eta ⁵ - di-n-propyl-fluorenyl group, eta ⁵ - isopropyl fluorenyl group, eta ⁵ - diisopropyl fluorenyl group, eta ^{5-n-butyl-fluorenyl} group, eta ^{5-sec-butylfluorenyl} group, eta ^{5-tert-butyl-fluorenyl} group, eta ⁵ - di-n-Buchirufuruore Le group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ - di -tert- butyl-fluorenyl group, eta ^{5-n-pentyl-fluorenyl} group, eta ⁵ - Neopentyl fluorenyl group, η ⁵ -n-hexyl fluorenyl group, η ⁵ -n-octyl fluorenyl group, η ⁵ -n-decyl fluorenyl group, η ⁵ -n-dodecyl fluorenyl group, η ⁵ -phenyl fluorenyl group Nyl group, η ⁵ -diphenylfluorenyl group, η ⁵ -methylphenylfluorenyl group, η ⁵ -naphthylfluorenyl group, η ⁵ -trimethylsilylfluorenyl group, η ⁵ -bis (trimethylsilyl) fluorenyl group, eta ⁵ - triethylsilyl fluorenyl group, eta ⁵ such -tert- butyldimethylsilyl fluorenyl group and the like, as the Cp ² η ⁵ - also be mentioned pentamethylcyclopentadienyl group Can do. Among these, preferably eta ⁵ as Cp ¹ - cyclopentadienyl group, eta ^{5-3-methylcyclopentadienyl} group, eta ⁵ -3-tert-butylcyclopentadienyl group, eta ⁵ - tetramethyl cyclopentadienyl group, eta ⁵ - indenyl group, eta ⁵ - fluorenyl group, eta ^{5-2,7-dimethyl} fluorenyl group, eta ^{5-3,6-dimethyl} fluorenyl group, eta ⁵ -2,7 -Di-tert-butylfluorenyl group, η ⁵ -3,6-di-tert-butylfluorenyl group, preferably Cp ² and preferably Cp ¹ and η ⁵ -pentamethylcyclopentadienyl It is a group.

X ¹ , X ² , X ³ , and X ⁴ in the general formulas [1] and [2] are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon oxy group, or a disubstituted amino group.

Examples of the halogen atom represented by X ^{1 to} X ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group for X ^{1 to} X ⁴ include an alkyl group, an aralkyl group, an aryl group, and a diene.

Examples of the alkyl group represented by X ^{1 to} X ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, and n. -Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like can be mentioned.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, --Fluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchlorooctyl Group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopenta group A decyl group, a perbromoeicosyl group, etc. are mentioned.
These alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group.

Examples of the aralkyl group represented by X ^{1 to} X ⁴ include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethylphenyl). Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4, 6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3, 4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetra Lamethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) ) Methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n -Hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthrace An nylmethyl group etc. are mentioned.
All of these aralkyl groups are partially substituted with halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkoxy groups such as methoxy and ethoxy groups; aryloxy groups such as phenoxy groups; aralkyloxy groups and the like. May be.

Examples of the aryl group represented by X ^{1 to} X ⁴ include a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, and 2,5-xylyl group. 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl Group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2, 3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. It is done.
All of these aryl groups are partially substituted with halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkoxy groups such as methoxy and ethoxy groups; aryloxy groups such as phenoxy groups; aralkyloxy groups and the like. May be.

As the diene of X ^{1 to} X ⁴ , 1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,4-diphenyl-1,3-butadiene, 1,4-bis (4-methylphenyl) ) -1,3-butadiene and the like.

Examples of the hydrocarbon oxy group represented by X ^{1 to} X ⁴ include an alkoxy group, an aralkyloxy group, an aryloxy group, a carboxylate group, and a β-diketonate group.

Examples of the alkoxy group represented by X ^{1 to} X ⁴ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, neopentoxy group, An n-hexoxy group, an n-octoxy group, an n-dodesoxy group, an n-pentadesoxy group, an n-icosoxy group, and the like can be given.
All of these alkoxy groups are partially substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups and the like May be.

Examples of the aralkyloxy group represented by X ^{1 to} X ⁴ include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, and (2,3-dimethyl). Phenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, 3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, 2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) ) Methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy Group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group , (Tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group And anthracenylmethoxy group.
These aralkyloxy groups are all partially halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; May be substituted.

Examples of the aryloxy group represented by X ^{1 to} X ⁴ include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy Group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5- Tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethyl group Noxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decyl Examples thereof include aryloxy groups such as phenoxy group, n-tetradecylphenoxy group, naphthoxy group, and anthracenoxy group.
All of these aryloxy groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; May be substituted.

Examples of the carboxylate group of X ^{1 to} X ⁴ include an acetate group, a propionate group, a butyrate group, a neopentanoate group, a 2-ethylhexanoate group, a laurate group, a stearate group, a benzoate group, and a naphthenoate group. Examples include carboxylate groups.
These carboxylate groups are all partially halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; and aralkyloxy groups. May be substituted.

Examples of the β-diketonate group of X ^{1 to} X ⁴ include β-diketonate groups such as acetylacetonate group, 2,2,6,6-tetramethyl-3,5-heptanedionate group, benzoylacetonate group, etc. Is mentioned.
These β-diketonate groups are all partially halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; and aralkyloxy groups. May be substituted.

The disubstituted amino group of X ^{1 to} X ⁴ is an amino group substituted with two hydrocarbon groups, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples thereof include alkyl groups such as n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group; aryl groups such as phenyl group. Examples of the disubstituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group. Group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert -A butyldimethylsilylamino group etc. are mentioned, Preferably they are a dimethylamino group and a diethylamino group.

X ^{1 to} X ⁴ are preferably methyl, ethyl, isopropyl, tert-butyl, neopentyl, benzyl, phenyl, methoxy, ethoxy, t-butoxy, benzyloxy, phenoxy, 2 , 6-dimethylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-tert-butylphenoxy group, propionate group, 2-ethylhexanoate group, acetylacetonate group, 2,2,6,6-tetra Methyl-3,5-heptanedionate group, dimethylamino group, diethylamino group, 2,4-hexadiene or 1,4-diphenyl-1,3-butadiene, more preferably methyl group, benzyl group, phenyl group , Methoxy group, ethoxy group, phenoxy group, 2,6-diisopropylphenoxy group, dimethyl Amino group, a diethylamino group.

In the general formula [1], Z ^{_{is, SiR * 2, CR * 2}} , SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * 2 SiR * 2, GeR * 2 or BR ^* (wherein, R ^* is a hydrogen atom, a hydrocarbon group, a hydrocarbon group or a disubstituted amino group, if R ^* is more, each R ^* may be different be the same as each other A plurality of R ^{* s} may be combined to form a monocyclic or polycyclic ring).

Examples of the hydrocarbon group, hydrocarbon oxy group or disubstituted amino group of R ^* include the hydrocarbon group, hydrocarbon oxy group or disubstituted amino group described in X ^{1 to} X ⁴ . Further, examples of the group in which a plurality of R ^{* s} form a ring include alkylene groups such as a tetramethylenediyl group and a pentamethylenediyl group. R ^* is preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an alkylene group, more preferably a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a methoxy group, a tetramethylenediyl group, or a penta A methylenediyl group.

  Specific examples of Z include, for example, dimethylsilylene, ethylmethylsilylene, diethylsilylene, methylphenylsilylene, diphenylsilylene, dimethoxysilylene, methylene, ethylidene, isopropylene, ethylmethylmethylene, diethylmethylene, methylphenylmethylene, diphenylmethylene, cyclopentene. , Cyclohexene, tetraethyldisilylene, tetraphenyldisilylene, ethylene, tetramethylethylene, tetraphenylethylene, dimethylgermylene, diphenylgermylene, methylborene, phenylborene, etc., among which dimethylsilylene, diphenylsilylene, methylene, iso Propylene, diphenylmethylene or ethylene.

In the general formula [1], Y is a divalent hydrocarbon group containing a hetero atom bonded to M by an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, and represents —O—, —S—, —NR ^5. -, -PR ^6- , alkyleneoxy group, alkylenethio group, alkyleneamino group, alkylenephosphino group, phenyleneoxy group, phenylenethio group, phenyleneamino group, phenylenephosphino group, silyleneoxy group, silyleneamino group, etc. I can give you. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydrocarbon group or a substituted silyl group. R ⁵ and R ⁶ are preferably each independently an alkyl group or an aryl group, more preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a tert-butyl group, a cyclohexyl group, or a phenyl group It is a group.

  Examples of the alkyleneoxy group for Y include a methyleneoxy group, an ethyleneoxy group, a trimethyleneoxy group, and a dimethylmethyleneoxy group.

  Examples of the alkylenethio group for Y include a methylenethio group, an ethylenethio group, a trimethylenethio group, and a dimethylmethylenethio group.

  Examples of the alkyleneamino group for Y include a methylenethio group, an ethylenethio group, a trimethylenethio group, and a dimethylmethylenethio group.

（一般式［５］において、Ａ²は酸素原子、硫黄原子、−ＮＲ⁷−または−ＰＲ⁸−を表しＭと結合する基である。Ｒ¹、Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に水素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基または置換シリル基を表し、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は任意に結合して単環または多環を形成していてもよい。Ｒ⁷およびＲ⁸はそれぞれ独立に水素原子、炭化水素基または置換シリル基を表す。） The phenyleneoxy group, phenylenethio group, phenyleneamino group or phenylenephosphino group in Y is represented, for example, by the following general formula [5].

(In General Formula [5], A ² represents an oxygen atom, a sulfur atom, —NR ⁷ — or —PR ⁸ —, and is a group bonded to M. R ¹ , R ² , R ³ and R ⁴ are each independently selected. Represents a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon oxy group or a substituted silyl group, and R ¹ , R ² , R ³ and R ⁴ may be arbitrarily bonded to form a monocyclic or polycyclic ring. R ⁷ and R ⁸ each independently represents a hydrogen atom, a hydrocarbon group or a substituted silyl group.

R ⁷ and R ⁸ are preferably each independently an alkyl group or an aryl group, more preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a tert-butyl group, a cyclohexyl group, or a phenyl group It is a group.

Examples of the halogen atom, hydrocarbon group or hydrocarbon oxy group represented by R ^{1 to} R ⁴ include the halogen atom, hydrocarbon group or hydrocarbon oxy group described as X ^{1 to} X ^4. As the substituted silyl group of R ^{1 to} R ⁴ , a methylsilyl group, an ethylsilyl group, a phenylsilyl group, a dimethylsilyl group, a diethylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, Triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n- Examples include hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, etc. It is possible.

R ^{1 to} R ⁴ are preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or a silyl group, and more preferably a hydrogen atom, a chlorine atom, a methyl group, a tert-butyl group, or a neopentyl group. , Phenyl group, adamantyl group, methoxy group, trimethylsilyl group, or tert-butyldimethylsilyl group.

In the general formula [2], T represents a hydrocarbon oxy group, a disubstituted amino group, or a trisubstituted phosphinoimino group. Examples of the hydrocarbon oxy group or disubstituted amino group of T include the hydrocarbon oxy groups or disubstituted amino groups described in X ^{1 to} X ⁴ .

（一般式［６］におけるＲ⁹は水素原子、炭化水素基または置換シリル基を表す。） The trisubstituted phosphinoimino group in T represents a group of the following general formula [6].

(R ⁹ in the general formula [6] represents a hydrogen atom, a hydrocarbon group or a substituted silyl group.)

Examples of the hydrocarbon group or substituted silyl group for R ⁹ include the hydrocarbon group described for X ^{1 to} X ⁴ or the substituted silyl group described for R ^{1 to} R ⁴ . Preferably, methyl group, ethyl group, isopropyl group, tert-butyl group, neopentyl group, cyclopentyl group, neohexyl group, cyclohexyl group, phenyl group, benzyl group, trimethylsilyl group, tert-butyldimethylsilyl group, or triphenylsilyl group And particularly preferably a methyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group or a trimethylsilyl group.

  T is preferably a methoxy group, an ethoxy group, a t-butoxy group, a benzyloxy group, a phenoxy group, a 2-methylphenoxy group, a 2-isopropylphenoxy group, a 2-tert-butylphenoxy group, a 2-phenylphenoxy group, 3 -Methylphenoxy group, 3-isopropylphenoxy group, 3-tert-butylphenoxy group, 3-phenylphenoxy group, 4-methylphenoxy group, 4-isopropylphenoxy group, 4-tert-butylphenoxy group, 4-phenylphenoxy group 2,6-dimethylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diphenylphenoxy group, trimethylphosphineimino group, tri-tert-butylphosphineimino group , Triphenylphosphie An imino group, more preferably a methoxy group, t-butoxy group, phenoxy group, 2-methylphenoxy group, 2-isopropylphenoxy group, 2-tert-butylphenoxy group, 2-phenylphenoxy group, 2,6- Dimethylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diphenylphenoxy group, trimethylphosphineimino group, tri-tert-butylphosphineimino group, triphenylphosphineimino group It is a group.

  Specific examples of the compound represented by the general formula [1] include dimethylsilylene (methylamide) (cyclopentadienyl) titanium dichloride, dimethylsilylene (ethylamide) (cyclopentadienyl) titanium dichloride, dimethylsilylene (n -Propylamide) (cyclopentadienyl) titanium dichloride, dimethylsilylene (isopropylamide) (cyclopentadienyl) titanium dichloride, dimethylsilylene (tert-butylamide) (cyclopentadienyl) titanium dichloride, dimethylsilylene (phenylamide) (Cyclopentadienyl) titanium dichloride, dimethylsilylene (cyclohexylamide) (cyclopentadienyl) titanium dichloride, etc. Cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadiene Enyl, sec-butylcyclopentadienyl, isobutylcyclopentadienyl, tert-butylcyclopentadienyl, di-tert-butylcyclopentadienyl, tert-butyldimethylsilylcyclopentadienyl, phenylcyclopentadienyl, Compound changed to indenyl, methylindenyl, phenylindenyl or di-tert-butylfluorenyl, dimethylsilylene to diethylsilylene, diphenylsilylene, dimethoxysilylene, methylene Compounds changed to ethylene or isopropylidene, compounds changed from amide to phosphide, compounds changed from titanium to zirconium or hafnium, dichloride to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide, Examples include transition metal complexes such as diisopropoxide, 2,4-hexadiene or compounds changed to 1,4-diphenyl-1,3-butadiene. These compounds represented by the general formula [1] are used alone or in combination of two or more.

（一般式［４］において、Ｍは元素の周期律表の第４族の遷移金属原子を示し、Ｃｐ¹はシクロペンタジエン型アニオン骨格を有する基を示す。Ｘ¹、Ｘ²、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基、置換シリル基または２置換アミノ基を示す。Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は任意に結合して単環または多環を形成していてもよい。ＺはＳｉＲ^* ₂、ＣＲ^* ₂、ＳｉＲ^* ₂ＳｉＲ^* ₂、ＣＲ^* ₂ＣＲ^* ₂、ＣＲ^*＝ＣＲ^*、ＣＲ^* ₂ＳｉＲ^* ₂、ＧｅＲ^* ₂またはＢＲ^*（ここでＲ^*は、水素原子、炭化水素基、炭化水素オキシ基または２置換アミノ基を表し、Ｒ^*が複数ある場合、夫々のＲ^*は互いに同じであっても異なっていてもよく、複数あるＲ^*は結合して単環または多環を形成してもよい。）で示される２価の基を示す。Ａ¹は酸素原子または硫黄原子を示す。） The transition metal compound represented by the general formula [1] is preferably a transition metal compound represented by the following general formula [4].

(In the general formula [4], M represents a group 4 transition metal atom in the periodic table of elements, and Cp ¹ represents a group having a cyclopentadiene type anion skeleton. X ¹ , X ² , R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon oxy group, a substituted silyl group or a disubstituted amino group, wherein R ¹ , R ² , R ³ and R ⁴ are bonded to any good .Z also form a monocyclic or polycyclic ring _{^{SiR * 2, CR * 2,}} SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * ₂ SiR ^* _2, GeR ^* ₂ or BR ^* (here R ^*, a hydrogen atom, a hydrocarbon group, a hydrocarbon group or a disubstituted amino group, if R ^* is more, each R ^* are each or different and the same, the plurality of R ^* bonded to form a monocyclic or polycyclic .A ¹ showing a divalent group represented by which may be.) Represents an oxygen atom or a sulfur atom.)

Specific examples of the compound represented by the general formula [4] include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert- Butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) Titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) Titanium Dichlorai , Methylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride ,
Methylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methyl Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert -Butyl-5-chloro-2-phenoxy) titanium dichloride,
Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) tita Um dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro- 2-phenoxy) titanium dichloride,
Methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5 -Chloro-2-phenoxy) titanium dichloride,
Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( Fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, iso Ropyridene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride ,
Isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phen Xyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5- Chloro-2-phenoxy) titanium dichloride,
Isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclo) Ntadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-to Methylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) ) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo) Ntadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo) Pentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Isopropylidene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, isopropylidene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl) 5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride Id, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) ) Titanium dichloride,
Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl) -5-chloro-2-phenoxy) titanium dichloride,
Diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert- Tilcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) ) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethyl) Rylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenyl Methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,
Diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3- ert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, etc., and titanium of these compounds to zirconium or hafnium Modified compounds, dichloride to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide, diisopropoxide, 2,4-hexadiene or 1,4-diphenyl-1,3-butadiene Modified compounds,
(Cyclopentadienyl) to (methylcyclopentadienyl), (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (tetramethylcyclopentadienyl), (ethylcyclopentadienyl), (n -Propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl), (isobutylcyclopentadienyl), (tert-butylcyclopentadienyl), (di-tert-butyl) Cyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (indenyl), (methylindenyl), (phenylindenyl) or (di-tert-butylfluorene) Nyl), (3,5-dimethyl-2- (Phenoxy) to (2-phenoxy), (3-methyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), (3-phenyl-5-methyl-2-phenoxy), ( 3-tert-butyldimethylsilyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), (3,5-dimethyl-2-thiophenoxy), (2-thiophenoxy), (3-methyl-2- Thiophenoxy), (3,5-di-tert-butyl-2-thiophenoxy), (3-phenyl-5-methyl-2-thiophenoxy), (3-tert-butyldimethylsilyl-2-thiophenoxy) Alternatively, a transition metal complex such as a compound changed to (3-trimethylsilyl-2-thiophenoxy) can be used.

Specific examples of the compound represented by the general formula [4] include dimethylsilyl (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2- Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Silyl (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride , Dimethyl Ryl (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride , Dimethylsilyl (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride , Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride
Dimethylsilyl (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopenta Enyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl ( Methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethyl Silyl (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride Roraido,
Dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylshi Ru (n-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl- 2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert- Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopenta) Dienyl) 3,5 diamyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) Titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titan Mujikuroraido, dimethylsilyl (tert- butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride Dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2 -Phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5 -Methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethyl) Cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) Titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl- 2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titan Mujikuroraido, dimethylsilyl (trimethylsilyl cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silyl (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (full Renyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-diamil -2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride, etc., and (cyclopentadienyl) of these compounds (dimethyl) Clopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl), (Isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (indenyl), (methylindenyl), (phenylindenyl) or (di-tert-butyl) A compound changed to (fluorenyl), (2-phenoxy) as (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethylsilyl-2-phenoxy), (2-thiophenoxy), (3-phenyl-2-thiophenoxy) (3-trimethylsilyl-2-thiophenoxy) or a compound changed to (3-tert-butyldimethylsilyl-2-thiophenoxy), a compound obtained by changing dimethylsilyl to diethylsilyl, diphenylsilyl, or dimethoxysilyl, titanium Compound changed to zirconium or hafnium, dichloride is dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide, diisopropoxide, 2,4-hexadiene or 1,4-diphenyl-1 And transition metal complexes such as compounds changed to 3-butadiene. These compounds represented by the general formula [4] are used alone or in combination of two or more.

  Specific examples of the compound represented by the general formula [2] include dichloro (cyclopentadienyl) (trimethylphosphinimine) titanium, dichloro (cyclopentadienyl) (triethylphosphinimine) titanium, dichloro (cyclopenta). Dienyl) (tri-n-propylphosphinimine) titanium, dichloro (cyclopentadienyl) (triisopropylphosphineimine) titanium, dichloro (cyclopentadienyl) (tri-n-butylphosphineimine) titanium, dichloro (cyclo Pentadienyl) (tri-sec-butylphosphineimine) titanium, dichloro (cyclopentadienyl) (triisobutylphosphinimine) titanium, dichloro (cyclopentadienyl) (tri-tert-butyl) Sphinimine) titanium, dichloro (cyclopentadienyl) (tri-n-pentylphosphineimine) titanium, dichloro (cyclopentadienyl) (tri-sec-pentylphosphineimine) titanium, dichloro (cyclopentadienyl) (triiso) Pentylphosphineimine) titanium, dichloro (cyclopentadienyl) (tri-tert-pentylphosphineimine) titanium, dichloro (cyclopentadienyl) (tineopenentylphosphinimine) titanium, dichloro (cyclopentadienyl) (tricyclopentyl) Phosphinimine) titanium, dichloro (cyclopentadienyl) (tri-n-hexylphosphineimine) titanium, dichloro (cyclopentadienyl) (tri-sec-hexyl) Sphinimine) titanium, dichloro (cyclopentadienyl) (triisohexylphosphineimine) titanium, dichloro (cyclopentadienyl) (tri-tert-hexylphosphineimine) titanium, dichloro (cyclopentadienyl) (trineohexylphosphine) Imine) titanium, dichloro (cyclopentadienyl) (tricyclohexylphosphineimine) titanium, dichloro (cyclopentadienyl) (triphenylphosphineimine) titanium, dichloro (cyclopentadienyl) (tolylphosphineimine) titanium, dichloro (Cyclopentadienyl) [tris (trimethylsilyl) phosphinimine] titanium, dichloro (cyclopentadienyl) [tris (butyldimethylsilyl) phos Finimine] titanium, etc., compounds in which the titanium of these compounds is changed to zirconium or hafnium, cyclopentadienyl is dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl , Ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, isobutylcyclopentadienyl, tert-butylcyclopentadienyl Tert-butyldimethylsilylcyclopentadienyl, phenylcyclopentadienyl, indenyl, methylindenyl, phenylindenyl, fluorenyl or di-tert-butylfull Compound changed to rhenyl, dichloro is dibromo, diiodo, butadiene, butadiene, pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, 2,3-dimethylbutadiene, 1,3-heptadiene, 2,4-heptadiene 2,3-dimethyl-1,3-pentadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 3,4-dimethyl-2,4-hexadiene, 5,5-dimethyl-1 , 3-hexadiene, 2,2,7,7-tetramethyl-3,5-octadiene, 2,4,5,7-tetramethyl-3,5-octadiene, 1-phenylbutadiene, 2-phenylbutadiene, 1 , 4-diphenylbutadiene, 2,3-diphenylbutadiene, (chloro) (methyl), (benzyl) (chloro), Chloro) (methoxy) or (chloro) (transition metal compounds such compounds modified phenoxy) and the like.

  Further, specific compounds represented by the above general formula [2] include, for example, dichloro (cyclopentadienyl) (phenoxy) titanium, dichloro (cyclopentadienyl) (2-methylphenoxy) titanium, dichloro (cyclopenta). Dienyl) (2-isopropylphenoxy) titanium, dichloro (cyclopentadienyl) (2-tert-butylphenoxy) titanium, dichloro (cyclopentadienyl) (2-phenylphenoxy) titanium, dichloro (cyclopentadienyl) (3-methylphenoxy) titanium, dichloro (cyclopentadienyl) (3-isopropylphenoxy) titanium, dichloro (cyclopentadienyl) (3-tert-butylphenoxy) titanium, dichloro (cyclopentadienyl) ( -Phenylphenoxy) titanium, dichloro (cyclopentadienyl) (4-methylphenoxy) titanium, dichloro (cyclopentadienyl) (4-isopropylphenoxy) titanium, dichloro (cyclopentadienyl) (4-tert-butylphenoxy) ) Titanium, dichloro (cyclopentadienyl) (4-phenylphenoxy) titanium, dichloro (cyclopentadienyl) (2,6-dimethylphenoxy) titanium, dichloro (cyclopentadienyl) (2,6-diisopropylphenoxy) Titanium, dichloro (cyclopentadienyl) (2,6-di-tert-butylphenoxy) titanium, dichloro (cyclopentadienyl) (2,6-diphenylphenoxy) titanium, etc. Compounds in which nium is changed to zirconium or hafnium, cyclopentadienyl is dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, ethylcyclopentadienyl, n-propyl Cyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, isobutylcyclopentadienyl, tert-butylcyclopentadienyl, tert-butyldimethylsilylcyclopentadienyl , Phenylcyclopentadienyl, indenyl, methylindenyl, phenylindenyl, fluorenyl or di-tert-butylfluorenyl compound, dichloro is dibromo, diiodo Butadiene, butadiene, pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, 2,3-dimethylbutadiene, 1,3-heptadiene, 2,4-heptadiene, 2,3-dimethyl-1,3 Pentadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 3,4-dimethyl-2,4-hexadiene, 5,5-dimethyl-1,3-hexadiene, 2,2,7 , 7-tetramethyl-3,5-octadiene, 2,4,5,7-tetramethyl-3,5-octadiene, 1-phenylbutadiene, 2-phenylbutadiene, 1,4-diphenylbutadiene, 2,3- Diphenylbutadiene, (chloro) (methyl), (benzyl) (chloro), (chloro) (methoxy) or (chloro) (phenoxy) Transition metal compounds such modified compounds. These compounds represented by the general formula [2] are used alone or in combination of two or more.

Component (ii) of the present invention is a chromium compound represented by the following general formula [3].
CrJ _j K _k [3]
(In General Formula [3], j represents an integer of 0 to 5, k represents an integer of 0 to 6. However, 3 ≦ j + k ≦ 6 is satisfied. Cr represents a chromium atom. J represents an oxygen atom. Represents a halogen atom, a hydrocarbon group, a hydrocarbon oxy group or a disubstituted amino group, and when there are a plurality of J, each J may be the same or different from each other, and K is a lone electron pair or a π electron. Represents a group bonded to a chromium atom, and when there are a plurality of K, each K may be the same as or different from each other.)

Examples of the halogen atom, hydrocarbon group, hydrocarbonoxy group or disubstituted amino group of J in the general formula [3] include the halogen atom, hydrocarbon group, hydrocarbonoxy group or 2 described in X ^{1 to} X ^4. Examples of substituted amino groups can be given.

  J is preferably fluoro, chloro, bromo, iodo, methyl, butyl, allyl, trimethylsilylmethyl, methoxy, ethoxy, isopropoxy, tert-butoxy, acetate, propionate, Butyrate group, neopentanoate group, 2-ethylhexanoate group, laurate group, stearate group, benzoate group, naphthenoate group, acetylacetonate group, trifluoroacetylacetonate group, hexafluoroacetylacetonate group, 2 , 2,6,6, -tetramethyl-3,5-heptanedionate group, benzoylacetonate group, more preferably fluoro group, chloro group, acetate group, 2-ethylhexanoate group, naphthenoate group, Acetylacetonate group, hexafluoroa A cetylacetonate group, 2,2,6,6, -tetramethyl-3,5-heptanedionate group, and benzoylacetonate group.

K in the general formula [3] represents a group bonded to a chromium atom by a lone electron pair or π electron.
The group bonded to the chromium atom by the lone pair is a neutral ligand bonded to the chromium atom by a coordinate bond, for example, ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane; methanol, ethanol, isopropanol, Alcohols such as 2-ethylhexanol; esters such as ethyl acetate, isopropyl acetate and butyl acetate; triethylamine, N, N, N ′, N′-tetramethylethylenediamine, 1,4,7-trimethyl-1,4,7- Amines such as triazacyclononane; pyridines such as pyridine, 4-methylpyridine, 4-ethylpyridine, 4-isopropylpyridine, 4-phenylpyridine, 2,6-dimethylpyridine, quinoline; trimethylphosphine, Liethylphosphine, tributylphosphine, triphenylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, 1,2-bis (dimethylphosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,2-bis (diphenyl) Phosphino) ethane, phosphines such as 1,3-bis (diphenylphosphino) propane; phosphine oxides such as trimethylphosphine oxide, triethylphosphine oxide and triphenylphosphine oxide; nitriles such as acetonitrile and benzonitrile; end-on type Nitrogen molecule: carbon monoxide and the like, preferably tetrahydrofuran, dioxane, isopropanol, 2-ethylhexanol, ethyl acetate, butyl acetate, 1,4,7-trime Til-1,4,7-triazacyclononane, pyridine, 4-ethylpyridine, 4-isopropylpyridine, 4-phenylpyridine, tributylphosphine, triphenylphosphine or triphenylphosphine oxide.

  The group bonded to the chromium atom by the π electron is a neutral ligand bonded to the chromium atom by multiple bond orbitals, for example, olefins such as ethylene and propylene; butadiene, 2,4-hexadiene, 1,4 -Dienes such as diphenylbutadiene; ketones such as acetone and benzophenone; side-on type nitrogen molecules, and the like, preferably olefins or dienes, more preferably ethylene, butadiene, 2,4-hexadiene, Or 1,4-diphenylbutadiene.

  Specific examples of the compound represented by the general formula [3] include chromium (II) dimethyl, chromium (III) trimethyl, chromium (IV) tetrachloride, chromium (III) tris (η-allyl), dichrome ( II) tetrakis (η-allyl), chromium (IV) tetrakis (trimethylsilylmethyl), chromium (IV) tetraethoxide, chromium (IV) tetraisopropoxide, chromium (IV) tetrakis (tert-butoxide), chromium (II ) Bisacetate, chromium (III) tetra (acetate), chromium (II) bispropionate, chromium (III) trispropionate, chromium (III) trisbutyrate, chromium (II) bis (2-ethylhexano) Ate), chromium (III) tris (2-ethylhexanoate), chromium (III) Squirrel (oxy-2-ethylhexanoate), chromium (III) tris (dichloroethyl hexanoate), chromium (II) bis (neopentanoate), chromium (III) tris (neopentanoate), chromium (II) bis (laurate), chromium (III) tris (laurate), chromium (II) bis (stearate), chromium (III) tris (stearate), chromium (II) bis (benzoate), chromium (III) Tris (benzoate), chromium (II) bis (naphthenoate), chromium (III) tris (naphthenoate), chromium (II) oxalate, chromium (II) bis (acetylacetonate), chromium (III) tris (acetylacetonate) Chromium (III) tris (trifluoroacetylacetonate Chromium (III) tris (hexafluoroacetylacetonate), chromium (III) (2,2,6,6-tetramethyl-3,5-heptanedionate), chromium (III) tris (benzoylacetonate), Chromium (II) difluoride, Chromium (III) trifluoride, Chromium (II) dichloride, Chromium (III) trichloride, Chromium (II) dibromide, Chromium (III) tribromide, Chromium (II) diiodide, Chromium (III) A triiodide etc. are mentioned.

  Further, trichlorotrianiline chromium (III), dichlorobis (pyridine) chromium (II), dichlorobis (4-ethylpyridine) chromium (II), trichlorotripyridine chromium (III), trichlorotris (4-isopropylpyridine) chromium (III ), Trichlorotris (4-ethylpyridine) chromium (III), trichlorotris (4-phenylpyridine) chromium (III), trichloro (1,4,7-trimethyl-1,4,7-triazacyclononane) chromium ( III), dichlorobis (triphenylphosphine oxide) chromium (II), trichlorotris (triphenylphosphine) chromium (III), trichlorobis (tributylphosphine) chromium (III) dimer, trichlorotris (ethyl acetate) (III), trichlororobis (butyl acetate) chromium (III), trichlorotris (tetrahydrofuran) chromium (III), trichlorotris (dioxane) chromium (III), trichlorotris (isopropanol) chromium (III), trichlorotris ( 2-ethylhexanol) chromium (III) and the like. These compounds represented by the general formula [3] are used alone or in combination of two or more.

Component (iii) of the present invention is the following component (A) and / or component (B).
(A): One or more aluminum compounds selected from the following (A1) to (A3) (A1) Organoaluminum compound represented by the general formula E ¹ _a AlU _3-a (A2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having a structure represented by _b (A3) a linear aluminoxane having a structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ ₂ (the above ( In A1) to (A3), a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, c represents an integer of 1 or more, and E ¹ , E ^2, and E ³ are carbonized. represents a hydrogen group, if E ¹ is more, a plurality of E ¹ may be different be the same as each other. Further, a plurality of E ² may be different be the same as each other, a plurality there E ³ is optionally different from one another identical .U is or hydrogen atom It represents a halogen atom, if U is more, a plurality of U may be different be the same as each other.)
(B): One or more boron compounds selected from the following (B1) to (B3) (B1) Boron compounds represented by the general formula BQ ¹ Q ² Q ³ (B2) General formula G ⁺ (BQ ⁴ Q ⁵ Boron compound represented by Q ⁶ Q ⁷ ) ⁻ (B3) Boron compound represented by general formula (LH) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ⁻ (in the above (B1) to (B3) , B represents a trivalent boron atom, Q ^{1 to} Q ¹¹ represent a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, and Q ^{1 to} Q ¹¹ represent G ⁺ represents an inorganic or organic cation, L represents a neutral Lewis base, and (L—H) ⁺ represents a Bronsted acid.

In general formula E ¹ _a AlU _3-a of (A1), E ¹ is a hydrocarbon group, preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl having 1 to 8 carbon atoms. a group, if E ¹ is more, a plurality of E ¹ may be different be the same as each other. U is a hydrogen atom or a halogen atom, and when there are a plurality of U, the plurality of U may be the same or different from each other. a is a number satisfying 0 <a ≦ 3, and preferably 2 or 3.

Specific examples of (A1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexyl. Dialkylaluminum chlorides such as aluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, dipropiol Aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride.
Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

In general formula {-Al (E ² ) —O—} _b of (A2), E ² is a hydrocarbon group, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal Examples of the alkyl group include a pentyl group and a neopentyl group, and a methyl group and an isobutyl group are preferable. A plurality of E ² may be the same as or different from each other. Moreover, b is an integer greater than or equal to 2, Preferably b is an integer of 2-40.

In general formula E ³ {-Al (E ³ ) —O—} _c AlE ³ ₂ in (A3), E ³ is a hydrocarbon group, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group. And alkyl groups such as an isobutyl group, a normal pentyl group, and a neopentyl group, preferably a methyl group and an isobutyl group. A plurality of E ³ may be the same as or different from each other. C is an integer of 1 or more, and preferably c is an integer of 1 to 40.

  There is no restriction | limiting in particular about the manufacturing method of (A2) and (A3), A well-known method is used. For example, a method in which a solution in which a trialkylaluminum (such as trimethylaluminum) is dissolved in an appropriate organic solvent (such as benzene or aliphatic hydrocarbon) is contacted with water, or a metal salt (copper sulfate) containing crystal water Examples thereof include a method of producing a product by bringing a hydrate and the like into contact with a trialkylaluminum (such as trimethylaluminum).

In the general formula BQ ¹ Q ² Q ³ of (B1), B is a trivalent boron atom, and Q ^{1 to} Q ³ are halogen atoms, hydrocarbon groups (including halogenated hydrocarbon groups), substituted silyl groups , An alkoxy group or a disubstituted amino group, and Q ^{1 to} Q ³ may be the same or different. In Q ^{1 to} Q ³ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-butyl group, a sec-butyl group, Phenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,6-di-tert-butylphenyl group, 2,4,6-trimethylphenyl group, trifluoromethyl group, 2,3,4, Examples include 5,6-pentafluorophenyl group and 2,6-bis (trifluoromethyl) phenyl group. The substituted silyl group is a silyl group substituted with a hydrocarbon group, and examples thereof include a trimethylsilyl group and a triethylsilyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a t-butoxy group. The disubstituted amino group is an amino group substituted with two hydrocarbon groups, and examples thereof include a dimethylamino group and a diethylamino group. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 2 to 2 carbon atoms. 20 is an amino group, more preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and further preferably a fluorinated hydrocarbon having 1 to 20 carbon atoms having at least one fluorine atom. And particularly preferably a fluorinated aryl group having 6 to 20 carbon atoms and having at least one fluorine atom.

  Specific examples of (B1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, and tris. (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane and the like are mentioned, but most preferably, tris (pentafluorophenyl) ) Borane.

In the general formula G ⁺ (BQ ⁴ Q ⁵ Q ⁶ Q ⁷ ) ⁻ of (B2), B is a trivalent boron atom, and Q ^{4 to} Q ⁷ are each a halogen atom or a hydrocarbon group (halogenated hydrocarbon group). A substituted silyl group, an alkoxy group or a disubstituted amino group, and Q ^{4 to} Q ⁷ may be the same or different. Specific examples and preferred groups of Q ^{4 to} Q ⁷ are the same as the specific examples and preferred groups of Q ^{1 to} Q ³ in the above (B1). Specific examples of (BQ ⁴ Q ⁵ Q ⁶ Q ⁷ ) ⁻ include tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5). -Tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3 5-bistrifluoromethylphenyl) borate and the like. G ⁺ is an inorganic or organic cation. Examples of the inorganic cation include ferrocenium cation, alkyl-substituted ferrocenium cation, and silver cation. Examples of the organic cation include triphenylmethyl cation. . G ⁺ is preferably a carbenium cation, particularly preferably a triphenylmethyl cation.

  Specific examples of the component (B2) include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyl. Examples thereof include tetrakis (pentafluorophenyl) borate and triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and triphenylcarbenium tetrakis (pentafluorophenyl) borate is preferable.

In the general formula (LH) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ⁻ of (B3), B is a trivalent boron atom, and Q ^{8 to} Q ¹¹ are each a halogen atom or a hydrocarbon group (halogen) A substituted silyl group, an alkoxy group, or a disubstituted amino group, and Q ^{4 to} Q ⁷ may be the same or different. Specific examples and preferred groups of Q ^{8 to} Q ¹¹ are the same as the specific examples and preferred groups of Q ^{1 to} Q ³ in the component (B1). ^{(BQ 8 Q 9 Q 10 Q} 11) - embodiment, preferred groups are, above in component ^{(B2) (BQ 4 Q 5} Q 6 Q 7) - specific examples of the same as the preferable groups. L is a neutral Lewis base, (LH) ⁺ is a Bronsted acid, and specific examples of the Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, And triarylphosphonium.

  Specific examples of the component (B3) include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n- Butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N- 2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, di Sopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate, preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate It is.

  When only the component (A) is used as the component (iii), the component (A) is preferably (A2) and / or (A3). Moreover, when using a component (A) and a component (B) as a component (iii), (A1) is easy to use as a component (A).

  In the method for producing an ethylene-based polymer of the present invention, ethylene is supplied as a monomer component, the component (i), the component (ii) and the component (iii) are used as catalyst components, and the component (i), component ( Polymerization is carried out in the presence of a catalyst obtained by contacting ii) and component (iii). As a method of bringing component (i), component (ii) and component (iii) into contact, any means may be used as long as component (i), component (ii) and component (iii) are in contact with each other. A method in which component (i), component (ii) and component (iii) are mixed and contacted with or without being diluted with a solvent, or separately supplied to a polymerization tank and contacted in a polymerization tank Can take the way. Here, component (i) to component (iii) may be used in combination of a plurality of types of compounds, respectively, but some of them may be mixed in advance or used separately. You may use by supplying to a tank.

  As the usage ratio of component (i) to component (iii), [number of moles of chromium atom contained in component (ii)] / [number of moles of transition metal atom contained in component (i)] is preferably It is 0.1-100, More preferably, it is 0.5-20. [Mole number of aluminum atom contained in component (A) of component (iii)] / [Mole number of transition metal atom contained in component (i)] is preferably 0.1 to 10,000, Preferably, it is 5 to 2000, and [number of moles of boron atom contained in component (B) of component (iii)] / [number of moles of transition metal atom contained in component (i)] is preferably 0.01. It is -100, More preferably, it is 0.5-10.

  When the components (i) to (iii) are used in a solution state, a state suspended in a solvent, or a slurry state, the concentration of each component depends on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. It is selected appropriately. In general, the concentration of component (i) is usually 0.001 to 200 μmol / liter, more preferably 0.001 to 100 μmol / liter in terms of the molar concentration of transition metal atoms contained in component (i), More preferably, it is 0.05-50 micromol / liter. The concentration of component (ii) is usually 0.001 to 250 μmol / liter, more preferably 0.001 to 150 μmol / liter, even more preferably in terms of the molar concentration of transition metal atoms contained in component (ii). Is 0.05 to 100 μmol / liter. About component (iii), the density | concentration of component (A) is 0.01-5000 mmol / liter normally in conversion of the molar concentration of the aluminum atom contained in component (A), More preferably, it is 0.1-2500 mmol / liter. Liters, more preferably 0.1 to 2000 mmol / liter, and the concentration of component (B) is usually 0.001 to 500 μmol / liter in terms of the molar concentration of boron atoms contained in component (B). Yes, more preferably from 0.01 to 250 μmol / liter, and even more preferably from 0.05 to 100 μmol / liter.

  As a method for producing the ethylene polymer of the present invention, any method such as a fixed bed reaction method, a gas phase reaction method, a solution reaction method using an appropriate solvent, and a slurry reaction method can be used. When a solvent is used, various solvents can be used under the condition that the catalyst is not deactivated. Examples of such solvents include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane; benzene, toluene Aromatic hydrocarbons such as; halogenated hydrocarbons such as methylene dichloride. In these production methods, either a continuous reaction or a batch reaction may be used.

  About reaction temperature in the manufacturing method of the ethylene-type polymer of this invention, it is -50-200 degreeC normally, Preferably it is -20-100 degreeC. The reaction pressure is usually 6 MPa or less. The reaction time is appropriately determined depending on the type of the ethylene-based polymer and the reaction apparatus, and is usually 1 minute to 20 hours.

  In the present invention, an ethylene polymer having an alkyl side chain can be produced by carrying out polymerization by supplying substantially only ethylene as the monomer component. In the present invention, an ethylene polymer having a large number of alkyl side chains can be produced with high activity.

Hereinafter, the present invention will be described in more detail with reference to examples.
I. Raw material (i) transition metal compound
(1) Dimethoxy [dimethylsilyl (tetramethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy)] titanium: synthesized by the method described in JP-A-2000-119287.
(2) Dichloro (pentamethylcyclopentadienyl) (2,6-diisopropylphenoxy) titanium: synthesized by the method described in JP-A-11-166010.
(3) Dichloro [dimethylsilyl (tetramethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy)] titanium: synthesized by the method described in JP-A-9-87313.
(4) Dichloro [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy)] titanium: synthesized by the method described in JP-A-9-87313.
(5) Dichloro [diphenylmethylene (cyclopentadienyl) (fluorenyl)] zirconium: A product of Boulder was used.
(Ii) Chromium compound Chromium (III) tris (2-ethylhexanoate): A 70% mineral oil product manufactured by Strem was used.
(Iii) Aluminum compound
(1) Trimethylaluminum (TMA): A toluene solution manufactured by Tosoh Finechem Co., Ltd. having an Al concentration of 1.0 mol / L was used.
(2) MMAO-3A: Tosoh Finechem, trade name MMAO-3A, and a toluene solution having an Al concentration of 1.52 mol / L were used.
(Iv) Boron compound (triphenylcarbenium) [tetrakis (pentafluorophenyl) borate] (TB): A 5 mmol / L toluene solution manufactured by Asahi Glass Co., Ltd. was used.

II. Analysis (1) Intrinsic viscosity [η]
It measured in the tetralin solution at 135 degreeC using the Ubbelohde viscometer.

(2) Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn)
It measured on the following conditions by the gel permeation chromatography (GPC). A calibration curve was prepared using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Equipment Millico Waters 150CV type column Tosoh TSK gelGMH6-HT 3 Measurement temperature 145 ° C
Solvent orthodichlorobenzene,
Sample concentration 5mg / 8ml

(3) Alkyl side chain amount of ethylene-based polymer It was determined by infrared spectroscopy using an infrared spectrophotometer (IR-810 manufactured by JASCO Corporation). The characteristic absorption of the alkyl branch was expressed as the number of ethyl branches (EB) per 1000 carbons of the ethylene-based polymer using a peak of 1378 cm ^{−1 to} 1303 cm ⁻¹ .

(4) Melting | fusing point of ethylene polymer It calculated | required on condition of the following using the differential scanning calorimeter (Seiko Co., Ltd. SSC-5200).
Temperature rise: 40 ° C to 150 ° C (10 ° C / min), hold for 5 minutes Cooling: 150 ° C to 10 ° C (5 ° C / min), hold for 10 minutes Measurement: 10 ° C to 160 ° C (5 ° C / min)

[Example 1]
The autoclave with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and then 200 ml of toluene was charged as a solvent, and the reactor was heated to 60 ° C. After raising the temperature, the ethylene pressure was fed while adjusting the pressure to 0.6 MPa. After the system was stabilized, 1.0 ml of a TMA toluene solution (moles in terms of aluminum atoms: 1.0 mmol) was added, followed by chromium ( III) A toluene solution of tris (2-ethylhexanoate) was added at 1.0 μmol in terms of chromium atom, and dimethoxy [dimethylsilyl (tetramethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl- 2-Phenoxy)] Titanium toluene solution was added in an amount of 1.0 μmol in terms of titanium atom, and finally a toluene solution of TB was added in an amount of 6.0 μmol in terms of boron atom. Polymerization was carried out for 60 minutes while adjusting the temperature to 60 ° C. As a result of the polymerization, an ethylene polymer having EB = 31, Mw = 1.6 × 10 ⁵ , and Mw / Mn = 3.0 was obtained. The polymerization activity was 3.5 × 10 ⁶ g per hour per 1 mol of titanium atom.

[Example 2]
It carried out similarly to Example 1 except having used 0.75 mmol of MMAO-3A in conversion of the aluminum atom instead of TB. As a result of the polymerization, an ethylene polymer having EB = 28, Mw = 2.4 × 10 ⁴ , and Mw / Mn = 3.2 was obtained. The polymerization activity was 3.0 × 10 ⁵ g per hour per 1 mol of titanium atom.

[Example 3]
The autoclave with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and then 200 ml of toluene was charged as a solvent, and the reactor was heated to 60 ° C. After raising the temperature, the ethylene pressure was fed while adjusting the pressure to 0.6 MPa. After the system was stabilized, 1.0 ml of a TMA toluene solution (moles in terms of aluminum atoms: 1.0 mmol) was added, followed by chromium ( III) A toluene solution of tris (2-ethylhexanoate) was added in an amount of 1.0 μmol in terms of chromium atom, and finally a toluene solution of TB was added in an amount of 3.0 μmol in terms of boron atom. The mixture was stirred for 30 minutes while adjusting the temperature to 60 ° C., and then a toluene solution of dichloro (pentamethylcyclopentadienyl) (2,6-diisopropylphenoxy) titanium was converted to 0.50 μmol in terms of titanium atoms and a toluene solution of TB. Polymerization was carried out for 30 minutes while adding 3.0 μmol in terms of boron atom and adjusting the temperature to 60 ° C. As a result of the polymerization, an ethylene polymer having EB = 29, Mw = 2.4 × 10 ⁵ , and Mw / Mn = 4.2 was obtained. The polymerization activity was 1.9 × 10 ⁷ g per hour per 1 mole of titanium atoms.

[Example 4]
Dichloro [dimethylsilyl (tetramethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy)] instead of dichloro (pentamethylcyclopentadienyl) (2,6-diisopropylphenoxy) titanium The same operation as in Example 3 was carried out except that 1.0 μmol of titanium was used in terms of titanium atom. As a result of the polymerization, an ethylene polymer having EB = 49, Mw = 1.1 × 10 ⁵ , and Mw / Mn = 2.3 was obtained. The polymerization activity was 1.9 × 10 ⁷ g per hour per mol of titanium atom.

[Example 5]
Instead of dichloro (pentamethylcyclopentadienyl) (2,6-diisopropylphenoxy) titanium, dichloro [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy)] titanium is replaced with titanium. The same operation as in Example 3 was performed except that 1.0 μmol in terms of atoms was used. As a result of the polymerization, an ethylene polymer having EB = 33, Mw = 4.2 × 10 ⁴ , and Mw / Mn = 2.2 was obtained. The polymerization activity was 3.4 × 10 ⁶ g per hour per 1 mol of titanium atom.

[Comparative Example 1]
Dimethoxy [dimethylsilyl (tetramethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy)] titanium instead of dichloro [diphenylmethylene (cyclopentadienyl) (fluorenyl)] zirconium The same procedure as in Example 1 was performed except that 0.50 μmol in terms of atoms was used. As a result of the polymerization, an ethylene polymer having EB = 9, Mw = 2.3 × 10 ⁵ , and Mw / Mn = 3.4 was obtained. The polymerization activity was 2.8 × 10 ⁷ g per hour per 1 mol of zirconium atoms.

Claims (3)

A process for producing an ethylene polymer having an alkyl side chain, wherein ethylene is supplied as a monomer component, and polymerization is carried out using the following components (i), (ii) and (iii) as catalyst components Manufacturing method.
(I) A transition metal compound represented by the following general formula [1] or [2].

(In the general formula [1], M represents a group 4 transition metal atom in the periodic table of elements, and Cp ¹ represents a group having a cyclopentadiene type anion skeleton. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, .Z indicating a hydrocarbon group or a disubstituted amino group is _{^{SiR * 2, CR * 2,}} SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = _{^{CR *, CR * 2 SiR *}} 2, GeR * 2 or BR ^* (wherein R ^* is a hydrogen atom, a hydrocarbon group, a hydrocarbon group or a disubstituted amino group, if R ^* is more, respectively R ^* in the formulas may be the same or different from each other, and a plurality of R ^* may combine to form a monocyclic or polycyclic group.) Y represents oxygen Hete bonded to M by an atom, sulfur atom, nitrogen atom or phosphorus atom A divalent hydrocarbon group containing a rho atom is shown.)

(In General Formula [2], M represents a transition metal atom of Group 4 of the periodic table of elements, and Cp ² represents a group having a cyclopentadiene type anion skeleton. X ³ and X ⁴ are each independently A hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbonoxy group or a disubstituted amino group, and T represents a hydrocarbonoxy group, a disubstituted amino group or a trisubstituted phosphinoimino group.
(Ii) Chromium compound represented by the following general formula [3] CrJ _j K _k [3]
(In General Formula [3], j represents an integer of 0 to 5, k represents an integer of 0 to 6. However, 3 ≦ j + k ≦ 6 is satisfied. Cr represents a chromium atom. J represents an oxygen atom. Represents a halogen atom, a hydrocarbon group, a hydrocarbon oxy group or a disubstituted amino group, and when there are a plurality of J, each J may be the same or different from each other, and K is a lone electron pair or a π electron. Represents a group bonded to a chromium atom, and when there are a plurality of K, each K may be the same as or different from each other.)
(Iii) The following component (A) and / or component (B)
(A): One or more aluminum compounds selected from the following (A1) to (A3) (A1) Organoaluminum compound represented by the general formula E ¹ _a AlU _3-a (A2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having the structure represented by _b (A3) linear aluminoxane having the structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ ₂ (the above ( In A1) to (A3), a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, c represents an integer of 1 or more, and E ¹ , E ^2, and E ³ represent carbonization. It represents a hydrogen group, if E ¹ is more, each E ¹ may be different be the same as each other. in addition, E ² each may be different, even the same as each other, respectively E ³ .al is optionally different from one another the same aluminum Hara The, O is .U representing an oxygen atom represents a hydrogen atom or a halogen atom, if U there are multiple, U of each may be different, even the same as each other.)
(B): One or more boron compounds selected from the following (B1) to (B3) (B1) Boron compounds represented by the general formula BQ ¹ Q ² Q ³ (B2) General formula G ⁺ (BQ ⁴ Q ⁵ Boron compound represented by Q ⁶ Q ⁷ ) ⁻ (B3) Boron compound represented by general formula (LH) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ¹¹ ) ⁻ (in the above (B1) to (B3) , B represents a trivalent boron atom, Q ^{1 to} Q ¹¹ represent a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, and Q ^{1 to} Q ¹¹ represent G ⁺ represents an inorganic or organic cation, L represents a neutral Lewis base, and (L—H) ⁺ represents a Bronsted acid. The method for producing an ethylene polymer according to claim 1, wherein component (i) is a transition metal compound represented by the following general formula [4].

(In the general formula [4], M represents a group 4 transition metal atom in the periodic table of elements, and Cp ¹ represents a group having a cyclopentadiene type anion skeleton. X ¹ , X ² , R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon oxy group, a substituted silyl group or a disubstituted amino group, wherein R ¹ , R ² , R ³ and R ⁴ are bonded to any good .Z also form a monocyclic or polycyclic ring _{^{SiR * 2, CR * 2,}} SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * ₂ SiR ^* _2, GeR ^* ₂ or BR ^* (here R ^*, a hydrogen atom, a hydrocarbon group, a hydrocarbon group or a disubstituted amino group, if R ^* is more, each R ^* are each or different and the same, the plurality of R ^* bonded to form a monocyclic or polycyclic .A ¹ showing a divalent group represented by which may be.) Represents an oxygen atom or a sulfur atom.) The method for producing an ethylene-based polymer according to claim 1 or 2, wherein the polymerization is carried out in the presence of the component (i), the component (ii) and the component (iii) that have been subjected to contact treatment.