JP2002080517A - Transition metal compound, catalyst for addition polymerization, and method for manufacturing addition polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transition metal compound useful for preparation of a catalyst for an addition polymerization under suppressing exothermic quantity of an initial stage of a polymerization and having a catalytic activity applicable in an industrial scale to produce such a catalyst for addition polymerization, and a method capable of efficiently manufacturing an addition polymer under suppressing the exothermic quantity at the initial stage of the polymerization and applicable in the industrial scale. SOLUTION: The transition metal compound is expressed by formula (1). (M is a metal atom in oxidized state having +3 valence and selected from Ti, Zr and Hf; A is a multidentate monoanionic ligand; E is O or S; D is a neutral ligand coordinating to M; (n) is an integer of 0-2). The catalyst for addition polymerization obtained by contacting the transition metal compound with an organoaluminium compound and/or a specific boron compound, and the method for manufacturing he addition polymer using this catalyst are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound having a polydentate monoanionic ligand having a heteroatom as a substituent, a catalyst for addition polymerization obtained by using the transition metal compound, and the addition polymerization. The present invention relates to a method for producing an addition polymer using a catalyst.

[0002]

2. Description of the Related Art Many reports have been made on a method for producing an addition polymer using a single-site catalyst comprising a metallocene complex or the like. For example, JP-A-58-193
No. 09 discloses a method for producing an olefin polymer using a metallocene complex and an aluminoxane. When addition polymerization of an olefin or the like is carried out in such a system, there is a problem that the initial heating value is large due to its high initial activity, and it is difficult to control the polymerization reaction.

[0003]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention is a transition metal compound which is useful for controlling an addition polymerization catalyst having a catalytic activity which can be industrially carried out while suppressing the calorific value at the initial stage of polymerization. It is an object of the present invention to provide a catalyst for addition polymerization, and to suppress the calorific value at the initial stage of polymerization, and to provide an efficient production method of an addition polymer which can be industrially carried out. .

[0004]

That is, the present invention relates to a transition metal compound represented by the following general formula (1). The present invention also relates to an addition polymerization catalyst obtained by bringing the transition metal compound into contact with the following (B) and / or the following (C), and a method for producing an addition polymer using the addition polymerization catalyst. Things. Wherein M represents a titanium atom, a zirconium atom or a hafnium atom in a +3 type oxidation state; A is a polydentate monoanionic ligand; R ¹ is an alkyl group, an aralkyl group, an aryl group, or Represents a substituted silyl group;
Is an oxygen atom or a sulfur atom; two Xs are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a disubstituted amino group And two Xs may be bonded to each other to form a ring; D represents a neutral ligand coordinated to M;
2 to 2. (B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by general formula E ¹ _a AlZ _3-a (B2) General formula ｛-Al (E ²⁾ -O-} cyclic aluminoxane (B3 having the structure represented by _b) the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
Linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer, and c represents an integer of 1 or more.) (C): One or more boron compounds selected from the following (C1) to (C3) (C1) Boron represented by the general formula BQ ¹ Q ² Q ³ A compound, (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- Boron compound represented (where B is a boron atom in a trivalent state, Q
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid. Hereinafter, the present invention will be described in more detail.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the transition compound represented by the above general formula (1), M represents a titanium atom, a zirconium atom or a hafnium atom, and a titanium atom is particularly preferred.

The neutral ligand coordinated to M represented by D in the above general formula (1) includes, for example, ether compounds such as diethyl ether, tetrahydrofuran and dibutyl ether, and tertiary compounds such as triethylamine and pyridine. Examples thereof include amine compounds, nitrile compounds such as acetonitrile, benzonitrile and the like, and are preferably tetrahydrofuran or pyridine.

The atom represented by E in the general formula (1) is an oxygen atom or a sulfur atom, particularly preferably an oxygen atom.

In the above general formula (1), the halogen atom for X is a fluorine atom, a chlorine atom, a bromine atom,
Examples thereof include an iodine atom and the like, and particularly preferred is a chlorine atom.

The alkyl group represented by X or R ¹ in the general formula (1) is preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, and n-butyl. Group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-
Octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group, ethyl group, isopropyl group, ter
It is a t-butyl group, an isobutyl group, or an amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 10 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,
Bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloro Ethyl group,
Trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, Perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group,
Perchloropentyl group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group,
Examples include a perbromohexyl group, a perbromooctyl group, a perbromododecyl group, a perbromopentadecyl group, a perbromoeicosyl group, and the like. All of 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, or an aralkyloxy group such as a benzyloxy group.

The aralkyl group for X or R ¹ in the general formula (1) is preferably an aralkyl group having 7 to 20 carbon atoms, for example, a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) group. ) Methyl group,
(4-methylphenyl) methyl group, (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, (3,5-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-tetramethylphenyl) 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,
Examples thereof include a (n-dodecylphenyl) methyl group, a naphthylmethyl group and an anthracenylmethyl group, and more preferably a benzyl group. All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aryl group represented by X or R ¹ in the general formula (1) is preferably an aryl group having 6 to 20 carbon atoms, such as phenyl, 2-tolyl, 3-tolyl, and 4-tolyl. , 2,3-xylyl group, 2,4-
Xylyl group, 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, Di-tert-butylphenyl group, di-ter
t-butylmethylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group,
Examples thereof include an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is more preferable. All of these aryl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The substituted silyl group represented by X or R ¹ in the general formula (1) is a silyl group substituted by a hydrocarbon group, wherein the hydrocarbon group is, for example, a methyl group, an ethyl group, an n- Alkyl groups having 1 to 10 carbon atoms such as propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, and phenyl group And the like. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group and the like. Di-substituted silyl group having 2 to 20 carbon atoms, trimethylsilyl group, triethylsilyl group, 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-hexylsilyl group, tricyclohexylsilyl group,
Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as a triphenylsilyl group, and a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group is preferable. All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

The alkoxy group represented by X in the general formula (1) is preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group, and the like, and more preferably. Methoxy, ethoxy, isopropoxy, or tert-
Butoxy group. All of these alkoxy groups are
Partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. You may.

The aralkyloxy group represented by X in the general formula (1) is preferably an aralkyloxy group having 7 to 20 carbon atoms, such as a benzyloxy group, a (2-methylphenyl) methoxy group and a (3-methylphenyl) group. ) Methoxy group, (4-methylphenyl) methoxy group, (2,
3-dimethylphenyl) 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-tetra (Methylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (se
(c-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-
(Decylphenyl) methoxy, naphthylmethoxy, anthracenylmethoxy, and the like, and more preferably a benzyloxy group. All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The aryloxy group represented by X in the general formula (1) is preferably an aryloxy group having 6 to 20 carbon atoms, such as phenoxy, 2-methylphenoxy, 3-methylphenoxy, and 4-methyl. Phenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,
6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-
Butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-
5-methylphenoxy group, 2-tert-butyl-6-
Methylphenoxy 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,
2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert- Butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2, 3,4,5-tetramethylphenoxy group, 2-
tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-
tert-butyl-3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl -3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5
-Dimethylphenoxy group, pentamethylphenoxy group,
Ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, s
ec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. All of these aryloxy groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The disubstituted amino group represented by X in the above formula (1) is an amino group substituted with two hydrocarbon groups or silyl groups, wherein the hydrocarbon group is, for example, a methyl group or an ethyl group. Alkyl groups having 1 to 10 carbon atoms such as n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group And an aryl group having 6 to 10 carbon atoms such as a phenyl group and an aralkyl group having 7 to 10 carbon atoms such as a benzyl group. Examples of the silyl group include a trimethylsilyl group and a tert-butyldimethylsilyl group. Can be Examples of such a disubstituted amino group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-sec-butylamino group, and a di-tert-butylamino group. Group, diisobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group and the like. And preferably a dimethylamino group, a diethylamino group, a diisopropylamino group, a di-tert-butylamino group, and a bistrimethylsilylamino group. Each of these disubstituted amino groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyl group such as a benzyloxy group. Part may be substituted with an oxy group or the like.

R ^{1 in the} general formula (1) is preferably an alkyl group or a substituted silyl group, and more preferably a methyl group, a tert-butyl group or a trimethylsilyl group.

The two Xs in the general formula (1) may be bonded to each other to form a ring. X is preferably a halogen atom, an alkyl group, an alkoxy group or an alkenediyl group, and more preferably a chlorine atom, a methyl group, a methoxy group, a 3-hexene-2,5-diyl group or a 1,4-diphenyl-2. -Butene-1,4-diyl group.

The polydentate monoanionic ligand represented by A in the above general formula (1) includes, for example, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group, A substituted fluorenyl group, a tris (pyrazolyl) borate group or a tris (substituted pyrazolyl) borate group;
Preferably, it is a substituted cyclopentadienyl group, a substituted indenyl group, or a substituted fluorenyl group.

A is preferably a polydentate monoanionic ligand represented by the following general formula (2). (Wherein Cp ¹ represents a group having a cyclopentadiene-type anion skeleton; G represents ¹ to 30 linking Cp ¹ and E)
Represents a substituent having three non-hydrogen atoms. )

In the general formula (2), Cp¹ Shown as
As a group having a cyclopentadiene-type anion skeleton
Is, for example, η^Five -Cyclopentadienyl group, η^Five −
Rucyclopentadienyl group, η^Five -Dimethylcyclopen
Tadienyl group, η^Five -Trimethylcyclopentadienyl
Group, η^Five A tetramethylcyclopentadienyl group, η^Five
-Ethylcyclopentadienyl group, η^Five -N-propyl
Cyclopentadienyl group, η^Five -Isopropylcyclope
Antadienyl group, η^Five -N-butylcyclopentadienyl
Group, η^Five -Sec-butylcyclopentadienyl group,
η^Five -Tert-butylcyclopentadienyl group, η^Five 
-N-pentylcyclopentadienyl group, η^Five -Neope
Ethyl cyclopentadienyl group, η^Five -N-hexylsi
Cloantadienyl group, η^Five -N-octylcyclodone
Tadienyl group, η^Five -Phenylcyclopentadienyl
Group, η^Five -Naphthylcyclopentadienyl group, η^Five −
Limethylsilylcyclopentadienyl group, η^Five -Trie
Tylsilylcyclopentadienyl group, η^Five -Tert-
Butyldimethylsilylcyclopentadienyl group, η^Five −
Indenyl group, η^Five -Methylindenyl group, η^Five −Jimme
Tilindenyl group, η^Five-Ethylindenyl group, η^Five −
n-propylindenyl group, η^Five -Isopropylindene
Nil group, η^Five -N-butylindenyl group, η^Five -Sec
-Butylindenyl group, η^Five -Tert-butylindene
Nil group, η^Five -N-pentylindenyl group, η^Five -Neo
Pentylindenyl group, η^Five -N-hexylindenyl
Group, η^Five -N-octylindenyl group, η^Five -N-dec
Ruindenyl group, η^Five -Phenylindenyl group, η^Five −
Methylphenylindenyl group, η^Five −Naphthylindeni
Group, η^Five A trimethylsilylindenyl group, η^Five −
Triethylsilylindenyl group, η^Five -Tert-butyl
Dimethylsilylindenyl group, η^Five -Tetrahydroin
Denenyl group, η^Five A fluorenyl group, η^Five -Methylfluor
Renyl group, η^Five -Dimethylfluorenyl group, η^Five −Echi
Lufluorenyl group, η^Five -Diethylfluorenyl group, η
^Five -N-propylfluorenyl group, η^Five -Di-n-pro
Pyrfluorenyl group, η^Five -Isopropylfluorenyl
Group, η^Five -Diisopropylfluorenyl group, η^Five -N-
Butylfluorenyl group, η^Five -Sec-butyl fluor
Nil group, η^Five -Tert-butylfluorenyl group, η^Five 
-Di-n-butylfluorenyl group, η^Five -Di-sec-
Butylfluorenyl group, η^Five -Di-tert-butyl ether
Fluorenyl group, η^Five -N-pentylfluorenyl group, η
^Five -Neopentylfluorenyl group, η^Five -N-hexyl
Fluorenyl group, η^Five -N-octylfluorenyl group,
η^Five -N-decylfluorenyl group, η^Five -N-dodecyl
Fluorenyl group, η ^Five A phenylfluorenyl group, η^Five 
-Di-phenylfluorenyl group, η^Five -Methylphenyl
Fluorenyl group, η^Five A naphthylfluorenyl group, η^Five 
A trimethylsilylfluorenyl group, η^Five -Bis-Tori
Methylsilylfluorenyl group, η^Five -Triethylsilyl
Fluorenyl group, η^Five -Tert-butyldimethylsilyl
And a fluorenyl group.^Five −
Clopentadienyl group, η^Five -Methylcyclopentadie
Nil group, η^Five -Tert-butylcyclopentadienyl
Group, η^Five A tetramethylcyclopentadienyl group, η^Five 
-An indenyl group, or η^Five -A fluorenyl group.

In the general formula (2), G represents Cp ¹ and E
And a substituent having 1 to 30 non-hydrogen atoms, for example, a methylene group; a 1,2-ethylene group,
A polymethylene group such as a propylene group; a cycloalkanediyl group; a silicon-containing hydrocarbon group such as a dialkylsilylene group or a silacycloalkanediyl group; a germanium-containing hydrocarbon group such as a dialkylgermylene group or a germiracycloalkanediyl group; An atom of group 16 of the periodic table such as an oxygen atom or a sulfur atom; a substituted phenylene group; and the like, and in some cases, a complex substituent obtained by combining these; a polymethylene group or a substituted phenylene group is preferable. A substituted phenyleneoxy group, a substituted phenylenethio group, or a group represented by the following general formula (4),
Particularly, a group represented by the following general formula (4) is preferable. (Wherein J represents an atom of Group 14 of the Periodic Table of the Elements;
R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, an aryloxy group or a di-substituted amino group, a plurality of R ² May be arbitrarily bonded to form a ring; m represents an integer of 0 to 4. )

That is, the transition metal compound represented by the general formula (1) is preferably a transition metal compound represented by the following general formula (3). (Wherein M represents a titanium atom, a zirconium atom or a hafnium atom in a +3 type oxidation state; Cp ¹ represents a group having a cyclopentadiene-type anion skeleton; J
Represents an atom belonging to Group 14 of the periodic table; R ² and R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, E represents an aryloxy group or a disubstituted amino group, and a plurality of R ² may be arbitrarily bonded to form a ring; m represents an integer of 0 to 4;
Is an oxygen or sulfur atom; R ¹ is an alkyl group,
Represents an aralkyl group, an aryl group, or a substituted silyl group; two Xs each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, X represents a disubstituted amino group, and two Xs may combine with each other to form a ring; D represents a neutral ligand coordinated to M; n represents an integer of 0 to 2. )

In the above general formula (3), J represents an atom belonging to Group 14 of the periodic table of the elements.
Examples thereof include a carbon atom, a silicon atom, and a germanium atom, and preferably a carbon atom or a silicon atom.

In the general formula (3), M, D, n,
X and Cp¹ Are the above-mentioned general formulas, respectively.
The same as those in (1) or (2). Also
R of the above general formula (3)^Two And R^Three Halogen in
Atom, alkyl group, aralkyl group, aryl group,
Ryl group, alkoxy group, aralkyloxy group, aryl
The oxy group and the disubstituted amino group are each represented by the general formula
The same as those in X of (1). m is benzene
Substituent R on the ring^Two Represents an integer of 0 to 4 representing the number of
And preferably, m is an integer of 0 to 2;
^Two Is preferably an alkyl group, an alkoxy group or
A substituted silyl group, more preferably an alkyl group.
is there. R^Three Preferably, each is independently
Group, alkoxy group, aryl group or aryloxy
Group or two R ^Three And J together
A rucandiyl group or a silacycloalkanediyl group.
More preferably, methyl group, ethyl group, methoxy
Group, an ethoxy group or a phenyl group.

Specific examples of the transition metal compound represented by the above general formula (1) include, for example, (methoxycyclopentadienyl) titanium dichloride, (ethoxycyclopentadienyl) titanium dichloride, (n-propoxycyclopentadienyl) ) Titanium dichloride,
(Isopropoxycyclopentadienyl) titanium dichloride, (n-butoxycyclopentadienyl) titanium dichloride, (t-butoxycyclopentadienyl) titanium dichloride, (trimethylsiloxycyclopentadienyl) titanium dichloride,
[(Methoxymethyl) cyclopentadienyl] titanium dichloride, [(ethoxymethyl) cyclopentadienyl] titanium dichloride, [(n-propoxymethyl) cyclopentadienyl] titanium dichloride, [(isopropoxymethyl) cyclopentadiene [Enyl] titanium dichloride, [(n-butoxymethyl) cyclopentadienyl] titanium dichloride,
[(T-butoxymethyl) cyclopentadienyl] titanium dichloride, [(trimethylsiloxymethyl)
Cyclopentadienyl] titanium dichloride,
[(Methoxyethyl) cyclopentadienyl] titanium dichloride, [(ethoxyethyl) cyclopentadienyl] titanium dichloride, [(n-propoxyethyl) cyclopentadienyl] titanium dichloride, [(isopropoxyethyl) cyclopentadiene [Enyl] titanium dichloride, [(n-butoxyethyl) cyclopentadienyl] titanium dichloride,
[(T-butoxyethyl) cyclopentadienyl] titanium dichloride, [(trimethylsiloxyethyl)
Cyclopentadienyl] titanium dichloride,
[(Methoxy-n-propyl) cyclopentadienyl]
Titanium dichloride, [(ethoxy-n-propyl) cyclopentadienyl] titanium dichloride,
[(N-propoxy-n-propyl) cyclopentadienyl] titanium dichloride, [(isopropoxy-
[n-propyl) cyclopentadienyl] titanium dichloride, [(n-butoxy-n-propyl) cyclopentadienyl] titanium dichloride, [(t-butoxy-n-propyl) cyclopentadienyl] titanium dichloride, [( Trimethylsiloxy-n-propyl) cyclopentadienyl] titanium dichloride,

[(Methoxydimethylsilyl) cyclopentadienyl] titanium dichloride, [(ethoxydimethylsilyl) cyclopentadienyl] titanium dichloride, [(n-propoxydimethylsilyl) cyclopentadienyl] titanium dichloride, [(iso Propoxydimethylsilyl) cyclopentadienyl] titanium dichloride, [(n-butoxydimethylsilyl) cyclopentadienyl] titanium dichloride,
[(T-butoxydimethylsilyl) cyclopentadienyl] titanium dichloride, [(trimethylsiloxydimethylsilyl) cyclopentadienyl] titanium dichloride, [(methoxydimethylsilylmethyl) cyclopentadienyl] titanium dichloride, [(ethoxydimethyl [Silylmethyl) cyclopentadienyl] titanium dichloride, [(n-propoxydimethylsilylmethyl) cyclopentadienyl] titanium dichloride, [(isopropoxydimethylsilylmethyl) cyclopentadienyl] titanium dichloride, [(n
-Butoxydimethylsilylmethyl) cyclopentadienyl] titanium dichloride, [(t-butoxydimethylsilylmethyl) cyclopentadienyl] titanium dichloride, [(trimethylsiloxydimethylsilylmethyl) cyclopentadienyl] titanium dichloride, [(methoxy Dimethylsilylethyl) cyclopentadienyl] titanium dichloride, [(ethoxydimethylsilylethyl) cyclopentadienyl] titanium dichloride, [(n-propoxydimethylsilylethyl) cyclopentadienyl] titanium dichloride,
[(Isopropoxydimethylsilylethyl) cyclopentadienyl] titanium dichloride, [(n-butoxydimethylsilylethyl) cyclopentadienyl] titanium dichloride, [(t-butoxydimethylsilylethyl) cyclopentadienyl] titanium dichloride, [(Trimethylsiloxydimethylsilylethyl) cyclopentadienyl] titanium dichloride, [(methoxydimethylsilyl-n-propyl) cyclopentadienyl] titanium dichloride, [(ethoxydimethylsilyl-n-propyl) cyclopentadienyl] titanium Dichloride, [(n-propoxydimethylsilyl-n-propyl) cyclopentadienyl] titanium dichloride, [(isopropoxydimethylsilyl-n
-(Propyl) cyclopentadienyl] titanium dichloride, [(n-butoxydimethylsilyl-n-propyl) cyclopentadienyl] titanium dichloride,
[(T-butoxydimethylsilyl-n-propyl) cyclopentadienyl] titanium dichloride, [(trimethylsiloxydimethylsilyl-n-propyl) cyclopentadienyl] titanium dichloride,

[(Methoxyphenyl) cyclopentadienyl] titanium dichloride, [(ethoxyphenyl) cyclopentadienyl] titanium dichloride,
[(N-propoxyphenyl) cyclopentadienyl]
Titanium dichloride, [(isopropoxyphenyl) cyclopentadienyl] titanium dichloride,
[(N-butoxyphenyl) cyclopentadienyl] titanium dichloride, [(t-butoxyphenyl) cyclopentadienyl] titanium dichloride, [(trimethylsiloxyphenyl) cyclopentadienyl] titanium dichloride, [(methoxyphenylmethyl)
Cyclopentadienyl] titanium dichloride,
[(Ethoxyphenylmethyl) cyclopentadienyl]
Titanium dichloride, [(n-propoxyphenylmethyl) cyclopentadienyl] titanium dichloride, [(isopropoxyphenylmethyl) cyclopentadienyl] titanium dichloride, [(n-butoxyphenylmethyl) cyclopentadienyl] titanium dichloride, [(T-butoxyphenylmethyl) cyclopentadienyl] titanium dichloride, [(trimethylsiloxyphenylmethyl) cyclopentadienyl]
Titanium dichloride, [(methoxyphenylethyl) cyclopentadienyl] titanium dichloride,
[(Ethoxyphenylethyl) cyclopentadienyl]
Titanium dichloride, [(n-propoxyphenylethyl) cyclopentadienyl] titanium dichloride, [(isopropoxyphenylethyl) cyclopentadienyl] titanium dichloride, [(n-butoxyphenylethyl) cyclopentadienyl] titanium dichloride, [(T-butoxyphenylethyl) cyclopentadienyl] titanium dichloride, [(trimethylsiloxyphenylethyl) cyclopentadienyl]
Titanium dichloride, [(methoxyphenyl-n-
Propyl) cyclopentadienyl] titanium dichloride, [(ethoxyphenyl-n-propyl) cyclopentadienyl] titanium dichloride, [(n-propoxyphenyl-n-propyl) cyclopentadienyl] titanium dichloride, [(isopropoxy [Phenyl-n-propyl) cyclopentadienyl] titanium dichloride, [(n-butoxyphenyl-n-propyl) cyclopentadienyl] titanium dichloride, [(t-butoxyphenyl-n-propyl) cyclopentadienyl] titanium Dichloride, [(trimethylsiloxyphenyl-n-propyl) cyclopentadienyl] titanium dichloride,

{[Dimethyl (methoxyphenyl) methyl] cyclopentadienyl} titanium dichloride,
{[Dimethyl (ethoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (n-propoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (isopropoxyphenyl) methyl] cyclopentadienyl {Titanium dichloride, {[dimethyl (n-butoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (t-butoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (trimethylsiloxyphenyl) Methyl] cyclopentadienyltitanium dichloride,
{[Dimethyl (methoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (ethoxyphenyl) silyl] cyclopentadienyl}
Titanium dichloride, {[dimethyl (n-propoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (isopropoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (n-butoxyphenyl) silyl] ] Cyclopentadienyl dititanium dichloride,
{[Dimethyl (t-butoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (trimethylsiloxyphenyl) silyl] cyclopentadienyl} titanium dichloride,

{[(6-methyl-1-methoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-ethoxy-6-methylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[( 6-methyl-1-n-propoxyphenyl)
Methyl] cyclopentadienyl {titanium dichloride,} [(6-methyl-1-isopropoxyphenyl)
Methyl] cyclopentadienyl} titanium dichloride, {[(1-n-butoxy-6-methylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-t-butoxy-6-methylphenyl) methyl] Cyclopentadienyl} titanium dichloride, {[(6-methyl-1-trimethylsiloxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1-methoxyphenyl) methyl] cyclopentadienyl {Titanium dichloride, {[dimethyl (1-ethoxy-6-methylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1-n-propoxyphenyl) methyl] cyclopentadienyl} titanium Dichloride, [Dimethyl (6-methyl-1-
Isopropoxyphenyl) methyl] cyclopentadienyl {titanium dichloride,} [dimethyl (1-n-
[Butoxy-6-methylphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (1
-T-butoxy-6-methylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1-trimethylsiloxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6- Methyl-1-methoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-ethoxy-6-methylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1- n-propoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1-isopropoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-n-
[Butoxy-6-methylphenyl) silyl] cyclopentadienyl {titanium dichloride, {[dimethyl (1
-T-butoxy-6-methylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1-trimethylsiloxyphenyl) silyl] cyclopentadienyl} titanium dichloride,

{[(4,6-dimethyl-1-methoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-ethoxy-4,6-dimethylphenyl) methyl] cyclopentadienyl} titanium dichloride , {[(4,6-dimethyl-1-n-propoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(4,6-dimethyl-1-isopropoxyphenyl) methyl] cyclopentadienyl}
Titanium dichloride, {[(1-n-butoxy-
4,6-dimethylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-t-butoxy-4,6-dimethylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(4,6- [Dimethyl-1-trimethylsiloxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-dimethyl-1-methoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-ethoxy) -4,6-dimethylphenyl) methyl] cyclopentadienyl {titanium dichloride,} [dimethyl (4,6-dimethyl-1-n
-Propoxyphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (4,6-
Dimethyl-1-isopropoxyphenyl) methyl] cyclopentadienyl {titanium dichloride} {dimethyl (1-n-butoxy-4,6-dimethylphenyl)
Methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-t-butoxy-4,6-dimethylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-dimethyl-1)
-Trimethylsiloxyphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (4,6-dimethyl-1-methoxyphenyl) silyl]
Cyclopentadienyl dititanium dichloride,
{[Dimethyl (1-ethoxy-4,6-dimethylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-dimethyl-1-n-propoxyphenyl) silyl] cyclopentadienyl} titanium Dichloride, {[dimethyl (4,6-dimethyl-1-isopropoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-n-butoxy-4,6-dimethylphenyl) silyl] cyclopentadi Enil-titanium dichloride,
{[Dimethyl (1-tert-butoxy-4,6-dimethylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-dimethyl-1-trimethylsiloxyphenyl) silyl] cyclopentadienyl} Titanium dichloride,

{[(6-t-butyl-1-methoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl-1-ethoxyphenyl) methyl] cyclopentadienyl} titanium dichloride , {[(6-t-butyl-1-n-propoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl-1-isopropoxyphenyl) methyl] cyclopentadienyl} titanium Dichloride, {[(6-t-butyl-1-n-butoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-t-butoxy-6-t-
[Butylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl-1-trimethylsiloxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-
Butyl-1-methoxyphenyl) methyl] cyclopentadienyl {titanium dichloride,} [dimethyl (6
-T-butyl-1-ethoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-n-propoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-isopropoxyphenyl) methyl] cyclopentadienyl {titanium dichloride,} [dimethyl (6-t-butyl-1-
n-butoxyphenyl) methyl] cyclopentadienyl {titanium dichloride} {dimethyl (1-t-
[Butoxy-6-t-butylphenyl) methyl] cyclopentadienyl {titanium dichloride} {[dimethyl (6-t-butyl-1-trimethylsiloxyphenyl)]
[Methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-methoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-ethoxyphenyl)] [Silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-)
n-propoxyphenyl) silyl] cyclopentadienyl {titanium dichloride, {[dimethyl (6-t-
Butyl-1-isopropoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-n-butoxyphenyl) silyl] cyclopentadienyl} titanium dichloride,
{[Dimethyl (1-tert-butoxy-6-tert-butylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-tert-butyl-1-trimethylsiloxyphenyl) silyl] cyclopentadienyl} Titanium dichloride, {[(4,6-di-t-
Butyl-1-methoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(4,6-di-t-butyl-1-ethoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(4
6-di-t-butyl-1-n-propoxyphenyl) methyl] cyclopentadienyl {titanium dichloride, {[(4,6-di-t-butyl-1-isopropoxyphenyl) methyl] cyclopentadienyl {Titanium dichloride,} [(4,6-di-t-butyl-1-
[n-butoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-t-butoxy-4,6-di-t-butylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[4,6 −
Di-t-butyl-1-trimethylsiloxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-di-t-butyl-1-methoxyphenyl) methyl] cyclopentadienyl} titanium dichloride , {[Dimethyl (4,6-di-t-butyl-1-ethoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4
6-di-tert-butyl-1-n-propoxyphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (4,6-di-tert-butyl-1-isopropoxyphenyl) methyl] cyclopentadi Enil｝
Titanium dichloride, {[dimethyl (4,6-di-
[t-butyl-1-n-butoxyphenyl) methyl] cyclopentadienyl titanium dichloride, {[dimethyl (1-t-butoxy-4,6-di-t-butylphenyl) methyl] cyclopentadienyl} titanium Dichloride, ｛[dimethyl (4,6-di-t-butyl-1
-Trimethylsiloxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-di-t-butyl-1-methoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4 6-di-t-butyl-1-ethoxyphenyl) silyl] cyclopentadienyl {titanium dichloride,} [dimethyl (4,6-di-t-butyl-1-n-propoxyphenyl) silyl] cyclopentadienyl {Titanium dichloride, {[dimethyl (4,6-di-t-butyl-1-isopropoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-di-t-butyl-1-)
n-butoxyphenyl) silyl] cyclopentadienyl {titanium dichloride,} [dimethyl (1-t-
Butoxy-4,6-di-t-butylphenyl) silyl]
Cyclopentadienyl dititanium dichloride,
{[Dimethyl (4,6-di-t-butyl-1-trimethylsiloxyphenyl) silyl] cyclopentadienyl}
Titanium dichloride,

｛[(6-t-butyl-4-methyl-1-
[Methoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl-1-ethoxy-4-methylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl- 4-methyl-1-n-propoxyphenyl) methyl] cyclopentadienyltitanium dichloride,
{[(6-t-butyl-4-methyl-1-isopropoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-n-butoxy-6-t-butyl-4-methylphenyl) methyl Cyclopentadienyl} titanium dichloride, {[(1-t-butoxy-6-t-butyl-4-methylphenyl) methyl] cyclopentadienyl} titanium dichloride,
{[(6-t-butyl-4-methyl-1-trimethylsiloxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-
4-methyl-1-methoxyphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-ethoxy-4-methylphenyl) methyl] cyclopentadienyl} titanium dichloride,} [ Dimethyl (6-t-butyl-4-methyl-
1-n-propoxyphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (6-
[tert-butyl-4-methyl-1-isopropoxyphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (1-n-butoxy-6-t-butyl-4-methylphenyl) methyl] cyclopentadi Enyl {titanium dichloride,} [dimethyl (1-t
-Butoxy-6-t-butyl-4-methylphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (6-t-butyl-4-methyl-1-methyl)-
[Trimethylsiloxyphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (6-
t-butyl-4-methyl-1-methoxyphenyl) silyl] cyclopentadienyltitanium dichloride,
{[Dimethyl (6-tert-butyl-1-ethoxy-4-methylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-tert-butyl-4)
-Methyl-1-n-propoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-4-methyl-1-isopropoxyphenyl) silyl] cyclopentadienyl} titanium dichloride, ｛[Dimethyl (1-n-butoxy-6)
-T-butyl-4-methylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-t-butoxy-6-t-butyl-4-methylphenyl) silyl] cyclopentadienyl} titanium dichloride {{Dimethyl (6-t-butyl-4-methyl-1-trimethylsiloxyphenyl) silyl] cyclopentadienyl} titanium dichloride,

(Methylthiocyclopentadienyl) titanium dichloride, (ethylthiocyclopentadienyl) titanium dichloride, (n-propylthiocyclopentadienyl) titanium dichloride, (isopropylthiocyclopentadienyl) titanium dichloride, (n -Butylthiocyclopentadienyl) titanium dichloride, (t-butylthiocyclopentadienyl) titanium dichloride [(methylthiomethyl) cyclopentadienyl] titanium dichloride, [(ethylthiomethyl) cyclopentadienyl] titanium dichloride, [(N-propylthiomethyl) cyclopentadienyl] titanium dichloride, [(isopropylthiomethyl) cyclopentadienyl] titanium dichloride, [( n-butylthiomethyl) cyclopentadienyl] titanium dichloride, [(t-butylthiomethyl) cyclopentadienyl] titanium dichloride, [(methylthioethyl)
Cyclopentadienyl] titanium dichloride,
[(Ethylthioethyl) cyclopentadienyl] titanium dichloride, [(n-propylthioethyl) cyclopentadienyl] titanium dichloride, [(isopropylthioethyl) cyclopentadienyl] titanium dichloride, [(n-butylthio) Ethyl) cyclopentadienyl] titanium dichloride, [(t-butylthioethyl) cyclopentadienyl] titanium dichloride, [(methylthio-n-propyl) cyclopentadienyl] titanium dichloride, [(ethylthio-n-propyl) [Cyclopentadienyl] titanium dichloride, [(n-propylthio-n-propyl) cyclopentadienyl] titanium dichloride, [(isopropylthio-n-propyl) cyclopentadienyl] titanium dichloride Ride, [(n-butylthio -n
-(Propyl) cyclopentadienyl] titanium dichloride, [(t-butylthio-n-propyl) cyclopentadienyl] titanium dichloride,

{[Dimethyl (methylthiophenyl) methyl] cyclopentadienyl} titanium dichloride,
{[Dimethyl (ethylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (n-propylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (isopropylthiophenyl) methyl] cyclopenta Dienyl} titanium dichloride, {[dimethyl (n-butylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (t-butylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl ( Trimethylsilylthiophenyl) methyl] cyclopentadienyltitanium dichloride, {[dimethyl (methylthiophenyl) silyl] cyclopentadienyl} titanium dichloride,
{[Dimethyl (ethylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (n-propylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (isopropylthiophenyl) silyl] cyclopenta Dienyl} titanium dichloride, {[dimethyl (n-butylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (t-butylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl ( Trimethylsilylthiophenyl) silyl] cyclopentadienyltitanium dichloride,

{[(6-methyl-1-methylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-ethylthio-6-methylphenyl)
Methyl] cyclopentadienyl} titanium dichloride, {[(6-methyl-1-n-propylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(6-methyl-1-isopropylthiophenyl) methyl] Cyclopentadienyl} titanium dichloride, {[(1-n-butylthio-6-methylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-t-butylthio-6-methylphenyl) methyl] cyclopenta Dienyl {titanium dichloride, {[(6-methyl-1-trimethylsilylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1-methylthiophenyl) methyl] cyclopentadienyl} titanium Dichloride {[Dimethyl (1-ethylthio -
6-methylphenyl) methyl] cyclopentadienyl
Titanium dichloride, {[dimethyl (6-methyl-
1-n-propylthiophenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (6
-Methyl-1-isopropylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-n-butylthio-6-methylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1- [t-butylthio-6-methylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1-trimethylsilylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl) -1-methylthiophenyl) silyl] cyclopentadienyl {titanium dichloride,} [dimethyl (1-
Ethylthio-6-methylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1-n-propylthiophenyl) silyl] cyclopentadienyl} titanium dichloride,
{[Dimethyl (6-methyl-1-isopropylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-n-butylthio-6-methylphenyl) silyl] cyclopentadienyl} titanium dichloride,} [Dimethyl (1-t-butylthio-6-methylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-methyl-1-trimethylsilylthiophenyl) silyl] cyclopentadienyl} titanium dichloride,

{[(4,6-dimethyl-1-methylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-ethylthio-4,6-dimethylphenyl) methyl] cyclopentadienyl} titanium dichloride {{(4,6-dimethyl-1-n-propylthiophenyl) methyl] cyclopentadienyl}
Titanium dichloride, {[(4,6-dimethyl-1
-Isopropylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-n-butylthio-4,6-dimethylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-t
-Butylthio-4,6-dimethylphenyl) methyl] cyclopentadienyltitanium dichloride,
{[(4,6-dimethyl-1-trimethylsilylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-dimethyl-1-methylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[Dimethyl (1-ethylthio-4,6-dimethylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4
6-dimethyl-1-n-propylthiophenyl) methyl] cyclopentadienyltitanium dichloride,
{[Dimethyl (4,6-dimethyl-1-isopropylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-n-butylthio-
4,6-dimethylphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (1-t
-Butylthio-4,6-dimethylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-dimethyl-1-trimethylsilylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl ( 4,6-dimethyl-1-
Methylthiophenyl) silyl] cyclopentadienyl
Titanium dichloride, {[dimethyl (1-ethylthio-4,6-dimethylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-dimethyl-1-n-propylthiophenyl)
[Silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-dimethyl-1-isopropylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-n-butylthio-4,6-) Dimethylphenyl) silyl] cyclopentadienyl {titanium dichloride,} [dimethyl (1
-T-butylthio-4,6-dimethylphenyl) silyl] cyclopentadienyltitanium dichloride,
{[Dimethyl (4,6-dimethyl-1-trimethylsilylthiophenyl) silyl] cyclopentadienyl} titanium dichloride,

{[(6-t-butyl-1-methylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl-1-ethylthiophenyl) methyl] cyclopentadienyl} titanium Dichloride, {[(6-t-butyl-1-n-propylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl-1-isopropylthiophenyl) methyl] cyclopentadienyl ｝
Titanium dichloride, {[(6-t-butyl-1-
n-butylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-t-butylthio-6-t-butylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl -1-trimethylsilylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-methylthiophenyl) methyl] cyclopentadienyl} titanium dichloride,
{[Dimethyl (6-t-butyl-1-ethylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-n-propylthiophenyl) methyl] cyclopentadienyl {Titanium dichloride, {[dimethyl (6-t-butyl-1-isopropylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-n-butylthiophenyl) methyl] Cyclopentadienyl dititanium dichloride,
{[Dimethyl (1-t-butylthio-6-t-butylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-trimethylsilylthiophenyl) methyl] cyclopentadienyl} Titanium dichloride, {[dimethyl (6-t
-Butyl-1-methylthiophenyl) silyl] cyclopentadienyl {titanium dichloride} {[dimethyl (6-t-butyl-1-ethylthiophenyl) silyl]
Cyclopentadienyl dititanium dichloride,
{[Dimethyl (6-t-butyl-1-n-propylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-isopropylthiophenyl) silyl] cyclopentadienyl {Titanium dichloride,} [dimethyl (6-t-
[Butyl-1-n-butylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-t-butylthio-6-t-butylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-butyl-1-trimethylsilylthiophenyl) silyl] cyclopentadienyltitanium dichloride,

{[(4,6-di-tert-butyl-1-methylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(4,6-di-tert-butyl-methyl) phenyl]
1-ethylthiophenyl) methyl] cyclopentadienyl {titanium dichloride, {[(4,6-di-t-
Butyl-1-n-propylthiophenyl) methyl] cyclopentadienyltitanium dichloride,
{[(4,6-di-tert-butyl-1-isopropylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(4,6-di-tert-butyl-1-n-n)
-Butylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-t-butylthio-4,6-di-t-butylphenyl) methyl] cyclopentadienyl} titanium dichloride, {[4,6
-Di-t-butyl-1-trimethylsilylthiophenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (4,6-di-t-butyl-1-)
Methylthiophenyl) methyl] cyclopentadienyl
Titanium dichloride, {[dimethyl (4,6-di-
[t-butyl-1-ethylthiophenyl) methyl] cyclopentadienyl titanium dichloride, {[dimethyl (4,6-di-t-butyl-1-n-propylthiophenyl) methyl] cyclopentadienyl} titanium Dichloride, {[dimethyl (4,6-di-t-butyl-
1-isopropylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-di-t-butyl-1-n-butylthiophenyl) methyl] cyclopentadienyl} titanium dichloride,} [ Dimethyl (1-t-butylthio-4,6-
[Di-t-butylphenyl) methyl] cyclopentadienyl {titanium dichloride, {[dimethyl (4,6-
Di-t-butyl-1-trimethylsilylthiophenyl)
[Methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-di-t-butyl-1-methylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-di-t −
Butyl-1-ethylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (4,6-di-t-butyl-1-n-propylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[Dimethyl (4,6-di-t-butyl-1)
-Isopropylthiophenyl) silyl] cyclopentadienyl {titanium dichloride, {[dimethyl (4,
6-di-t-butyl-1-n-butylthiophenyl) silyl] cyclopentadienyl {titanium dichloride,} [dimethyl (1-t-butylthio-4,6-di-
t-butylphenyl) silyl] cyclopentadienyl}
Titanium dichloride, {[dimethyl (4,6-di-
t-butyl-1-trimethylsilylthiophenyl) silyl] cyclopentadienyl {titanium dichloride,

{[(6-t-butyl-4-methyl-1-)
Methylthiophenyl) methyl] cyclopentadienyl
Titanium dichloride, {[(6-t-butyl-1-
Ethylthio-4-methylphenyl) methyl] cyclopentadienyl {titanium dichloride,} [(6-t-
Butyl-4-methyl-1-n-propylthiophenyl)
Methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl-4-methyl-1-isopropylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[(1-n-butylthio-6)
-T-butyl-4-methylphenyl) methyl] cyclopentadienyl {titanium dichloride, {[(1-t
-Butylthio-6-t-butyl-4-methylphenyl)
Methyl] cyclopentadienyl} titanium dichloride, {[(6-t-butyl-4-methyl-1-trimethylsilylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-
Butyl-4-methyl-1-methylthiophenyl) methyl] cyclopentadienyl {titanium dichloride,
{[Dimethyl (6-t-butyl-1-ethylthio-4-)
Methylphenyl) methyl] cyclopentadienyl {titanium dichloride,} [dimethyl (6-t-butyl-
4-methyl-1-n-propylthiophenyl) methyl]
Cyclopentadienyl dititanium dichloride,
{[Dimethyl (6-t-butyl-4-methyl-1-isopropylthiophenyl) methyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-n-
Butylthio-6-t-butyl-4-methylphenyl) methyl] cyclopentadienyl {titanium dichloride,} [dimethyl (1-t-butylthio-6-t-butyl-4-methylphenyl) methyl] cyclopentadienyl {Titanium dichloride,} [dimethyl (6-t-
Butyl-4-methyl-1-trimethylsilylthiophenyl) methyl] cyclopentadienyl {titanium dichloride,} [dimethyl (6-t-butyl-4-methyl-
1-methylthiophenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (6-t-
Butyl-1-ethylthio-4-methylphenyl) silyl] cyclopentadienyl {titanium dichloride,
{[Dimethyl (6-t-butyl-4-methyl-1-n-
Propylthiophenyl) silyl] cyclopentadienyl {titanium dichloride,} [dimethyl (6-t-
Butyl-4-methyl-1-isopropylthiophenyl)
[Silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-n-butylthio-6-t-butyl-4-methylphenyl) silyl] cyclopentadienyl} titanium dichloride, {[dimethyl (1-t-
Butylthio-6-t-butyl-4-methylphenyl) silyl] cyclopentadienyl {titanium dichloride,} [dimethyl (6-t-butyl-4-methyl-1-methyl)
Trimethylsilylthiophenyl) silyl] cyclopentadienyltitanium dichloride,

[(Methoxyphenylthio) cyclopentadienyl] titanium dichloride, [(ethoxyphenylthio) cyclopentadienyl] titanium dichloride, [(n-propoxyphenylthio) cyclopentadienyl] titanium dichloride, [(iso [Propoxyphenylthio) cyclopentadienyl] titanium dichloride, [(n-butoxyphenylthio) cyclopentadienyl] titanium dichloride, [(t-butoxyphenylthio) cyclopentadienyl] titanium dichloride, [(trimethylsiloxyphenylthio )
Cyclopentadienyl] titanium dichloride,
[(6-Methyl-1-methoxyphenylthio) cyclopentadienyl] titanium dichloride, [(1-ethoxy-6-methylphenylthio) cyclopentadienyl] titanium dichloride, [(6-methyl-1-
n-propoxyphenylthio) cyclopentadienyl]
Titanium dichloride, [(6-methyl-1-isopropoxyphenylthio) cyclopentadienyl] titanium dichloride, [(1-n-butoxy-6-methylphenylthio) cyclopentadienyl] titanium dichloride, [(1- t-butoxy-6-methylphenylthio) cyclopentadienyl] titanium dichloride, [(6-methyl-1-trimethylsiloxyphenylthio) cyclopentadienyl] titanium dichloride,

[(4,6-dimethyl-1-methoxyphenylthio) cyclopentadienyl] titanium dichloride, [(1-ethoxy-4,6-dimethylphenylthio) cyclopentadienyl] titanium dichloride,
[(4,6-dimethyl-1-n-propoxyphenylthio) cyclopentadienyl] titanium dichloride,
[(4,6-dimethyl-1-isopropoxyphenylthio) cyclopentadienyl] titanium dichloride,
[(1-n-butoxy-4,6-dimethylphenylthio) cyclopentadienyl] titanium dichloride,
[(1-t-butoxy-4,6-dimethylphenylthio) cyclopentadienyl] titanium dichloride,
[(4,6-dimethyl-1-trimethylsiloxyphenylthio) cyclopentadienyl] titanium dichloride, [(6-t-butyl-1-methoxyphenylthio)
Cyclopentadienyl] titanium dichloride,
[(6-t-butyl-1-ethoxyphenylthio) cyclopentadienyl] titanium dichloride, [(6-
t-butyl-1-n-propoxyphenylthio) cyclopentadienyl] titanium dichloride, [(6-t
-Butyl-1-isopropoxyphenylthio) cyclopentadienyl] titanium dichloride, [(6-t-
Butyl-1-n-butoxyphenylthio) cyclopentadienyl] titanium dichloride, [(1-t-butoxy-6-t-butylphenylthio) cyclopentadienyl] titanium dichloride, [(6-t-butyl-
1-trimethylsiloxyphenylthio) cyclopentadienyl] titanium dichloride,

[(4,6-Di-tert-butyl-1-methoxyphenylthio) cyclopentadienyl] titanium dichloride, [(4,6-di-tert-butyl-1-ethoxyphenylthio) cyclopentadienyl [Enyl] titanium dichloride, [(4,6-di-t-butyl-1-n-propoxyphenylthio) cyclopentadienyl] titanium dichloride, [(4,6-di-t-butyl-1-
Isopropoxyphenylthio) cyclopentadienyl]
Titanium dichloride, [(4,6-di-t-butyl-1-n-butoxyphenylthio) cyclopentadienyl] titanium dichloride, [(1-t-butoxy-
4,6-di-t-butylphenylthio) cyclopentadienyl] titanium dichloride, [(4,6-di-t
-Butyl-1-trimethylsiloxyphenylthio) cyclopentadienyl] titanium dichloride, [(6-
t-butyl-4-methyl-1-methoxyphenylthio)
Cyclopentadienyl] titanium dichloride,
[(6-t-butyl-1-ethoxy-4-methylphenylthio) cyclopentadienyl] titanium dichloride, [(6-t-butyl-4-methyl-1-n-propoxyphenylthio) cyclopentadienyl ] Titanium dichloride, [(6-t-butyl-4-methyl-1-methyl)
Isopropoxyphenylthio) cyclopentadienyl]
Titanium dichloride, [(1-n-butoxy-6-
t-butyl-4-methylphenylthio) cyclopentadienyl] titanium dichloride, [(1-t-butoxy-6-t-butyl-4-methylphenylthio) cyclopentadienyl] titanium dichloride, [(6- t
-Butyl-4-methyl-1-trimethylsiloxyphenylthio) cyclopentadienyl] titanium dichloride,

[(Methoxyphenoxy) cyclopentadienyl] titanium dichloride, [(ethoxyphenoxy) cyclopentadienyl] titanium dichloride, [(n-propoxyphenoxy) cyclopentadienyl] titanium dichloride, [(isopropoxyphenoxy) [Cyclopentadienyl] titanium dichloride, [(n-butoxyphenoxy) cyclopentadienyl] titanium dichloride, [(t-butoxyphenoxy) cyclopentadienyl] titanium dichloride, [(trimethylsiloxyphenoxy) cyclopentadienyl] titanium Dichloride, [(6-methyl-
1-methoxyphenoxy) cyclopentadienyl] titanium dichloride, [(1-ethoxy-6-methylphenoxy) cyclopentadienyl] titanium dichloride, [(6-methyl-1-n-propoxyphenoxy) cyclopentadienyl] Titanium dichloride,
[(6-methyl-1-isopropoxyphenoxy) cyclopentadienyl] titanium dichloride,
(1-n-butoxy-6-methylphenoxy) cyclopentadienyl] titanium dichloride, [(1-t-
Butoxy-6-methylphenoxy) cyclopentadienyl] titanium dichloride, [(6-methyl-1-trimethylsiloxyphenoxy) cyclopentadienyl]
Titanium dichloride, [(4,6-dimethyl-1-
[Methoxyphenoxy) cyclopentadienyl] titanium dichloride, [(1-ethoxy-4,6-dimethylphenoxy) cyclopentadienyl] titanium dichloride, [(4,6-dimethyl-1-n-propoxyphenoxy) cyclopentadi [Enyl] titanium dichloride, [(4,6-dimethyl-1-isopropoxyphenoxy) cyclopentadienyl] titanium dichloride, [(1-n-butoxy-4,6-dimethylphenoxy) cyclopentadienyl] titanium dichloride,
[(1-t-butoxy-4,6-dimethylphenoxy)
Cyclopentadienyl] titanium dichloride,
[(4,6-dimethyl-1-trimethylsiloxyphenoxy) cyclopentadienyl] titanium dichloride, [(6-t-butyl-1-methoxyphenoxy) cyclopentadienyl] titanium dichloride, [(6
-T-butyl-1-ethoxyphenoxy) cyclopentadienyl] titanium dichloride, [(6-t-butyl-1-n-propoxyphenoxy) cyclopentadienyl] titanium dichloride, [(6-t-butyl-
1-isopropoxyphenoxy) cyclopentadienyl] titanium dichloride, [(6-t-butyl-1
-N-butoxyphenoxy) cyclopentadienyl] titanium dichloride, [(1-t-butoxy-6-t
-Butylphenoxy) cyclopentadienyl] titanium dichloride, [(6-t-butyl-1-trimethylsiloxyphenoxy) cyclopentadienyl] titanium dichloride,

[(4,6-Di-t-butyl-1-methoxyphenoxy) cyclopentadienyl] titanium dichloride, [(4,6-di-t-butyl-1-ethoxyphenoxy) cyclopentadienyl] Titanium dichloride, [(4,6-di-t-butyl-1-n-propoxyphenoxy) cyclopentadienyl] titanium dichloride, [(4,6-di-t-butyl-1-isopropoxyphenoxy) cyclopenta Dienyl] titanium dichloride, [(4,6-di-t-butyl-1-n)
-Butoxyphenoxy) cyclopentadienyl] titanium dichloride, [(1-t-butoxy-4,6-di-t-butylphenoxy) cyclopentadienyl] titanium dichloride, [(4,6-di-t-butyl -1
-Trimethylsiloxyphenoxy) cyclopentadienyl] titanium dichloride, [(6-t-butyl-4)
-Methyl-1-methoxyphenoxy) cyclopentadienyl] titanium dichloride, [(6-t-butyl-
1-ethoxy-4-methylphenoxy) cyclopentadienyl] titanium dichloride, [(6-t-butyl-4-methyl-1-n-propoxyphenoxy) cyclopentadienyl] titanium dichloride, [(6-t
-Butyl-4-methyl-1-isopropoxyphenoxy) cyclopentadienyl] titanium dichloride,
[(1-n-butoxy-6-t-butyl-4-methylphenoxy) cyclopentadienyl] titanium dichloride, [(1-t-butoxy-6-t-butyl-4-methylphenoxy) cyclopentadienyl ] Titanium dichloride, [(6-t-butyl-4-methyl-1-trimethylsiloxyphenoxy) cyclopentadienyl]
Titanium dichloride and the like, and compounds obtained by changing titanium of these compounds to zirconium and hafnium,
Compounds obtained by changing chloride to bromide, iodide, dimethylamide, diethylamide, n-butoxide, isopropoxide, cyclopentadienyl to dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, n-butyl Transition metal compounds such as cyclopentadienyl, tert-butyldimethylsilylcyclopentadienyl, compounds modified to indenyl, tetrahydroindenyl, fluorenyl, and octahydrofluorenyl are exemplified.

In the present invention, these transition metal compounds may be used in combination of two or more. Such transition metal compounds are described, for example, in JP-A-9-87313 and Q.A. Huang et al., Transition Met. Chem., 199.
And a strong base (organic alkali metal compound or organic alkali metal compound) is reacted with the ligand obtained by the method shown in 0, 15, 483. to produce a metal salt of the ligand. , 3
It is obtained by reacting a valent titanium, zirconium or hafnium compound with the metal salt. Alternatively, it is obtained by reacting a tetravalent titanium, zirconium or hafnium compound with a reducing agent and the metal salt.

The addition polymerization catalyst of the present invention is an addition polymerization catalyst obtained by bringing the above transition metal compound into contact with an activating cocatalyst. The addition polymerization catalyst of the present invention is preferably an addition polymerization catalyst obtained by bringing the above transition metal compound (A) into contact with the following (B) and / or the following (C). (B): one or more aluminum compounds selected from the following (B1) to (B3) (B1) an organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) a general formula ｛-Al (E ² ) -O-} cyclic aluminoxane having the structure represented by _b (B3) formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
Linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer, and c represents an integer of 1 or more.) (C): One or more boron compounds selected from the following (C1) to (C3) (C1) Boron represented by the general formula BQ ¹ Q ² Q ³ A compound, (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- Boron compound represented (where B is a boron atom in a trivalent state, Q
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid. Hereinafter, such an addition polymerization catalyst will be described in more detail.

(B) Aluminum Compound The aluminum compound (B) used in the present invention is at least one aluminum compound selected from the following (B1) to (B3). (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) Cyclic aluminoxane having a structure represented by the general formula （-Al (E ² ) -O-｝ _b (B3) General formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
Linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² , and E ³ are each a hydrocarbon group, and all E ¹ , all E ^2, and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. And c represents an integer of 1 or more.) As the hydrocarbon group for E ¹ , E ² or E ³ , a hydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkyl group is more preferable.

Specific examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; Dialkyl aluminum chloride such as dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, dihexyl aluminum chloride; alkyl aluminum dichloride such as methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, hexyl aluminum dichloride Dimethylal Examples thereof include dialkylaluminum hydrides such as minium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum or triisobutylaluminum.

[0050] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 In a linear aluminoxane (B3) having the structure shown,
Specific examples of E ² and E ³ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Examples thereof include an alkyl group such as an isobutyl group, a normal pentyl group, and a neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ²
And E ³ is a methyl group or an isobutyl group, and b
Is 2 to 40 and c is 1 to 40.

The above aluminoxane can be made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified. The aluminoxane produced by such a method is generally considered to be a mixture of a cyclic aluminoxane and a linear aluminoxane.

(C) Boron Compound In the present invention, the boron compound (C) includes (C1)
A boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C
2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q)
^{4) -} one or more boron compounds selected from boron compound represented by used.

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group, or a halogen atom. A substituted hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, 1 to 20
A halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms. Q ^{1 to} Q ³ are more preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, or 1
Halogenated hydrocarbon groups containing up to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably, Q ^{1 to} Q ⁴ each have at least one fluorine atom. 6 to 2 carbon atoms including atoms
0 is a fluorinated aryl group.

As specific examples of the compound (C1), tris (pentafluorophenyl) borane, tris (2,3,
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. And Q ^{1 to} Q ⁴ are Q ^{1 to} Q ³ in the above (C1).
Is the same as

[0056] formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

The formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is boron atom in the trivalent valence state ,
Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

[0059] formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
As (BQ ¹ Q ² Q ³ Q ⁴ ) ^{−, the same} as those described above can be mentioned.

As specific combinations of these, 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 N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned, and most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

The contact of the transition metal compound and the activating co-catalyst of the present invention in producing the addition polymerization catalyst obtained by contacting the above-mentioned transition metal compound with the activating co-catalyst is performed by contacting the transition metal compound with the activating co-catalyst. As long as the catalyst is formed, any method may be used, such as a method in which the transition metal compound and the activating cocatalyst are mixed and contacted with or without dilution with a solvent in advance, or separately in a polymerization tank. It is possible to adopt a method of supplying and contacting in a polymerization tank. Here, a plurality of types of activating cocatalysts may be used in combination, but some of them may be used by mixing them in advance, or they may be separately supplied to the polymerization tank for use. Needless to say, this is acceptable.

The amount of each component used is usually a molar ratio of (B) / transition metal compound (A) of 0.1 to 10,000, preferably 5 to 2,000, and a molar ratio of (C) / transition metal compound (A). It is desirable to use each component such that the ratio is between 0.01 and 100, preferably between 0.5 and 10.

The concentration when each component is used in the form of a solution or a suspension or slurry in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. The transition metal compound (A) is usually 0.001 to 200 mmol / L, more preferably 0.001 to 100 mmol / L, still more preferably 0.05 to 50 mmol / L, and (B) the equivalent of Al atom. In general, the concentration is 0.01 to 5000 mmol / L, more preferably 0.1 to 2500 mmol / L, and still more preferably 0.1 to 2000 mmol / L.
It is desirable to use each component so that it is usually in the range of 0.001 to 500 mmol / L, more preferably 0.01 to 250 mmol / L, and still more preferably 0.05 to 100 mmol / L.

[Polymerization] In the present invention, an addition polymerization catalyst obtained by bringing the above transition metal compound (A) into contact with the above (B) and / or the above (C) is used. When using an addition polymerization catalyst obtained by contacting the transition metal compound (A) with the transition metal compound (B), the cyclic aluminoxane (B2) and / or the linear aluminoxane (B3) may be used as (B). Is preferred. Further, another preferred embodiment of the addition polymerization catalyst includes an addition polymerization catalyst obtained by bringing the transition metal compounds (A), (B) and (C) into contact with each other. The above (B1) is easy to use.

In the present invention, an addition polymer is produced by subjecting an addition-polymerizable monomer to addition polymerization using the above-mentioned catalyst for addition polymerization. The monomer is preferably an olefin, and the addition polymer is preferably an olefin polymer. The olefin may have 2 to 2 carbon atoms.
Zero olefins, particularly ethylene, α-olefins having 3 to 20 carbon atoms, diolefins having 4 to 20 carbon atoms, and the like can be used, and two or more monomers can be used at the same time. Specific examples of the olefin include linear olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, and decene-1, and 3-methylbutene-. Examples include branched olefins such as 1,3-methylpentene-1, 4-methylpentene-1, and 5-methyl-hexene-1, and vinyl hydrocarbons such as vinylcyclohexane, but the present invention is limited to the above compounds. It should not be done. Specific examples of the combination of monomers at the time of copolymerization include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and octene-1, ethylene and vinylcyclohexane, and propylene and butene-1. However, the present invention should not be limited to these combinations.

The polymerization method is not particularly limited either. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, and methylene dichloride and the like can be used. Solvent polymerization using a halogenated hydrocarbon as a solvent, slurry polymerization, gas-phase polymerization in a gaseous monomer, and the like are possible, and both continuous polymerization and batch polymerization are possible.

The polymerization temperature can usually range from -50 ° C. to 200 ° C., particularly preferably from -20 ° C. to 100 ° C., and the polymerization pressure is usually from normal pressure to 60 kg / cm ² G. In general, the polymerization time is appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can usually range from 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

[0068]

The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The properties of the polymers in the examples were measured by the following methods. (1) Intrinsic viscosity [η]: 1 using an Ubbelohde viscometer
It was measured in a tetralin solution at 30 ° C.

(2) Content of repeating unit derived from α-olefin in copolymer: characteristic absorption of ethylene and α-olefin using infrared spectrophotometer (IR-810, manufactured by JASCO Corporation) It was calculated as the number of short-chain branches per 1000 carbons (SCB).

(3) Melting point of copolymer: Seiko SSC-
Using 5200, it was obtained under the following conditions. 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)

(4) Molecular weight and molecular weight distribution: Determined using a gel permeation chromatograph (150, C manufactured by Waters) under the following conditions. Column: TSK gel GMH-HT Measurement temperature: 145 ° C Setting Measurement concentration: 10 mg / 10 ml-ortho-dichlorobenzene Note that the molecular weight distribution is the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn). Was evaluated.

Example 1 (1) Synthesis of 1-bromo-3-tert-butyl-5-methyl-2-phenol In a nitrogen atmosphere, 2-tert-tert-butyl was placed in a 500 ml four-necked flask equipped with a stirrer. 20.1 g (123 mmol) of butyl-4-methylphenol were dissolved in 150 ml of toluene, followed by 25.9 ml of tert-butylamine.
(18.0 g, 246 mmol) was added. The solution was cooled to -70 ° C and 10.5 ml of bromine (32.6
g, 204 mmol). This solution was kept at -70 ° C and stirred for 2 hours. Thereafter, the temperature is raised to room temperature, and 10
Washing with 100 ml of 100% diluted hydrochloric acid was performed three times. The organic layer obtained after the washing was dried using anhydrous sodium sulfate, the solvent was removed using an evaporator, and then purified using a silica gel column to obtain a colorless oil, 1-.
18.4 g (75.7 mmol) of bromo-3-tert-butyl-5-methyl-2-phenol were obtained. The yield was 62%.

(2) Synthesis of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene In a 100 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere, 1 -Bromo-3-ter
13.9 g of t-butyl-5-methyl-2-phenol
(57.2 mmol) was dissolved in 40 ml of acetonitrile, followed by 3.8 g (67.9 mmol) of potassium hydroxide.
l) was added. Further, 17.8 ml of methyl iodide (4
0.6 g, 286 mmol) was added and stirring continued for 12 hours. Thereafter, the solvent was removed by an evaporator, and 40 ml of hexane was added to the residue to extract hexane-soluble components.
The extraction was repeated three times. The solvent was removed from the extract, and a pale yellow oil, 1-bromo-3-tert-butyl-
13.8 g of 2-methoxy-5-methylbenzene (5
3.7 mmol). The yield was 94%.

(3) Synthesis of chlorodimethyl (3-tret-butyl-2-methoxy-5-methylphenyl) silane 31.5 ml of tetrahydrofuran, 139 of hexane
1.6 ml of n-butyllithium at −40 ° C. to a solution consisting of 45 ml of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene synthesized in the same manner as in the above (2). Mol / l hexane solution
115 ml was added dropwise over 20 minutes. After keeping the obtained mixture at -40 ° C for 1 hour, tetrahydrofuran
31.5 ml was added dropwise. Dichlorodimethylsilane 1
In a solution consisting of 31 g and 306 ml of hexane,
At −40 ° C., the mixture obtained above was added dropwise. The resulting mixture was heated to room temperature over 2 hours, and further stirred at room temperature for 12 hours. The solvent and excess dichlorodimethylsilane were distilled off from the reaction mixture under reduced pressure, and hexane-soluble components were extracted from the residue with hexane. Of chlorodimethyl (3-tert-butyl-2-methoxy-5-methylphenyl) silane was obtained. The yield is 84%
Met.

(4) (tetramethylcyclopentadienyl) dimethyl (3-tert-butyl-2-methoxy-
Synthesis of 5-methylphenyl) silane Chlorodimethyl (3-tert-) synthesized in the above (3)
Butyl-2-methoxy-5-methylphenyl) silane
In a solution consisting of 5.24 g and 50 ml of tetrahydrofuran, 2.73 g of tetramethylcyclopentadienyllithium was added at -35 ° C, the temperature was raised to room temperature over 2 hours, and further stirred at room temperature for 10 hours. . The solvent was distilled off from the obtained reaction mixture under reduced pressure.
A hexane-soluble component was extracted using hexane, and the solvent was distilled off from the obtained hexane solution under reduced pressure to obtain a yellow oily (tetramethylcyclopentadienyl) dimethyl (3
6.69 g of -tert-butyl-2-methoxy-5-methylphenyl) silane were obtained. The yield was 97%.

(5) Synthesis of [dimethyl (3-tert-butyl-2-methoxy-5-methylphenyl) silyl (tetramethylcyclopentadienyl)] titanium dichloride (tetramethylcyclopenta) synthesized in the above (4) 1.61 of n-butyllithium was added to a solution of 2.00 g of dienyl) dimethyl (3-tert-butyl-2-methoxy-5-methylphenyl) silane, 20 g of toluene and 1.25 g of triethylamine at 0 ° C. 3.84 ml of a mol / liter hexane solution was added dropwise, and then the temperature was raised to room temperature over 2 hours, and further kept at room temperature for 12 hours. At 0 ° C under nitrogen atmosphere, titanium trichloride
Tripyridine 2.09 g toluene suspension 20.9 g
Was added dropwise to the mixture obtained above, then, the temperature was raised to room temperature over 1 hour, and the mixture was heated under reflux for 10 hours. The reaction mixture was filtered, the solvent was distilled off from the filtrate, and the residue was recrystallized from a mixed solvent of toluene and hexane to give fine dimethyl [3- (tert-butyl-butyl) as a light green fine crystal.
0.46 g of 2-methoxy-5-methylphenyl) silyl (tetramethylcyclopentadienyl)] titanium dichloride was obtained. The yield was 17%. The spectrum data was as follows. Mass spectrum (CI, m / e) 473

(6) Polymerization A 1-liter autoclave with a stirrer having an internal volume of 1 liter was vacuum-dried and replaced with argon, and then 300 ml of toluene was used as a solvent.
And the reactor was heated to 60 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 1.0 m
Then, 2.0 μmol of [dimethyl (3-tert-butyl-2-methoxy-5-methylphenyl) silyl (tetramethylcyclopentadienyl)] titanium dichloride synthesized in the above (5) was charged. Subsequently, 6.0 μmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added. Polymerization was performed for 60 minutes while controlling the temperature at 60 ° C. The temperature inside the polymerization tank was 3.1 due to the initial heat generation at this time.
° C. As a result of the polymerization, an ethylene homopolymer having a melting point of 133.1 ° C. was added in an amount of 1
8.7 × 10 ⁶ g was produced per hour.

Example 2 A 0.4-liter autoclave with a stirrer having an inner volume of 0.4 liter was vacuum-dried and purged with argon, and then 190 ml of toluene as a solvent and 10 ml of hexene-1 as an α-olefin were charged. The temperature rose. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ^2. After the inside of the system was stabilized, 0.5 mmol of triisobutylaluminum was added, and then [dimethyl (3-tert-butyl-2-methoxy-) was added. 5-methylphenyl) silyl (tetramethylcyclopentadienyl)] titanium dichloride (1.0 μmol), and subsequently triphenylcarbeniumtetrakis (pentafluorophenyl) borate (3.0 μmol). Polymerization was performed for 60 minutes while controlling the temperature at 60 ° C. The temperature inside the polymerization tank was 1.9 due to the initial heat generation at this time.
° C. As a result of polymerization, SCB = 20.6, [η] =
1.17 dl / g, molecular weight (Mw) = 7.6 × 10 ⁴ ,
Molecular weight distribution (Mw / Mn) = 2.2, melting point 110.3
℃ ethylene - hexene-1 copolymer, a titanium compound 1mol per per hour, 1.5 × 10 ⁷ g
Manufactured.

Comparative Example 1 An autoclave with a stirrer having an inner volume of 0.4 liter was vacuum-dried and replaced with argon, and then 190 ml of toluene as a solvent and 10 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 60 ° C. The temperature rose. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ^2. After the inside of the system was stabilized, 0.50 mmol of triisobutylaluminum was added, and then [dimethyl (3-tert-butyl- 2-methoxy-5-methylphenyl) silyl (tetramethylcyclopentadienyl)] titanium trichloride 1.0
μmol, followed by triphenylcarbenium tetrakis (pentafluorophenyl) borate 3.0
μmol was introduced. While adjusting the temperature to 60 ° C, 6
Polymerization was performed for 0 minutes. The temperature inside the polymerization tank increased by 11.5 ° C. due to the initial heat generation at this time. As a result of the polymerization, the ethylene-hexene-1 copolymer was converted into 1.1 × 10 4
⁷ g were produced.

Example 3 An autoclave with a stirrer having an inner volume of 0.4 liter was vacuum-dried and purged with argon, and then 190 ml of toluene as a solvent and 10 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 60 ° C. The temperature rose. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ^2, and after the inside of the system was stabilized, 1.0 mmol of a toluene solution of MMAO type 3A manufactured by Tosoh Akzo Co., Ltd. was added thereto in an amount of 1.0 mmol in terms of Al. 3-t
tert-butyl-2-methoxy-5-methylphenyl)
Silyl (tetramethylcyclopentadienyl)] titanium dichloride (1.0 μmol) was added. 60 ° C
The polymerization was carried out for 60 minutes while adjusting the temperature to. At this time, no temperature increase in the polymerization tank due to the initial heat generation was observed. As a result of polymerization, SCB = 14.8, [η] = 1.71.
dl / g, molecular weight (Mw) = 7.1 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 1.9, melting point of 114.7 ° C.
3.0 × 10 ⁶ g was produced per hour and per hour.

[Embodiment 4] In the embodiment 2, α used
Polymerization was carried out in the same manner except that the olefin was changed to butene-1 10 g. The temperature inside the polymerization tank increased by 2.6 ° C. due to the initial heat generation at this time. As a result of the polymerization, SCB =
15.2, [η] = 1.26 dl / g, molecular weight (Mw)
= 7.5 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 2.
7. An ethylene-butene-1 copolymer having a melting point of 93.9 ° C.
1.5 × 10 ⁷ g were produced.

Example 5 Polymerization was carried out in the same manner as in Example 2, except that triisobutylaluminum was changed to the same molar amount of triethylaluminum. The temperature inside the polymerization tank increased by 0.3 ° C. due to the initial heat generation at this time. As a result of polymerization, SCB = 12.7, [η] = 1.23
dl / g, molecular weight (Mw) = 3.4 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 2.2, melting point of 116.8 ° C.
1.3 × 10 ⁷ g was produced per ol / hour.

Example 6 Polymerization was carried out in the same manner as in Example 2 except that triisobutylaluminum was changed to the same molar amount of trimethylaluminum. The temperature inside the polymerization tank rose by 0.4 ° C. due to the initial heat generation at this time. As a result of polymerization, SCB = 9.6, [η] = 2.13d
1 / g, molecular weight (Mw) = 16.8 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 8.3, melting point of 119.9 ° C.
7.7 × 10 ⁶ g was produced per hour and per hour.

[Embodiment 7] In the embodiment 2,
Nilcarbenium tetrakis (pentafluorophenyl
B) Use the same molar amount of borate as [dimethylanilinium]
[Tetrakis (pentafluorophenyl) borate]
Polymerization was carried out in the same manner except for the change. First at this time
No temperature increase in the polymerization tank due to the initial heat generation was observed.
As a result of polymerization, SCB = 18.6, melting point was 114.1 ° C.
An ethylene-hexene-1 copolymer is converted to a titanium compound
1.9 × 10 per 1 mol / hour ⁶ g manufacture
did.

Example 8 A 1-liter autoclave with a stirrer having an inner volume of 1 liter was vacuum-dried and replaced with argon. After that, 300 ml of toluene was charged as a solvent, and the temperature of the reactor was raised to 40 ° C. After the temperature was raised, the propylene pressure was adjusted to 4 kg / cm ² and fed. After the inside of the system was stabilized, 1.25 mmol of triisobutylaluminum was added, followed by [dimethyl (3-tert-butyl-2-methoxy-). 5
-Methylphenyl) silyl (tetramethylcyclopentadienyl)] titanium dichloride 5.0 μmol
And then triphenylcarbenium tetrakis (pentafluorophenyl) borate 15.0 μmo
1 was charged. Polymerization was performed for 60 minutes while controlling the temperature at 40 ° C. The temperature inside the polymerization tank increased by 5.2 ° C. due to the initial heat generation at this time. As a result of the polymerization, the molecular weight (Mw) =
1.04 × 10 ⁶ , molecular weight distribution (Mw / Mn) = 2.
2, mesotriad 0.283, racemic triad 0.
162 as the titanium compound 1
1.6 × 10 ⁶ g was produced per mol and per hour.

[Example 9] A stirrer was put into an autoclave having an inner volume of 0.1 liter, dried under vacuum, replaced with argon and charged with 25 ml of toluene as a solvent. 6.
0 mmol, followed by [dimethyl (3-tert-
Butyl-2-methoxy-5-methylphenyl) silyl (tetramethylcyclopentadienyl)] titanium dichloride (6.0 μmol). In addition, 1,
3.24 g of 3-butadiene was introduced, and polymerization was carried out for 60 minutes while controlling the temperature at 25 ° C. As a result of the polymerization, the molecular weight (Mw) = 4.6 × 10 ⁵ , and the molecular weight distribution (Mw / M
n) = 1.8, 1,3-butadiene homopolymer (geometric isomer ratio of the double bond in the polymer chain is [1,4-c
is]: [1,4-trans]: [1,2-bond] =
0.830: 0.070: 0.100) was produced in an amount of 4.0 × 10 ⁴ g per hour per 1 mol of the titanium compound.

Example 10 An autoclave with a stirrer having an internal volume of 1 liter was vacuum-dried and purged with argon. After that, 300 ml of toluene as a solvent and 1.0 ml of 5-hexen-1-ol as a comonomer were charged, and a reactor was charged at 40 ml.
The temperature was raised to ° C. After raising the temperature, triethyl aluminum 20
mmol, and the mixture was fed while adjusting the ethylene pressure to 6 kg / cm ² , and stirring was continued for 15 minutes. After the system was stabilized, [dimethyl (3-tert-butyl-2-methoxy-5-methylphenyl) silyl (tetramethylcyclopentadienyl)] titanium dichloride5.
0 μmol, followed by triphenylcarbenium tetrakis (pentafluorophenyl) borate 1
5.0 μmol was added. Polymerization was performed for 60 minutes while controlling the temperature at 40 ° C. At this time, no temperature increase in the polymerization tank due to the initial heat generation was observed. As a result of the polymerization, the terminal alcohol content, 0.68 wt%, [η] = 4.96
dl / g of ethylene-hexen-1-ol copolymer per 1 mol of titanium compound, per hour,
1.2 × 10 ⁵ g was produced.

[Example 11] A stirrer with an internal volume of 1 liter
Vacuum dried autoclave, purged with argon and dissolved
300 ml of toluene as medium, vinyl as comonomer
Charge 15 ml of cyclohexane and raise the reactor to 60 ° C
Warmed. After heating, ethylene pressure is increased to 6 kg / cm ^Two Adjust to
While the system is stabilized, triisobutyl
0.75 mmol of aluminum, [dimethyl (3-te
rt-butyl-2-methoxy-5-methylphenyl) si
Ryl (tetramethylcyclopentadienyl)] titanium
1.5 μmol of mudichloride was added, followed by trichloride.
Phenylcarbenium tetrakis (pentafluorophen
4.5 μmol of (nyl) borate was charged. At 60 ° C
The polymerization was carried out for 60 minutes while controlling the temperature. At this time
No temperature rise in polymerization tank due to initial heat generation
Was. As a result of the polymerization, the content of vinylcyclohexane units =
Echile with 4.1 wt%, [η] = 2.27 dl / g
-Vinylcyclohexane copolymer with titanium compound 1
1.9 × 10 per mol / hour⁶ g manufactured
Was.

[0089]

As described above in detail, according to the present invention, a transition metal compound useful for adjusting an addition polymerization catalyst having a catalytic activity that can be industrially carried out while suppressing the calorific value at the beginning of polymerization, and Such an addition polymerization catalyst is provided, and an efficient production method of an addition polymer that can suppress industrial heating and can be industrially implemented is provided.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J028 AA01A AB01A AC01A AC09A AC27A BA00A BA01B BB00A BB01B BC15B BC25B CA17C EB02 EB04 EB05 EB07 EB08 EB10 EC01 EC02 EC03 GB01 4J128 AA01 AB01 AC01 BA00ABC BC01 AD01 EB04 EB05 EB07 EB08 EB10 EC01 EC02 EC03 GB01

Claims (8)

[Claims] 1. A transition metal compound represented by the following general formula (1). Wherein M represents a titanium atom, a zirconium atom or a hafnium atom in a +3 type oxidation state; A is a polydentate monoanionic ligand; R ¹ is an alkyl group, an aralkyl group, an aryl group, or Represents a substituted silyl group;
Is an oxygen atom or a sulfur atom; two Xs are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a disubstituted amino group And two Xs may be bonded to each other to form a ring; D represents a neutral ligand coordinated to M;
2 to 2. ) 2. The transition metal compound according to claim 1, wherein A is a polydentate monoanionic ligand represented by the following general formula (2). (Wherein Cp ¹ represents a group having a cyclopentadiene-type anion skeleton; G represents ¹ to 30 linking Cp ¹ and E)
Represents a substituent having three non-hydrogen atoms. ) 3. The transition metal compound according to claim 1, wherein the transition metal compound is represented by the following general formula (3). (Wherein M represents a titanium atom, a zirconium atom or a hafnium atom in a +3 type oxidation state; Cp ¹ represents a group having a cyclopentadiene-type anion skeleton; J
Represents an atom belonging to Group 14 of the periodic table; R ² and R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, E represents an aryloxy group or a disubstituted amino group, and a plurality of R ² may be arbitrarily bonded to form a ring; m represents an integer of 0 to 4;
Is an oxygen or sulfur atom; R ¹ is an alkyl group,
Represents an aralkyl group, an aryl group, or a substituted silyl group; two Xs each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, X represents a disubstituted amino group, and two Xs may combine with each other to form a ring; D represents a neutral ligand coordinated to M; n represents an integer of 0 to 2. ) 4. The transition metal compound according to claim 1, wherein E is an oxygen atom. 5. The transition metal compound according to claim 1, wherein M is a titanium atom. 6. The transition metal compound according to claim 1, wherein R ¹ is a methyl group. 7. A catalyst for addition polymerization obtained by bringing the transition metal compound according to claim 1 into contact with the following (B) and / or the following (C). (B): one or more aluminum compounds selected from the following (B1) to (B3) (B1) an organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) a general formula ｛-Al (E ² ) -O-} cyclic aluminoxane having the structure represented by _b (B3) formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
Linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer, and c represents an integer of 1 or more.) (C): One or more boron compounds selected from the following (C1) to (C3) (C1) Boron represented by the general formula BQ ¹ Q ² Q ³ A compound, (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- Boron compound represented (where B is a boron atom in a trivalent state, Q
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid. ) 8. A method for producing an addition polymer using the catalyst for addition polymerization according to claim 7.