JP2000186111A - Catalyst for olefin polymerization and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst for efficiently and inexpensively producing an olefin-based polymer, etc., without requiring an aftertreatment after polymerization since a large amount of metal component is not left in a produced polymer, comprising a transition metal compound and a silane compound- treated clay. SOLUTION: This catalyst comprises (A) a transition metal compound, (B) a silane compound-treated clay showing an absorption peak of infrared absorption spectrum in the range of 1090-1050 cm-1 or 1015-995 cm-1 and preferably further (C) an organometallic compound of the groups 1, 2, 13 and 14 of the periodic table. The component B is preferably obtained by treating a laminar silicate, a mineral belonging to smectite group, a compound having a smectite structure or a compound obtained by treating montmorillonite with a silane compound. A transition metal complex of the group 4 to 6 of the periodic table containing a conjugated five-membered ring as a ligand or a transition metal complex of the group 8-10 of the periodic table containing an organic ligand bonded to a transition metal through a nitrogen atom or a phosphorus atom is preferable as the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for olefin polymerization, a method for producing the same, and a method for producing an olefin polymer. More specifically, the present invention relates to a highly active olefin polymerization catalyst, a method for efficiently producing the same, and a method for producing a high-quality olefin polymer with high productivity using the olefin polymerization catalyst.

[0002]

2. Description of the Related Art In recent years, for producing an olefin polymer by polymerizing olefins in the presence of a catalyst, a method using a catalyst comprising a metallocene compound and an aluminoxane has been proposed (Japanese Patent Application Laid-Open No. 58-119309). And JP-A-2-167307). The polymerization method using these catalysts has a very high polymerization activity per transition metal and a high molecular weight distribution as compared with the method using a conventional Ziegler-Natta catalyst comprising a titanium compound or a vanadium compound and an organoaluminum compound. It is known that a polymer having a narrow particle size can be obtained.

[0003] A method has also been proposed in which a transition metal compound, an aluminoxane or an organoaluminum compound is used as a catalyst component, and an olefin is polymerized using a catalyst in which these are supported on an inorganic oxide such as silica or alumina (Japanese Patent Application Laid-Open (JP-A) No. 2002-110630). JP-A-61-108610, JP-A-1-101
No. 303). However, in these methods described above, in order to obtain sufficient polymerization activity, a large amount of aluminoxane is required, so that the activity per aluminum is low, which is not only uneconomical, but also that the produced polymer contains aluminum. There is a problem that a large amount of the catalyst remains, so that the catalyst residue must be removed from the polymer.

[0004] A method using clay minerals as a catalyst component has also been proposed (JP-A-5-25214,
JP-A-5-301917, JP-A-7-33814
However, in such a method, pretreatment of clay minerals with organoaluminum, especially expensive and highly dangerous methylaluminoxane or trimethylaluminum, is indispensable, and the activity per aluminum is not sufficient, and the production of clay minerals is not sufficient. There was a disadvantage that the amount of catalyst residue in the product was large.

Furthermore, in the method using these clay minerals as a catalyst component, it is necessary to suspend the clay mineral in water, repeatedly treat it with magnesium chloride or the like, and then perform hydrochloric acid treatment, washing and other operations over a long period of time. There was a problem.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above point of view, and can prepare a catalyst for olefin polymerization in a short time, is inconvenient to handle, has poor storage stability, and has a high risk. Since a large amount of organoaluminum used in the entire polymerization system can be significantly reduced without using a large amount of methylaluminoxane or trimethylaluminum, a large amount of metal does not remain in the produced polymer. It is an object of the present invention to provide an olefin polymerization catalyst for efficiently and inexpensively producing an olefin polymer, and further a syndiotactic sterically controlled styrene polymer, and a method for producing the olefin polymer. It is the purpose.

[0007]

According to the present invention, there is provided an olefin polymerization catalyst comprising a transition metal compound and a silane compound-treated clay exhibiting an absorption peak in a specific wavelength region in an infrared absorption spectrum. The inventors have found that the object can be achieved, and have completed the present invention based on these findings.

That is, the gist of the present invention is as follows. (1) The transition metal compound has an absorption peak in the infrared absorption spectrum of 1090 to 1050 cm ^-1 or 1015 to 9
An olefin polymerization catalyst comprising a clay treated with a silane compound that appears in an area of 95 cm ^-1 . (2) The catalyst for olefin polymerization according to the above (1), wherein the silane compound-treated clay is a silane compound-treated clay obtained by treating a layered silicate with a silane compound. (3) the silane compound-treated clay is a silane compound-treated clay obtained by treating a mineral belonging to the smectite group or a compound having a smectite structure with a silane compound;
The olefin polymerization catalyst according to the above (1) or (2). (4) The catalyst for olefin polymerization according to any one of (1) to (3), wherein the silane compound-treated clay is a silane compound-treated clay obtained by treating montmorillonite with a silane compound. (5) The transition metal compound has a transition metal complex of Groups 4 to 6 of the periodic table having a conjugated five-membered ring as a ligand, or an organic ligand bonded to a transition metal via a nitrogen atom or a phosphorus atom. The olefin polymerization catalyst according to any one of the above (1) to (4), which is a transition metal complex of Groups 8 to 10 of the periodic table. (6) The above-mentioned (1) to (1) to further containing an organometallic compound belonging to Group 1 of the periodic table, Group 2, Group 13 or Group 14.
The catalyst for olefin polymerization according to any one of (5). (7) As the silane compound, general formula [1],

[0009]

Embedded image

[In the formula (1), R represents a carbon atom, a silicon atom or a hydrogen atom at the substituent moiety directly bonding to the silicon atom, and X represents a substituent moiety directly bonding to the silicon atom. When the atom is a halogen atom, an oxygen atom or a nitrogen atom, and a plurality of R and X are present, the plurality of R or X may be the same or different. n is an integer of 2 or 3. The absorption peak of the infrared absorption spectrum obtained by the contact treatment between the silane compound represented by the formula (1) and clays is 1090 to 1050 cm ^-1 or 1015 to 9
A method for producing an olefin polymerization catalyst, comprising subjecting a silane compound-treated clay appearing in an area of 95 cm ^-1 to a contact treatment with a transition metal compound. (8) A method for producing an olefin polymer in which olefin is polymerized using the olefin polymerization catalyst according to any one of (1) to (6). (9) A method for producing an olefin polymer in which olefin is polymerized using the olefin polymerization catalyst obtained by the method described in (7).

[0011]

Embodiments of the present invention will be described below in detail. 1. Components of Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention is prepared by bringing (a) a transition metal compound into contact with (b) clays and (c) a silane compound represented by the general formula [1]. Contact treatment with a silane compound-treated clay in which the absorption peak of the obtained infrared absorption spectrum appears in the region of 1090 to 1050 cm ^-1 or 1015 to 995 cm ^-1 , and if necessary, further (d)
It is prepared by adding an organic metal compound of Group 1, Group 2, Group 13 and Group 14 of the periodic table. Each component suitably used for preparing these catalysts will be described. (A) Transition metal compound As the (a) transition metal compound used in the present invention, a transition metal compound of Groups 4 to 6 or a Group 8 to 10 of the periodic table is used. Of these, periodic table 4-6
As the group transition metal compound, those represented by the following general formulas [2] to [4] can be preferably mentioned from the viewpoint of activity, and as the transition metal compounds of groups 8 to 10 of the periodic table, And those represented by the following general formula [5] are preferred.

[0012]

Embedded image

[Wherein Q¹Is the two conjugated five-membered ligand
(C_FiveH_5-abR¹ _b) And (C_FiveH _5-acR^Two _c)
Q represents a crosslinkable bonding group;^TwoIs a conjugated five-membered ligand
(C_FiveH _5-adR^Three _d) And Z¹A binding group that crosslinks the group
Show. R¹, R^TwoAnd R^ThreeRepresents a hydrocarbon group,
Rogen atom, alkoxy group, silicon-containing hydrocarbon group, phosphorus
-Containing hydrocarbon group, nitrogen-containing hydrocarbon group or boron-containing hydrocarbon
Represents a hydrogen group, and a is 0, 1 or 2. b, c and d
Is an integer of 0 to 5 when a = 0, and
Each time is an integer of 0-4, and when a = 2, each is 0
Represents an integer of 1 to 3. (P + q) is (M¹The valence of 2)
Yes, r is M¹Shows the valence of M¹Is group 4 to 6 of the periodic table
Transition metal, M^TwoIndicates a transition metal of Groups 8 to 10 of the periodic table
And (u + v) is M^TwoShows the valence of Also, L¹, L^Two
Represents a ligand having a coordination bond, and X represents¹, Y¹,
Z¹X^Two, Y^TwoAre covalent or ionic, respectively
Represents a sex ligand, X^TwoRepresents a covalent ligand
I have. Note that L¹, L^Two, X^TwoAnd Y^TwoRespectively
They may combine with each other to form a ring structure. ] This Q¹And Q^TwoSpecific examples of (1) methylene
Group, ethylene group, isopropylene group, methylphenyl
Tylene group, diphenylmethylene group, cyclohexylene group
C1-C4 alkylene groups such as cycloalkylene
Group or its side chain lower alkyl or phenyl substituent,
(2) Silylene group, dimethylsilylene group, methylphenyl
Lusilylene group, diphenylsilylene group, disilylene group,
Silylene groups such as tetramethyldisilylene groups, oligos
Rylene group or its lower-chain lower alkyl or phenyl group
(3) (CH_Three)_TwoGe group, (C₆H_Five)_TwoGe
Group, (CH_Three)_TwoP group, (C₆H_Five)_TwoP group, (C_FourH
₉) N group, (C₆H_Five) N group, (CH_Three) B group, (C_Four
H₉) B group, (C₆H_Five) B group, (C₆H_Five) Al-based,
(CH_ThreeO) Germanium such as Al group, phosphorus, nitrogen,
Hydrocarbon groups containing boron or aluminum (lower alkyl
Group, phenyl group, hydrocarbyloxy group (preferably
Lower alkoxy group), etc.]. these
Of these, alkylene and silylene groups are preferred from the viewpoint of activity.
New

Further, (C ₅ H _5-ab R ¹ _b ) and (C ₅ H
_5-ac R ² _c ) and (C ₅ H _5-ad R3 _d ) are conjugated five-membered ring ligands, and R ¹ , R ² and R ³ are a hydrocarbon group, a halogen atom, an alkoxy group, It represents a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, and a is 0, 1 or 2.
b, c and d each represent an integer of 0 to 5 when a = 0, an integer of 0 to 4 when a = 1, and an integer of 0 to 3 when a = 2. Here, the hydrocarbon group preferably has 1 to 20 carbon atoms, and particularly preferably has 1 to 12 carbon atoms. This hydrocarbon group may be bonded as a monovalent group to a cyclopentadienyl group which is a conjugated five-membered ring group, and when there are a plurality of these, two of them are bonded to each other to form a cyclopentadienyl group. A ring structure may be formed together with a part of the pentadienyl group. That is, typical examples of the conjugated five-membered ring ligand are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and examples of the alkoxy group include
Those having 1 to 12 carbon atoms are preferred. Examples of the silicon-containing hydrocarbon group include -Si (R ⁴ ) (R ⁵ )
(R ⁶ ) (R ⁴ , R ⁵ and R ⁶ are a hydrocarbon group having 1 to 24 carbon atoms) and the like. Examples of the phosphorus-containing hydrocarbon group, the nitrogen-containing hydrocarbon group and the boron-containing hydrocarbon group are: ^{P- (R 7) (R 8} ), - N (R 7) (R 8) and -
B (R ⁷ ) (R ⁸ ) (R ⁷ and R ⁸ are a hydrocarbon group having 1 to 18 carbon atoms). When there are a plurality of R ¹ , R ² and R ³ , each of the plurality of R ¹ , the plurality of R ² and the plurality of R ³ may be the same or different. In the general formula [2], conjugated five-membered ring ligand _{(C 5 H 5-ab R} 1 b) and (C ₅ H _5-ac
R ² _c ) may be the same or different.

On the other hand, M ¹ represents a transition metal element belonging to Groups 4 to 6 of the periodic table, and specific examples thereof include titanium, zirconium, hafnium, vanadium, niobium, molybdenum, tungsten and the like. And titanium, zirconium and hafnium are preferred from the viewpoint of activity. Z ¹ is a covalent ligand, specifically, a halogen atom, oxygen (—O—), sulfur (—S—),
An alkoxy group having 1 to 20, preferably 1 to 10 carbon atoms;
A thioalkoxy group having 1 to 20, preferably 1 to 12 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a phosphorus-containing hydrocarbon having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms Represents a group. X ¹ and Y ¹ are a covalent ligand or a bonding ligand, specifically, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms. , 1 to 20 carbon atoms, preferably 1
An alkoxy group, an amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (for example, diphenylphosphine group) or a silicon-containing carbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Hydrogen group (for example, trimethylsilyl group), carbon number 1-20, preferably 1-1
2 represents a hydrocarbon group or a boron compound containing halogen (for example, B (C ₆ H ₅ ) ₄ , BF ₄ ). Of these, a halogen atom and a hydrocarbon group are preferred. X ¹ and Y ¹
They may be the same or different. Also,
X ² is a covalent ligand, specifically a halogen atom, a hydrocarbylamino group or a hydrocarbyloxy group, preferably an alkoxy group.

(I) Specific examples of the transition metal compounds represented by the general formulas [2] and [3] include the following compounds. Bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadi (Enyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyltitanium dichloride, bis (indenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (cyclopentadienyl) Titanium chlorohydride,
Bis (cyclopentadienyl) methyltitanium chloride, bis (cyclopentadienyl) ethyltitanium chloride, bis (cyclopentadienyl) phenyltitanium chloride, bis (cyclopentadienyl) dimethyltitanium, bis (cyclopentadienyl) Diphenyltitanium, bis (cyclopentadienyl) dineopentyltitanium, bis (cyclopentadienyl) dihydrotitanium, (cyclopentadienyl) (indenyl) titanium dichloride, (cyclopentadienyl)
(Fluorenyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (Tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl zirconium dichloride, bis (indenyl) zirconium dichloride,
Bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium chlorohydride, bis (cyclopentadienyl) methyl zirconium chloride, bis (cyclopentadienyl) ethyl zirconium chloride, bis (cyclopentadienyl) phenyl zirconium chloride , Bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) dineopentyl zirconium, bis (cyclopentadienyl) dihydrozirconium, (cyclopentadienyl) ( Transition metals having two conjugated five-membered ring ligands without a cross-linking group, such as indenyl) zirconium dichloride and (cyclopentadienyl) (fluorenyl) zirconium dichloride Compounds,

Methylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, methylenebis (indenyl) titanium chlorohydride, ethylenebis (indenyl) methyltitanium chloride, ethylenebis (indenyl) methoxychlorotitanium, ethylenebis (indenyl) titanium Diethoxide, ethylenebis (indenyl) dimethyltitanium, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylenebis (2-methylindenyl) titanium dichloride, ethylenebis (2,4-dimethyl) Indenyl) titanium dichloride, ethylenebis (2-methyl-4-trimethylsilylindenyl) titanium dichloride, ethylenebis (2,4-dimethyl) -5,6,7-trihydroindenyl) titanium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) titanium dichloride, ethylene (2-methyl-4 -T-butylcyclopentadienyl)
(3′-t-butyl-5′-methylcyclopentadienyl) titanium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) Titanium dichloride, isopropylidenebis (2-methylindenyl) titanium dichloride, isopropylidenebis (indenyl) titanium dichloride, isopropylidenebis (2,4-dimethylindenyl) titanium dichloride, isopropylidene (2,4-dimethylcyclopenta Dienyl) (3'5'-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-
t-butyl-5'-methylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl) (3
4-dimethylcyclopentadienyl) titanium chlorohydride, methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) dimethyltitanium, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) diphenyltitanium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) titanium dichloride, methylene ( Cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (2,3 , 4,5-tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) titanium dichloride, isopropylidene (cyclopentadienyl) Fluorenyl) titanium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (2,5-dimethyl-cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl ) Titanium dichloride,
Ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenyl Methylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride,
Cyclohexylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ′,
4'-dimethylcyclopentadienyl) titanium dichloride, methylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, methylenebis (indenyl) zirconium chlorohydride, ethylenebis (indenyl) methylzirconium chloride, ethylenebis (indenyl) methoxy Chlorozirconium, ethylenebis (indenyl) zirconium diethoxide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylenebis (2,4-dimethylindenyl)
Zirconium dichloride, ethylenebis (2-methyl-
4-trimethylsilylindenyl) zirconium dichloride, ethylenebis (2,4-dimethyl-5,6,7-
Trihydroindenyl) zirconium dichloride, ethylene (2,4-dimethylcyclopentadienyl)
(3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, ethylene (2-methyl-4-t-butylcyclopentadienyl) (3′-t-butyl-5 ′
-Methylcyclopentadienyl) zirconium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2-methyl Indenyl) zirconium dichloride,
Isopropylidenebis (indenyl) zirconium dichloride, isopropylidenebis (2,4-dimethylindenyl) zirconium dichloride, isopropylidene (2,4-dimethylcyclopentadienyl) (3′5 ′)
-Dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'-methylcyclopentadienyl) zirconium dichloride,
Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium chlorohydride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) dimethyl zirconium, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) diphenyl zirconium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium Dichloride, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (Cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (3,4-dimethylcyclopenta Dienyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl)
(3,5-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (2,
5-dimethylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3) hafnium diethoxide, ethylenebis (indenyl) dimethylhafnium 4-diethylcyclopenta Dienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (2.5) -Dimethylcyclopentadienyl) (3 ′,
4'-dimethylcyclopentadienyl) zirconium dichloride, methylenebis (indenyl) hafnium dichloride, ethylenebis (indenyl) hafnium dichloride, methylenebis (indenyl) hafnium chlorohydride, ethylenebis (indenyl) methylhafnium chloride, ethylenebis (indenyl) methoxy Chlorohafnium, ethylenebis (indenyl) hafnium diethoxide, ethylenebis (indenyl) dimethylhafnium, ethylenebis (4,5,6,7-tetrahydroindenyl) hafnium dichloride, ethylenebis (2
-Methylindenyl) hafnium dichloride, ethylenebis (2,4-dimethylindenyl) hafnium dichloride, ethylenebis (2-methyl-4-trimethylsilylindenyl) hafnium dichloride, ethylenebis (2,4-dimethyl-5,6 , 7-Trihydroindenyl) hafnium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) hafnium dichloride, ethylene (2-methyl-4-t-butyl) Cyclopentadienyl)
(3'-t-butyl-5'-methylcyclopentadienyl) hafnium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) Hafnium dichloride, isopropylidenebis (2-methylindenyl) hafnium dichloride, isopropylidenebis (indenyl) hafnium dichloride, isopropylidenebis (2,4-dimethylindenyl) hafnium dichloride, isopropylidene (2,4-dimethylcyclopenta Dienyl) (3'5'-dimethylcyclopentadienyl) hafnium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-
t-butyl-5'-methylcyclopentadienyl) hafnium dichloride, methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) hafnium dichloride, methylene (cyclopentadienyl) (3
4-dimethylcyclopentadienyl) hafnium chlorohydride, methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) dimethylhafnium, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) diphenylhafnium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) hafnium dichloride, methylene ( Cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium dichloride, isopropylidene (cyclopentadienyl) (2,3 , 4,5-Tetramethylcyclopentadienyl) hafnium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) hafnium dichloride, isopropylidene (cyclopentadienyl) Fluorenyl) hafnium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, isopropylidene (2,5-dimethyl-cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) hafnium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl ) Hafnium dichloride,
Ethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenyl Methylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride, cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ′,
A transition metal compound having two conjugated five-membered ring ligands bridged by an alkylene group such as 4′-dimethylcyclopentadienyl) hafnium dichloride;

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (4,5
6,7-tetrahydroindenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2,4-
Dimethylindenyl) titanium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoin Benzyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-naphthylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) titanium dichloride, phenylmethylsilylenebis (indenyl) titanium dichloride, Phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, phenylmethylsilylenebis (2,4
-Dimethylindenyl) titanium dichloride, phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl)
Titanium dichloride, phenylmethylsilylene (2,
3,5-trimethylcyclopentadienyl) (2 ′,
4 ', 5'-trimethylcyclopentadienyl) titanium dichloride, phenylmethylsilylenebis (tetramethylcyclopentadienyl) titanium dichloride,
Diphenylsilylenebis (2,4-dimethylindenyl) titanium dichloride, diphenylsilylenebis (indenyl) titanium dichloride, diphenylsilylenebis (2-methylindenyl) titanium dichloride, tetramethyldisilylenebis (indenyl) titanium dichloride, tetramethyl Disilylene bis (cyclopentadienyl) titanium dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) ( Tramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) titanium dichloride, Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (2
7-di-t-butylfluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethyl Silylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (2-
Ethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2 ′, 7′-diethyl -T-butylfluorenyl) titanium dichloride, dimethylsilylene (2.5
-Dimethylcyclopentadienyl) (2 ', 7'-di-
t-butylfluorenyl) titanium dichloride, dimethylsilylene (2-ethylcyclopentadienyl)
(2 ', 7'-di-t-butylfluorenyl) titanium dichloride, dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl)
Titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrfluorenyl) titanium dichloride, dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethylsilylene (ethylcyclopentadienyl) (Octahydrofluorenyl) titanium dichloride, dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6
7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2,4
-Dimethylindenyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl)
Zirconium dichloride, dimethylsilylenebis (2-
Methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylene Bis (indenyl) zirconium dichloride, phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, phenylmethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, phenylmethylsilylene (2,4 -Dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5 '-Trimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilylenebis (2,4
-Dimethylindenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, diphenylsilylenebis (2-methylindenyl) zirconium dichloride, tetramethyldisilylenebis (indenyl) zirconium dichloride, tetramethyldisilylenebis (cyclopentadiyl) (Enyl) zirconium dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ( Tetraethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene Pentadienyl) (2,7-di -
t-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2, 5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2
-Ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2 ′, 7′- Di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (2 ′,
7'-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (2 ', 7'-di-t-butylfluorenyl)
Zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrfluorenyl) zirconium dichloride, dimethylsilylene (Dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) (octahydrofluoride Nyl) zirconium dichloride, dimethylsilylenebis (indenyl) hafnium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) hafnium dichloride Dimethylsilylenebis (2-methylindenyl) hafnium dichloride, dimethylsilylenebis (2,4-dimethylindenyl) hafnium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethyl Cyclopentadienyl) hafnium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) hafnium dichloride, dimethylsilylenebis (2-methyl-
4-naphthylindenyl) hafnium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) hafnium dichloride, phenylmethylsilylenebis (indenyl) hafnium dichloride, phenylmethylsilylenebis (4,5,6,7-tetrahydro Indenyl) hafnium dichloride, phenylmethylsilylenebis (2,4-dimethylindenyl) hafnium dichloride, phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) hafnium Dichloride, phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dichloride, phenylmethylsilylenebis (tetramethylcyclo (Antadenyl) hafnium dichloride, diphenylsilylenebis (2,4-dimethylindenyl) hafnium dichloride, diphenylsilylenebis (indenyl) hafnium dichloride, diphenylsilylenebis (2-methylindenyl) hafnium dichloride, tetramethyldisilylenebis (indenyl) Hafnium dichloride, tetramethyldisilylenebis (cyclopentadienyl) hafnium dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-dimethyl Cyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) hafnium dichloride, dimethyi Rusilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (triethyl Cyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (2 , 7-Di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) hafnium dichloride Len (2-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilylene (2,5-dimethyl-cyclopentadienyl)
(Fluorenyl) hafnium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilylene (2.5
-Diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2 ′, 7′-di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (2,5- Dimethylcyclopentadienyl) (2 ′,
7'-di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (2 ', 7'-di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (diethylcyclo) Pentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrfluorenyl)
Hafnium dichloride, dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, dimethylsilylene (diethylcyclopentadienyl) A transition metal compound having two silylene group-bridged conjugated five-membered ring ligands such as (octahydrofluorenyl) hafnium dichloride;

Dimethylgermylene bis (indenyl)
Titanium dichloride, dimethylgermylene (cyclopentadienyl) (fluorenyl) titanium dichloride, methylaluminylenebis (indenyl) titanium dichloride, phenylamylenebis (indenyl) titanium dichloride, phenylphosphylenebis (indenyl) titanium dichloride, ethylborenebis ( (Indenyl) titanium dichloride, phenylamylenebis (indenyl) titanium dichloride, phenylamylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylgermylenebis (indenyl)
Zirconium dichloride, dimethylgermylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylaluminylenebis (indenyl) zirconium dichloride, phenylamylenebis (indenyl) zirconium dichloride, phenylphosphylenebis (indenyl) zirconium dichloride, ethylborenebis ( (Indenyl) zirconium dichloride, phenylamylenebis (indenyl) zirconium dichloride, phenylamylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylgermylenebis (indenyl) hafnium dichloride, dimethylgermylene (cyclopentadienyl) ( Fluorenyl) hafnium dichloride, methylaluminylenebis (indenyl)
Hafnium dichloride, phenylamylenebis (indenyl) hafnium dichloride, phenylphosphylenebis (indenyl) hafnium dichloride, ethylborenebis (indenyl) hafnium dichloride, phenylamylenebis (indenyl) hafnium dichloride, phenylamylene (cyclopentadienyl) ( A transition metal compound having two conjugated five-membered ligands bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, such as fluorenyl) hafnium dichloride;

Pentamethylcyclopentadienyl-bis (phenyl) aminotitanium dichloride, indenyl-bis (phenyl) aminotitanium dichloride, pentamethylcyclopentadienyl-bis (trimethylsilyl) aminotitanium dichloride, pentamethylcyclopentadienylphenoxy Titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl)
t-butylaminotitanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylaminotitanium dichloride, dimethylsilylene (tetrahydroindenyl) decylaminotitanium dichloride, dimethylsilylene (tetrahydroindenyl) [bis (trimethylsilyl) amino] titanium dichloride Dimethylgermylene (tetramethylcyclopentadienyl) phenylaminotitanium dichloride, pentamethylcyclopentadienyltitanium trimethoxide, pentamethylcyclopentadienyltitanium trichloride, pentamethylcyclopentadienyl-bis (phenyl) amino Zirconium dichloride, indenyl-bis (phenyl) aminozirconium dichloride,
Pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride, pentamethylcyclopentadienylphenoxyzirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) t-butylaminozirconium dichloride, dimethylsilylene (tetramethylcyclopentadiyl Enyl) phenylaminozirconium dichloride, dimethylsilylene (tetrahydroindenyl) decylaminozirconium dichloride, dimethylsilylene (tetrahydroindenyl) [bis (trimethylsilyl) amino] zirconium dichloride, dimethylgermylene (tetramethylcyclopentadienyl) phenylaminozirconium Dichloride, pentamethylcyclopentadienyl zirconium trimethoxide, N-methylcyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl-bis (phenyl) aminohafnium dichloride, indenyl-bis (phenyl) aminohafnium dichloride, pentamethylcyclopentadienyl-bis (trimethylsilyl) aminohafnium dichloride, Pentamethylcyclopentadienylphenoxyhafnium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) t-butylaminohafnium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylaminohafnium dichloride, dimethylsilylene (tetrahydroindenyl) decyl Amino hafnium dichloride, dimethyl silylene (tetrahydroindenyl) [bis (trimethylsilyl) amido ] Conjugated five-membered ring ligands such as hafnium dichloride, dimethylgermylene (tetramethylcyclopentadienyl) phenylaminohafnium dichloride, pentamethylcyclopentadienyl hafnium trimethoxide, and pentamethylcyclopentadienyl hafnium trichloride. A transition metal compound having one,

(1,1′-dimethylsilylene) (2,
2′-isopropylidene) -bis (cyclopentadienyl) titanium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) -bis (cyclopentadienyl) titanium dichloride, (1,1 '-
Dimethylsilylene) (2,2'-isopropylidene)-
Bis (cyclopentadienyl) dimethyltitanium,
(1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) dibenzyltitanium, (1,1′-dimethylsilylene) (2
2′-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilyl) titanium, (1,1 ′
-Dimethylsilylene) (2,2'-isopropylidene)
-Bis (cyclopentadienyl) bis (trimethylsilylmethyl) titanium, (1,2′-dimethylsilylene) (2,1′-ethylene) -bis (indenyl) titanium dichloride, (1,1′-dimethylsilylene)
(2,2′-ethylene) -bis (indenyl) titanium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) -bis (indenyl) titanium dichloride, (1,1′-dimethylsilylene) (2,2'-
(Cyclohexylidene) -bis (indenyl) titanium dichloride, (1,1′-dimethylsilylene) (2,
2′-isopropylidene) -bis (cyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride,
1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) dimethylzirconium, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadiene) Enyl) dibenzylzirconium, (1,1'-dimethylsilylene)
(2,2′-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilyl) zirconium,
(1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilylmethyl) zirconium, (1,2′-dimethylsilylene) (2,1′-ethylene) -Bis (indenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-ethylene) -bis (indenyl) zirconium dichloride, (1,1'-ethylene)
(2,2'-dimethylsilylene) -bis (indenyl)
Zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-cyclohexylidene) -bis (indenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (Cyclopentadienyl) hafnium dichloride, (1,
1′-dimethylsilylene) (2,2′-dimethylsilylene) -bis (cyclopentadienyl) hafnium dichloride, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadiene) Enyl) dimethylhafnium, (1,1'-dimethylsilylene)
(2,2'-isopropylidene) -bis (cyclopentadienyl) dibenzylhafnium, (1,1'-dimethylsilylene) (2,2'-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilyl) ) Hafnium, (1,1'-dimethylsilylene) (2,2 '
-Isopropylidene) -bis (cyclopentadienyl)
Bis (trimethylsilylmethyl) hafnium, (1,
2′-dimethylsilylene) (2,1′-ethylene) -bis (indenyl) hafnium dichloride, (1,1′-
(Dimethylsilylene) (2,2′-ethylene) -bis (indenyl) hafnium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) -bis (indenyl) hafnium dichloride, (1,1′- Transition metal compounds having two conjugated five-membered ring ligands in which ligands are double-bridged, such as dimethylsilylene) (2,2′-cyclohexylidene) -bis (indenyl) hafnium dichloride. In the compounds described in the above-mentioned, a chlorine atom of these compounds is replaced with a bromine atom, an iodine atom, a hydrogen atom, a methyl group, a phenyl group, a benzyl group, a methoxy group,
Those substituted with a dimethylamino group and the like can be mentioned. Among the above-mentioned compounds, a transition metal compound having one conjugated five-membered ring ligand is particularly preferably used in the production of a styrene-based polymer.

(II) Specific examples of the transition metal compound represented by the general formula [4] include the following compounds. Tetra-n-butoxytitanium, tetra-i-
Propoxy titanium, tetraphenoxy titanium,
Examples thereof include tetracrezoxytitanium, tetrachlorotitanium, tetrakis (diethylamino) titanium, tetrabromotitanium, and compounds in which titanium is replaced with zirconium or hafnium. Among these transition metal compounds, an alkoxy titanium compound, an alkoxy zirconium compound and an alkoxy hafnium compound are preferred.

(III) In the transition metal compound represented by the general formula [5], M ² represents a transition metal belonging to Groups 8 to 10 of the periodic table. And the like, of which nickel, palladium and iron are preferred. L ¹ and L ² each represent a ligand having a coordination bond, and X ² and Y ² each represent a ligand having a covalent bond or an ionic bond. Here, X ² and Y ² are, as described above, specifically a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
10 to 10 alkoxy groups, imino groups, amino groups, 1 carbon atom
-20, preferably 1-12, phosphorus-containing hydrocarbon groups (e.g., diphenylphosphine groups, etc.) or 1-2 carbon atoms.
0, preferably 1 to 12 silicon-containing hydrocarbon groups (eg, trimethylsilyl group, etc.), 1 to 20, preferably 1 to 12 carbon atoms, or halogen-containing boron compounds (eg, B (C ₆ H ₅ ) ₄ and BF ₄ ). Of these, a halogen atom and a hydrocarbon group are preferred. X ² and Y ² may be the same or different. Further, specific examples of L ¹ and L ² include triphenylphosphine; acetonitrile; benzonitrile;
1,2-bisdiphenylphosphinoethane; 1,3-bisdiphenylphosphinopropane; 1,1′-bisdiphenylphosphinoferrocene; cyclooctadiene; pyridine; quinoline; N-methylpyrrole; Phosphorane and the like can be mentioned. Note that the above L ¹ , L ² , X
² and Y ² may be bonded to each other to form a ring structure.

Specific examples of the transition metal compound represented by the general formula [5] include dibromobistriphenylphosphine nickel, dichlorobistriphenylphosphine nickel, dibromodiacetonitrile nickel, dibromodibenzonitrile nickel, dibromo (1,2- Bisdiphenylphosphinoethane) nickel, dibromo (1,
3-bisdiphenylphosphinopropane) nickel, dibromo (1,1′-diphenylbisphosphinoferrocene) nickel, dimethylbistriphenylphosphinenickel, dimethyl (1,2-bisdiphenylphosphinoethane) nickel, methyl (1,2 -Bisdiphenylphosphinoethane) nickel tetrafluoroborate,
(2-diphenylphosphino-1-phenylethyleneoxy) phenylpyridine nickel, dichlorobistriphenylphosphine palladium, dichlorodibenzonitrile palladium, dichlorodiacetonitrile palladium,
Dichloro (1,2-bisdiphenylphosphinoethane)
Examples include palladium, bistriphenylphosphine palladium bistetrafluoroborate, bis (2,2′-bipyridine) methyliron tetrafluoroborate etherate, and the following compounds.

[0025]

Embedded image

Wherein Me represents a methyl group. Among them, cations such as methyl (1,2-bisdiphenylphosphinoethane) nickel tetrafluoroborate, bistriphenylphosphine palladium bistetrafluoroborate, and bis (2,2'-bipyridine) methyl iron tetrafluoroborate etherate A type complex or a compound represented by the above formula is preferably used. In the catalyst of the present invention, the transition metal compound of the component (a) is
One type may be used or two or more types may be used in combination.

(B) Clays Clay or clay mineral As the component (b), clay or clay mineral is used. Clay is an aggregate of fine hydrated silicate minerals, and refers to a substance that exhibits plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. In addition, the clay mineral refers to a hydrated silicate that is a main component of the clay.

These are not limited to natural products, and may be artificially synthesized. Ion-exchange layered compound As the component (b), an ion-exchange layered compound is further used. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force to each other, and means a compound whose contained ions are exchangeable. Some clay minerals are ion-exchangeable layered compounds.

For example, phyllosilicic acids are mentioned as clay minerals. The phyllosilicic acids include phyllosilicic acid and phyllosilicates. Examples of the phyllosilicate include, as natural products, montmorillonite belonging to the smectite group, saponite, hectorite, illite belonging to the mica group, sericite, and mixed layer minerals of the smectite group and the mica group or the mica group and the vermiculite group. .

Further, as synthetic products, tetrasilicon mica,
Laponite, smecton and the like. In addition, α-
Zr (HPO ₄ ) ₂ , γ-Zr (HPO ₄ ) ₂ , α-T
Examples thereof include ion-exchange compounds having a layered crystal structure that are not clay minerals, such as i (HPO ₄ ) ₂ and γ-Ti (HPO ₄ ) ₂ .

Clays and clay minerals which do not belong to the ion-exchangeable layered compound. Specific examples of the component (b) include, if the content of montmorillonite is low, a clay called bentonite, and a wood section containing many other components in montmorillonite. There are clay, gairome clay, sepiolite exhibiting a fibrous form, palygorskite, and amorphous or low-crystalline allophane and imogolite.

In the present invention, when the component (b) is brought into contact with (c) a silane compound and, if necessary, (d) an alkylating agent, the component (b) in the clay, clay mineral and ion-exchange layered compound is used. It is also preferable to perform a chemical treatment from the viewpoint of removing impurities or changing the structure and function. Here, the chemical treatment refers to either a surface treatment for removing impurities adhering to the surface or a treatment for affecting the crystal structure of the clay. Specifically, acid treatment, alkali treatment, salt treatment, organic substance treatment and the like can be mentioned.

The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as aluminum, iron and magnesium in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic complex, and the like are formed, and the surface area, the interlayer distance, and the like can be changed. By utilizing the ion exchange property and replacing the exchangeable ions between the layers with another bulky ion, it is also possible to obtain an interlayer material in which the layers are expanded. The above-mentioned component (b) may be used as it is, may be one to which water is newly added and adsorbed, or may be one subjected to heat dehydration treatment. As the component (b), clay or clay mineral is preferred from the viewpoint of activity, and phyllosilicic acids are preferred.

(C) Silane Compound In the present invention, a highly active catalyst can be obtained by using a raw material component obtained by treating the clay with the silane compound. Preferred as the silane compound used as the component (c) is the silane compound represented by the general formula [1].

In the silane compound represented by the general formula [1], a silicon atom is contained in a molecule and a plurality of bissilyl compounds [X
_4-n Si (CH ₂ ) _m SiX _4-n ] (m is 1 to 10, n
Represents 1, 2 or 3. ) And polynuclear polysiloxanes and polysilazanes. The substituent R in the general formula [1] includes an alkyl group, a phenyl group, a silyl group, and a hydride group.
Among these, an alkyl group is preferred. Further, examples of the substituent X include halide, hydroxide, alkoxide, amide, and the like. Preferred is halide, and more preferred is chloride.

Specific examples of the silane compound include trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, t-butyldimethylsilyl chloride, t-butyldiphenylsilyl chloride,
Trialkylsilyl chlorides such as phenethyldimethylsilyl chloride, dimethylsilyl dichloride, diethylsilyl dichloride, diisopropylsilyl dichloride,
Dialkylsilyl dichlorides such as di-n-hexylsilyl dichloride, dicyclohexylsilyl dichloride, docosylmethylsilyl dichloride, bis (phenethyl) silyl dichloride, methylphenethylsilyl dichloride, diphenylsilyl dichloride, dimesitylsilyl dichloride, and ditolysilyl dichloride. Is mentioned.

Further, halides in which the above-mentioned chloride moiety is replaced by another halogen element, bis (trimethylsilyl) amide, bis (triethylsilyl) amide, bis (triisopropylsilyl) amide, bis (dimethylethylsilyl) amide, bis (dimethylethylsilyl) amide (Diethylmethylsilyl) amide, bis (dimethylphenylsilyl) amide, bis (dimethyltolyl) amide, bis (dimethylmesityl)
Conventional disilazane such as amide, trialkylsilyl hydroxides such as trimethylsilyl hydroxide, triethylsilyl hydroxide, triisopropylsilyl hydroxide, tert-butyldimethylsilyl hydroxide and phenethyldimethylsilyl hydroxide, and peralkylpolysiloxy polyol Polysilanols, bis (methyldichlorosilyl) methane, 1,
Bissilyls such as 2-bis (methyldichlorosilyl) ethane, bis (methyldichlorosilyl) octane, bis (triethoxysilyl) ethane, dimethylchlorosilane,
Examples include silanes having a hydride such as (N, N-dimethylamino) dimethylsilane and diisobutylchlorosilane. As the component (c), one type may be used from among these, but in some cases, two or more types may be arbitrarily combined and used. (D) Organometallic compounds of Groups 1, 2, 13 or 14 of the Periodic Table In the present invention, if necessary, the component (d) may be a Group 1 of the Periodic Table, a Group 2 or a Group 2 of the Periodic Table. A Group 13 or Group 14 organometallic compound is used. The first group of the periodic table, the second
There are various types of organometallic compounds belonging to the Group 13, Group 13 or Group 14, for example, the general formula [6]

[0038]

Embedded image

[Wherein R ⁹ and R ¹⁰ each have 1 carbon atom.
And X represents a hydrogen atom or a halogen atom. Also, m is 0 <m ≦ 3, and n is 0 ≦ n
<3. And the alkyl group-containing aluminum compound represented by the formula: Among the alkyl groups having 1 to 8 carbon atoms represented by R ⁹ and R ¹⁰ in the general formula [6], an alkyl group having 1 to 4 carbon atoms is preferable, and the value of m is preferably 2 or 3, Most preferred is 3
It is. Further, the value of n in the same expression is preferably 0 or 1.

The general formula [7]

[0041]

Embedded image

[0042] [wherein, R in R ⁹ is the formula (6) ⁹
Has the same meaning as An alkyl group-containing magnesium compound represented by the general formula [8]:

[0043]

Embedded image

[0044] [wherein, R in R ⁹ is the formula (6) ⁹
Has the same meaning as And the like. Alkyl group-containing zinc compounds represented by the formula: Specific examples of the organometallic compounds belonging to Group 1, Group 2, Group 13 or Group 14 of the periodic table include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, triisopropylaluminum. Trialkylaluminums such as n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and di-t-butylaluminum chloride; and dialkylaluminum methoxide and dimethylaluminum ethoxide. Le Kill aluminum alkoxide, dimethyl aluminum hydride, diethyl aluminum hydride,
And dialkylaluminum hydrides such as diisobutylaluminum hydride. Further, dialkylmagnesium such as dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium and butylethylmagnesium and dialkylzinc such as dimethylzinc, diethylzinc, ethyl-n-propylzinc and diisopropylzinc are used. Can be mentioned. Among these compounds, trialkylaluminum and dialkylaluminum monohalide are preferably used.

The component (d) has the following general formula:

A linear alumoxane represented by [9], a cyclic alumoxane represented by the following general formula [10], and a mixture thereof can be used.

[0046]

Embedded image

[Wherein, R ¹¹ is a group having 1 to 20 carbon atoms.
Denotes an alkyl group, which may be the same or different. L is an integer of 2 to 40, and N is an integer of 1 to 50. ] The above formula

Carbon number 1 represented by R ¹¹ in [9] and [10]
The alkyl group having 20 to 20 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, various butyl groups and the like.
L in the formula is preferably 2 to 30. Specific examples of these alumoxanes include methylalumoxane, ethylalumoxane, isobutylalumoxane, and the like.

Next, as for the method of contacting the component (d) with another catalyst component, the catalyst is prepared by treating the transition metal compound of the component (a) or the silane compound-treated clay of the component (b). Prior to this, a contact treatment can be performed in advance.
As described above, by performing the treatment with the component (d) in advance, the polymerization activity of the obtained olefin polymerization catalyst can be improved. Further, after the contact treatment of both the components (a) and (b), the contact treatment with the component (d) may be performed. Further, when a polymerization operation of an olefin is performed using a catalyst prepared by contacting the component (d) or a catalyst prepared without contacting the component (d), the polymerization reactor contains ( The contact treatment may be performed by adding the component (d). As described above, when the component (d) is added to the polymerization reactor, the effect of impurities present in the polymerization system and inhibiting olefin polymerization can be reduced.

2. Catalyst Preparation Method In the present invention, in order to produce a silane compound-treated viscosity that gives characteristic absorption to a specific region in an infrared absorption spectrum used for preparing a catalyst component, clays are intercalated with tertiary ammonium hydrochloride. The obtained layered compound may be treated with a silane compound, or the hydrogen-type clay obtained by previously performing an acid treatment may be treated with a silane compound. As described above, the clay treated with the silane compound has an absorption peak in the infrared absorption spectrum of 1090.
~1050cm ^-1 region or 1015~995cm ^-1
By preparing a catalyst for olefin polymerization using a substance which is expressed in the above region, a high polymerization activity can be obtained.

In order to prepare such a silane compound-treated clay, first, the clay as the component (b) is added to water,
An aqueous colloidal solution of clays is prepared. Next, the silane compound of the component (c) is added to the aqueous clay colloid solution thus prepared, and the mixture is heated and stirred, whereby the clay is treated with the silane compound. The temperature at which this treatment is performed can be carried out at -30 to 100 ° C, but it is preferable to carry out the treatment at a temperature near 100 ° C in order to shorten the catalyst preparation time. And this processing time is
It is not limited depending on the type of clay used and the processing temperature, but may be 0.5 to 24 hours.

When the catalyst for olefin polymerization of the present invention is produced, the clay is treated with the silane compound of the component (c), preferably the silane compound represented by the general formula [1]. Accordingly, the absorption peak at the infrared absorption spectrum, the region of 1090～1050Cm ^-1, preferably be obtained region of 1090～1060Cm ^-1, or a silane compound of a clay which is expressed in the region of 1015～995Cm ^-1 . Depending on the type of the silane compound when the clays are treated with these silane compounds, for example, when a compound having a methyl group or an ethyl group is used as the silane compound, 1090 to 1
An area of 050cm ^-1, it is possible to obtain a silane compound of a clay expressing an absorption peak in both the region of 1015~995cm ^-1.

The absorption peak of the infrared absorption spectrum observed in the silane compound-treated clay thus obtained is an absorption peak that is not observed in the raw material clays. This is a unique absorption peak that appears only in the treated product that has been subjected to contact treatment with clays using. The proportion of the silane compound of the component (c) used in the contact treatment of the clays is 0.001 to 1000, preferably 0.1 to 1,000, in terms of moles of silicon atoms per 1 kg of the weight of the clays of the component (b). 01 to 100. If the number of moles of this silane compound is 0.001 or less, the polymerization activity of the catalyst is low, and if it exceeds 1,000, the activity may be reduced again.

Thus, when the clay colloid aqueous solution is treated with the silane compound, the clay colloid aqueous solution changes into a clay slurry. The clay slurry can be obtained as a solid by adding water again, washing, filtering through a filter and drying. When the component (d) is added to the silane compound-treated clay thus obtained and used, the silane compound-treated clay 1
The number of moles of the metal atom of the component (d) per kg may be 0.1 to 1000, preferably 1 to 100. If the addition ratio is less than 0.1, the effect of improving the polymerization activity is not sufficient, and even if the amount ratio exceeds 1,000, the activity improvement corresponding thereto cannot be obtained. In this contact treatment, it is preferable to use a method in which both components are suspended or dissolved in an organic solvent, for example, pentane, hexane, heptane, toluene xylene, and mixed.

Next, when the transition metal component (a) is brought into contact with the thus-obtained silane compound-treated clay, the moles of metal atoms in the transition metal component per 1 kg of the silane compound-treated clay are used. In numbers, 0.0001-
0.5, preferably 0.001 to 0.2. If the addition ratio of the transition metal component is less than 0.0001, the effect of improving the polymerization activity is not sufficient, and if it exceeds 0.5, the polymerization activity per transition metal is reduced. . Further, upon or after the contact of each of these catalyst components, a polymer such as polyethylene, polypropylene, polystyrene, or silica,
The contact operation may be performed in the presence of an inorganic oxide solid such as alumina.

3. Production of Olefin Polymer An olefin polymer can be produced by homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst. Here, the olefin means an α-olefin, a diene, a cyclic olefin and a styrene-based compound, and the olefin-based polymer is a homopolymer or copolymer of an α-olefin and a homopolymer of a styrene-based compound. It means a polymer or a copolymer, and further a copolymer with an α-olefin and a styrene compound. Further, as the comonomer used in the production of the styrene-based copolymer, unsaturated carboxylic acids, unsaturated esters, and other various unsaturated compounds generally used as a styrene comonomer can be used. .

(1) Monomers preferably used for polymerization: ethylene, propylene, 1-butene, 1-pentene, 1
-Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene, 6-phenyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-butene , 3-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, 3,
3-dimethyl-1-pentene, 3,4-dimethyl-1-
Α-olefins such as pentene, 4,4-dimethyl-1-pentene and vinylcyclohexane, dienes such as 1,3-butadiene, 1,4-butadiene and 1,5-hexadiene, hexafluoropropene and tetrafluoroethylene , 2-fluoropropene, fluoroethylene, 1,
Halogen-substituted α-olefins such as 1-difluoroethylene, 3-fluoropropene, trifluoroethylene and 3,4-dichloro-1-butene, cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5
-Ethyl norbornene, 5-propylnorbornene,
And cyclic olefins such as 5,6-dimethylnorbornene and 5-benzylnorbornene. As the styrene monomer, in addition to styrene, p-methylstyrene,
p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, pt-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-
Alkyl such as isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, mesitylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene and 3,5-dimethylstyrene Styrenes, p-methoxystyrene,
Alkoxystyrenes such as o-methoxystyrene and m-methoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m
Halogenated styrenes such as -bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, furthermore, trimethylsilylstyrene, vinyl benzoate, divinylbenzene And the like.

(2) Polymerization conditions The polymerization reaction was carried out using butane, pentane, hexane, toluene,
The reaction is performed in the presence of a solvent such as a hydrocarbon such as cyclohexane or a liquefied α-olefin, or in the absence of a solvent. The temperature is −50 ° C. to 250 ° C., and the pressure is not particularly limited, but is preferably in the range of normal pressure to 2000 kgf / cm ² . Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

(3) Styrene-based polymer As the styrene-based polymer obtained by using the above-mentioned catalyst, a styrene-based polymer having a high degree of syndiotactic structure can be produced. In this styrenic polymer, a syndiotactic structure having a high styrene chain portion is a syndiotactic structure having a high stereochemical structure, that is, a phenyl group which is a side chain to a main chain formed from carbon-carbon bonds. And substituted phenyl groups have a steric structure alternately located in opposite directions.
The tacticity is quantified by nuclear magnetic resonance ( ¹³ C-NMR) using isotope carbon. The tacticity measured by this method is the ratio of the presence of a plurality of continuous structural units.
The number of triads can be indicated by a triad, and the number of triads can be indicated by a pentad. This styrene polymer having a syndiotactic structure is 75%
As described above, polystyrenes having a syndiotacticity of preferably 85% or more, or 30% or more, preferably 50% or more in racemic pentad, and mixtures thereof, or copolymers containing these as a main component.

[0059]

[Example 1]

(1) Preparation of Silane Compound Treated Clay A 500 ml of distilled water was placed in a 2 liter three-necked flask, and 2.5 g of Na-montmorillonite [Kunimine Kogyo Co., Ltd .;
Was slowly added. After the addition, the aqueous clay colloid solution was stirred at room temperature for 2 hours. Then, 1 ml of diethyldichlorosilane was gradually dropped into this aqueous solution of clay colloid using diethyldichlorosilane as a silane compound. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, heated to 100 ° C., and stirred at the same temperature for 4 hours. During this 4 hour stirring, the clay colloid turned into a clay slurry.

Next, distilled water 5 was added to the obtained clay slurry.
After adding 00 ml, the mixture was filtered with a pressurizer (using a membrane filter having a membrane pore of 1 μm, air pressure was 1 kg / cm ² ). The time required for the filtration was 15 minutes. Then, the obtained solid was dried at room temperature under reduced pressure for 8 hours to obtain a silane compound-treated clay A. Powder 2 of clay A treated with silane compound thus obtained
mg and potassium bromide (200 mg) were weighed, placed in an agate mortar, and crushed and mixed. Then, the obtained mixed powder was molded by a tablet molding machine, and infrared absorption spectrum analysis was performed. First measurement result (spectrum A)
Shown in the figure. Next, 2 mg of powder of Na-montmorillonite as a raw clay and 200 mg of potassium bromide were weighed, crushed, mixed and molded in the same manner as described above, and subjected to infrared absorption spectrum analysis. FIG. 2 shows the measurement results (spectrum B). Then, the spectrum A and the spectrum B were compared, and a difference between the spectrum A and the spectrum B, that is, a characteristic peak newly developed by the treatment with the above-mentioned diethyldichlorosilane was calculated. The characteristic peaks developed here were the absorption peaks at 1071 cm ^-1 and 1009 cm ^-1 . This difference spectrum C is shown in FIG.

(2) Preparation of olefin polymerization catalyst Powder 1 of silane compound-treated clay A obtained in (1) above
g was suspended in 25 ml of toluene, 25 ml of a 0.5 mol / l toluene solution of triisobutylaluminum was added, and the mixture was stirred at 100 ° C. for 1 hour. Next, the obtained slurry was washed with toluene, and fresh toluene was added to adjust the total amount to 50%.
To milliliters. Next, 5 ml of the slurry was weighed into a Schlenk tube, and 1 ml of a toluene solution having a concentration of 1 μmol / ml of dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride as a transition metal compound was added thereto. Was added and stirred at room temperature for 30 minutes to prepare an olefin polymerization catalyst.

(3) Propylene polymerization Toluene 4 was placed in an autoclave having an internal volume of 1.6 liter.
After adding 00 ml and 2.0 mmol of triisobutylaluminum and raising the temperature to 70 ° C., 6 ml of the catalyst solution obtained in the above (2) (0.
(A catalyst containing 1 g of clay). Next, after the temperature in the autoclave was raised to 70 ° C. and held for 5 minutes,
Polymerization was carried out for 30 minutes while continuously supplying propylene so that a pressure of 5 kg / cm ² could be maintained. Thereafter, the polymerization was stopped by adding methanol. The polypropylene obtained by this polymerization reaction was separated by filtration, and then dried under reduced pressure at 90 ° C. for 12 hours. The yield of polypropylene was 29.4 g. And the polymerization activity per this catalyst was 588 g / g-catalyst / hour. Also,
The polymerization activity per zirconium metal in this catalyst was 6
It was 50 kg / g-Zr / hour.

Example 2 (1) Preparation of Clay B Treated with Silane Compound The procedure of Example 1 was repeated, except that triethylchlorosilane was used in place of diethyldichlorosilane used as the silane compound in (1). A silane compound-treated clay B was prepared in the same manner as in 1 (1). The obtained silane compound-treated clay B was also subjected to infrared absorption spectrum analysis in the same manner as described above. As a result, in the clay treated with triethylchlorosilane B, 1078 cm ⁻¹ , 106
Expression of characteristic absorption peaks were observed in 5 cm ^-1 and 1003 cm ^-1. The obtained difference spectrum D is shown in FIG.

(2) Preparation of olefin polymerization catalyst An olefin polymerization catalyst was prepared in the same manner as in Example 1, (2). (3) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in (3) of Example 1, except that the catalyst for olefin polymerization prepared in (2) was used. As a result, 20.8 g of a polymer was obtained. The polymerization activity per catalyst was 417 g / g-catalyst / hour. The polymerization activity per zirconium metal in the catalyst was 458 kg / g-Zr / hour.

Example 3 (1) Preparation of Clay Treated with Silane Compound The die used as a silane compound in (1) of Example 1 was used.
Use trimethylchlorosilane instead of rudichlorosilane
Except for using silane compound in the same manner as (1) of Example 1,
Preparation of treated clay C. The silane compound obtained here
In the same way as above, infrared absorption
Spectral analysis was performed. As a result, trimethylchlor
1086 cm for clay treated with silane C^-1, 107
2cm^-1, 1005cm^-1And 997cm ^-1Characteristic absorption
The expression of a peak of yield was observed. Obtained difference spectrum E
Is shown in FIG. (2) Preparation of catalyst for olefin polymerization
The silane compound-treated clay C obtained in the above (1)
Except for using the same olefin as in Example 1 (2),
A polymerization catalyst was prepared. (3) Polymerization of propylene Other than using the olefin polymerization catalyst prepared in (2) above
Is the polymerization of propylene in the same manner as in (3) of Example 1.
went. As a result, 31.8 g of a polymer was obtained. Touch
The polymerization activity per medium is 636 g / g-catalyst / hour.
Was. Also, the weight per zirconium metal in this catalyst
The total activity was 700 kg / g-Zr / hour.

Comparative Example 1 (1) Preparation of Clay D Treated with Silane Compound The procedure of (1) in Example 1 was repeated except that tetra-n-butylsilane was used instead of diethyldichlorosilane used as the silane compound. In the same manner as in Example 1, (1), a silane compound-treated clay C was prepared. The obtained silane compound-treated clay D was also subjected to infrared absorption spectrum analysis in the same manner as described above. As a result, in clay C treated with tetra-n-butylsilane, 1090 to 1050
No characteristic absorption peak was observed in the cm ^-1 region. (2) Preparation of Catalyst for Olefin Polymerization Example 1 was repeated except that silane compound-treated clay D obtained in (1) was used instead of silane compound-treated clay A used in (2) of Example 1. An olefin polymerization catalyst was prepared in the same manner as in (2). (3) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in (3) of Example 1, except that the catalyst for olefin polymerization prepared in (2) was used. As a result, 0.6 g of a polymer was obtained. The polymerization activity per catalyst was 12 g / g-catalyst / hour. Further, the polymerization activity per zirconium metal in the catalyst was 13 kg / g-Zr / hour.

[0067]

The catalyst for olefin polymerization of the present invention can be prepared in a short period of time, and has high polymerization activity. Polyolefin can be efficiently produced.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum (A) of the diethyldichlorosilane-treated clay prepared in Example 1.

FIG. 2 is an infrared absorption spectrum (B) of Na-montmorillonite used as a raw material in Example 1.

FIG. 3 is a difference spectrum diagram between an infrared absorption spectrum A and an infrared absorption spectrum B (C).

FIG. 4 is a difference spectrum diagram (D) between the infrared absorption spectrum of the triethylchlorosilane-treated clay prepared in Example 2 and the infrared absorption spectrum of the raw clay.

FIG. 5 is a difference spectrum diagram (E) between the infrared absorption spectrum of the trimethylchlorosilane-treated clay prepared in Example 3 and the infrared absorption spectrum of the raw clay.

 ──────────────────────────────────────────────────の Continuing on the front page F term (reference) 4J028 AA01A AB00A AB01A AC01A AC05A AC07A AC10A AC24A AC25A AC28A AC45A AC46A AC47A AC48A BA00A BA00B BA01B BB00A BB00B BB01B BC05B BC09B BC18B BC20B BC01EB30 GB01B30B01C

Claims (9)

[Claims] 1. A transition metal compound having an absorption peak of 1090 to 1050 cm ⁻¹ or 10
An olefin polymerization catalyst comprising a silane compound-treated clay which appears in a region of 15 to 995 cm ^-1 . 2. The olefin polymerization catalyst according to claim 1, wherein the silane compound-treated clay is a silane compound-treated clay obtained by treating a layered silicate with a silane compound. 3. The catalyst for olefin polymerization according to claim 1, wherein the silane compound-treated clay is a silane compound-treated clay obtained by treating a mineral belonging to the smectite group or a compound having a smectite structure with a silane compound. . 4. The catalyst for olefin polymerization according to claim 1, wherein the silane compound-treated clay is a silane compound-treated clay obtained by treating montmorillonite with a silane compound. 5. A transition metal compound in which the transition metal compound has a conjugated five-membered ring as a ligand, a transition metal complex of Groups 4 to 6 of the Periodic Table, or an organic ligand bonded to the transition metal via a nitrogen atom or a phosphorus atom. The catalyst for olefin polymerization according to any one of claims 1 to 4, which is a transition metal complex of Groups 8 to 10 of the periodic table having the following formula: 6. The periodic table of the first group, the second group, and the first group of the periodic table.
The catalyst for olefin polymerization according to any one of claims 1 to 5, comprising an organometallic compound of Group 3 and Group 14. 7. A silane compound represented by the general formula [1]: [In the formula (1), R is a carbon atom, a silicon atom or a hydrogen atom at a substituent site directly bonding to a silicon atom, and X is an atom at a substituent site directly bonding to a silicon atom. A halogen atom, an oxygen atom or a nitrogen atom;
And when a plurality of Xs are present, a plurality of Rs or Xs may be the same or different. n is an integer of 2 or 3. ] Absorption peak of the infrared absorption spectrum obtained by contact treatment with the silane compound and clays represented by the 1090～1050Cm ^-1 or 1015~995cm
^A process for producing a catalyst for olefin polymerization, comprising subjecting a transition metal compound to contact treatment with a silane compound-treated clay appearing in the region of ^-1 . 8. A method for producing an olefin polymer, wherein olefin polymerization is carried out using the olefin polymerization catalyst according to claim 1. Description: 9. A method for producing an olefin polymer, wherein olefin is polymerized using the olefin polymerization catalyst obtained by the method according to claim 7.