JP2001011112A - Olefin polymerization catalyst and production of catalyst and olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin polymerization catalyst having high activity, keeping the performance of homogeneous catalyst in spite of a heterogeneous catalyst and capable of producing an olefin polymer having high bulk density and good particle form in high efficiency. SOLUTION: The objective olefin polymerization catalyst is produced by the prepolymerization of a monomer M having a polymerizable double bond in a state containing a solution of a catalyst component dispersed in a medium X essentially incapable of dissolving a transition metal compound (a) and the produced polymer. The solution of the catalyst component is produced by dissolving at least the transition metal compound (a) in a solvent Y incompatible with the medium X.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for olefin polymerization containing a transition metal compound, a method for producing the catalyst, and a method for producing an olefin polymer using the catalyst.

[0002]

2. Description of the Related Art Olefin polymers have been used in a wide variety of applications. In recent years, a homogeneous catalyst soluble in an organic solvent, for example, a homogeneous complex catalyst such as a metallocene catalyst may be used instead of a solid titanium catalyst, which is a heterogeneous catalyst for olefin polymerization, which has been used so far. As a result, a specific olefin polymer obtained from a homogeneous catalyst, for example, an olefin polymer having a uniform polymer structure such as a narrow molecular weight distribution has been synthesized. In order to apply such a homogeneous catalyst to a slurry method, a gas phase method and the like that are currently industrially performed, it is preferable that the catalyst is solidified, and loading on a carrier has been attempted.

For example, homogeneous complex catalysts such as metallocene catalysts often use metallocene together with co-catalysts such as alumoxanes or boron compounds such as borane or borate having a fluorinated aromatic ring. Since alumoxanes are relatively easily bonded and supported on the surface of a carrier such as silica, alumoxanes are supported on silica. However, when complex catalysts such as metallocenes are activated using alumoxanes supported on a solid, catalytic performance such as activity is reduced as compared to the case of a non-supported homogeneous system, and the molecular weight and stereoregularity of the produced polymer are reduced. Sex is also often reduced.

On the other hand, attempts have been made to support complex catalysts such as metallocenes, or co-catalyst borane and borates. However, these do not have a functional group chemically bonded to a carrier, and are therefore not polymerized under polymerization conditions. It is eluted in the medium, which causes remarkable deterioration of the particle properties of the produced polymer and adhesion of the amorphous polymer to the polymerization vessel wall and the like.

Attempts have also been made to introduce functional groups into complex catalysts such as metallocenes or cocatalyst borane and borates, and to carry these components by covalent bonds. In addition, the cost may be higher than the above, and the catalytic performance may be lowered due to the introduction of a functional group which is not originally related to the polymerization.

As described above, a heterogeneous catalyst (solid catalyst) which has been solidified without impairing the performance of the homogeneous catalyst has not been obtained so far. There is a demand for a highly active catalyst for olefin polymerization, which does not impair the performance of a homogeneous catalyst, has a high bulk density, and can obtain an olefin polymer having good particle properties.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and impairs the performance of a homogeneous catalyst even with a heterogeneous catalyst. It is an object of the present invention to provide a highly active olefin polymerization catalyst capable of efficiently producing an olefin polymer having a high bulk density and good particle properties without any problem. Another object of the present invention is to propose a method for producing an olefin polymerization catalyst capable of efficiently producing the olefin polymerization catalyst at low cost. Another object of the present invention is to propose a method for producing an olefin polymer which can efficiently produce an olefin polymer having a high bulk density and good particle properties by using the olefin polymerization catalyst. .

[0008]

The present invention relates to the following olefin polymerization catalyst, a method for producing the olefin polymerization catalyst, and a method for producing an olefin polymer. (1) A monomer (M) having a polymerizable double bond is prepolymerized in a state in which the catalyst component is dispersed in a medium (X) in which the transition metal compound (a) and the produced polymer are not substantially dissolved. The catalyst for olefin polymerization, wherein the catalyst component contains at least a transition metal compound (a). (2) Prepolymerizing a monomer (M) having a polymerizable double bond in a state in which a solution of a catalyst component is dispersed in a medium (X) in which a transition metal compound (a) and a produced polymer are not substantially dissolved. Wherein the solution of the catalyst component is a solution in which at least the transition metal compound (a) is dissolved in a solvent (Y) incompatible with the medium (X). . (3) The catalyst for olefin polymerization according to the above (1) or (2), wherein the transition metal compound (a) is a compound containing a transition metal belonging to Group 4 of the periodic table. (4) The catalyst component, in addition to the transition metal compound (a),
The olefin polymerization catalyst according to any one of the above (1) to (3), which comprises the organic boron compound (b) and / or the organic aluminum oxy compound (c). (5) The olefin polymer according to any one of claims 1 to 4, wherein the medium (X) in which the transition metal compound (a) and the produced polymer are not substantially dissolved is a fluorine-containing organic compound (X-1). catalyst. (6) The olefin polymerization catalyst according to any one of the above (2) to (5), wherein the solvent (Y) incompatible with the medium (X) is a hydrocarbon compound. (7) The olefin polymerization catalyst according to any one of the above (1) to (6), which is obtained by prepolymerization in the presence of a dispersion stabilizer (d). (8) A monomer (M) having a polymerizable double bond is prepolymerized in a state in which the catalyst component is dispersed in a medium (X) in which the transition metal compound (a) and the produced polymer are not substantially dissolved. A method for producing an olefin polymerization catalyst, wherein the catalyst component contains at least a transition metal compound (a). (9) A monomer (M) having a polymerizable double bond is prepolymerized in a state where a solution of a catalyst component is dispersed in a medium (X) in which a transition metal compound (a) and a produced polymer are not substantially dissolved. A solution of the catalyst component, wherein the solution of the catalyst component is a solution in which at least the transition metal compound (a) is dissolved in a solvent (Y) incompatible with the medium (X). A method for producing a polymerization catalyst. (10) A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of the above (1) to (7).

<< Transition Metal Compound (a) >> The transition metal compound (a) used as a catalyst component in the present invention is a compound of the Periodic Table Groups 3 to 12 (IUPAC Inorganic Chemical Nomenclature Revised Edition (1)
989) according to the family numbers 1 to 18),
Preferably, it is a compound containing a Group 3 to Group 10 and more preferably Group 4 transition metal atom.

The transition metal compound (a) used in the present invention
Examples include a transition metal compound represented by the following formula (1). M ¹ L ¹ x (1) (In the formula (1), M ¹ is a transition metal atom, x is a valence of the transition metal atom M ¹ , and L ¹ is a ligand coordinated to the transition metal atom. )

In the above formula (1), specific examples of the transition metal atom represented by M ¹ include transition metal atoms of Group 4 of the periodic table such as zirconium, titanium and hafnium. Of these, zirconium is preferred.
In the formula (1), x is the valence of the transition metal atom M ^1, illustrating a coordinated number of ligands L ¹ to the transition metal atom M ^1.

In the above formula (1), L ¹ represents a ligand which coordinates to the transition metal atom M ¹ , and at least one L ¹ is a ligand having a cyclopentadienyl skeleton; L ¹ other than the ligand having a dienyl skeleton has ¹ carbon atom.
-20 hydrocarbon groups, halogenated hydrocarbon groups having 1-20 carbon atoms, oxygen-containing groups, sulfur-containing groups, silicon-containing groups, halogen atoms or hydrogen atoms.

Examples of the ligand having a cyclopentadienyl skeleton in L ¹ include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethyl Cyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group And alkyl-substituted cyclopentadienyl groups such as methylbutylcyclopentadienyl group and hexylcyclopentadienyl group, or indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group and the like. it can. These groups may be substituted with a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom, or the like.

The transition metal compound (a) represented by the formula (1) is a ligand L ¹ having a cyclopentadienyl skeleton.
When two or more ligands having two or more cyclopentadienyl skeletons are bonded to each other via a divalent bonding group such as an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group, May be. Two ligands having such a cyclopentadienyl skeleton are represented by 2
Examples of the transition metal compound (a) bonded via a valent bonding group include a transition metal compound (a) represented by the following formula (2).

In the transition metal compound (a) represented by the formula (1), specific examples of the transition metal compound in which the transition metal atom M ¹ is zirconium are shown below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl)
Methyl zirconium monochloride, bis (cyclopentadienyl) zirconium phenoxymonochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, Bis (butylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (octylcyclopentadienyl) zirconium dichloride,
Bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (methyl Butylcyclopentadienyl) zirconium dichloride, bis (methylhexylcyclopentadienyl) zirconium dichloride, bis (ethylbutylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopenta Dienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylbenzylcyclopentadienyl) dichloride Benzalkonium dichloride, bis (ethylhexyl cyclopentadienyl) zirconium dichloride, bis (methylcyclohexyl cyclopentadienyl) zirconium dichloride, bis (trimethylsilyl cyclopentadienyl) zirconium dichloride and the like.

In the transition metal compounds exemplified above,
Disubstituted cyclopentadienyl rings include 1,2- and 1,3-substituted, and tri-substituted include 1,2,3- and 1,2,4-substituted. Alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-. Further, in the above transition metal compounds, compounds in which zirconium is replaced by titanium or hafnium can also be mentioned.

In the transition metal compound (a) represented by the formula (1), a compound having a cyclopentadienyl skeleton
Examples of the bridge type transition metal compound (a) in which two ligands are bonded via a divalent bonding group include a compound represented by the following formula (2).

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In the formula (2), M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, preferably zirconium. R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and may be a hydrocarbon group having 1 to 20 carbon atoms;
-20, a halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom. R ¹ , R ² , R ³ and R ⁴
In the groups represented by, a part of the groups adjacent to each other may be bonded to form a ring together with the carbon atoms to which those groups are bonded. When a ring is formed, a condensed ring is formed. In addition, R ¹ , R ² , R ³ and R ⁴ are respectively shown at two places. For example, R ¹ and R ¹ may be the same group or different groups. Among the groups represented by R, those having the same suffix represent a preferable combination when forming a ring by inheriting them.

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{1 to} R ⁴ in the above formula (2) include:
Examples include the same alkyl group, cycloalkyl group, alkenyl group, arylalkyl group, and aryl group as L ¹ in the formula (1). The ring formed by combining the hydrocarbon groups represented by R ^{1 to} R ⁴ includes a benzene ring; a condensed ring such as a naphthalene ring, an acenaphthene ring, and an indene ring. These rings may be substituted with an alkyl group such as methyl, ethyl, propyl, butyl and the like.

In the formula (2), examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{1 to} R ⁴ include groups in which the hydrocarbon group having 1 to 20 carbon atoms is substituted by halogen. Can be Specific examples of the silicon-containing group represented by R ^{1 to} R ⁴ in the formula (2) include the formula (1)
The same mono-hydrocarbon-substituted silyl and L ¹ in, di-hydrocarbon-substituted silyl, tri hydrocarbon-substituted silyl, silyl ethers of hydrocarbon-substituted silyl, a silicon-substituted alkyl groups, such as silicon-substituted aryl group.

Specific examples of the oxygen-containing group represented by R ^{1 to} R ⁴ in the formula (2) include the same hydroxy group, alkoxy group, aryloxy group and arylalkoxy group as L ¹ in the formula (1). And so on. In the formula (2), examples of the sulfur-containing group represented by R ^{1 to} R ⁴ include a substituent in which oxygen of the oxygen-containing group is substituted with sulfur.

In the formula (2), the nitrogen-containing group represented by R ^{1 to} R ⁴ is an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; And an arylamino group or an alkylarylamino group such as diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino.

In the formula (2), examples of the phosphorus-containing groups represented by R ^{1 to} R ⁴ include phosphino groups such as dimethylphosphino and diphenylphosphino. In the formula (2), examples of the halogen atom represented by R ^{1 to} R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among the groups represented by R ^{1 to} R ⁴ in the above formula (2), a hydrocarbon group having 1 to 20 carbon atoms is preferable, and particularly a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl is preferred. A benzene ring formed by combining hydrocarbon groups, a hydrogen atom on a benzene ring formed by combining hydrocarbon groups is methyl, ethyl, n-propyl, i
so-propyl, n-butyl, iso-butyl, ter
It is preferably a group substituted with an alkyl group such as t-butyl.

In the above formula (2), X ¹ or X ² may be the same or different from each other, and may be a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group. , A sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom.

In the formula (2), the hydrocarbon group having 1 to 20 carbon atoms, the halogenated hydrocarbon group having 1 to 20 carbon atoms, the oxygen-containing group and the halogen atom represented by X ¹ or X ² include ^The same groups and atoms as ^{1 to} R ⁴ can be mentioned.

In the above formula (2), X¹Or X^TwoIndicated by
Examples of the sulfur-containing group include: ¹~ R^FourSame group as
Rabi ni methyl sulfonate, trifluoromethane sulf
Phonate, phenyl sulfonate, benzyl sulf
, P-toluenesulfonate, trimethylbenzene
Benzene sulfonate, triisobutylbenzene sulf
, P-chlorobenzenesulfonate, pentane
Sulfonates such as fluorobenzenesulfonates
Groups: methyl sulfinate, phenyl sulfinate,
Benzene sulfinate, p-toluene sulfinate
G, trimethylbenzenesulfinate, pentafluo
Sulfinate groups such as robenzenesulfinate
Can be illustrated.

In the above formula (2), X¹Or X^TwoIndicated by
Examples of the silicon-containing group include: ¹~ R^FourSame as silicon
Substituted alkyl group, silicon-substituted aryl group, etc.
You. In the above formula (2), X¹Or X^TwoOf the group represented by
Among them, halogen atoms and hydrocarbon groups having 1 to 20 carbon atoms
Or a sulfonate group.

In the above formula (2), Y ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, or a divalent hydrocarbon group. Germanium-containing group, divalent tin-containing group, -O-, -CO-, -S
-, - SO -, - SO 2 -, - Ge -, - Sn -, - N
^{R 5 -, - P (R} 5) -, - P (O) (R 5) -, - BR 5 - or -AlR ⁵ - [however, R ⁵ may be the same or different, said R ¹ hydrocarbon group having the same carbon number of 1 to 20 and to R ^4, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom].

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by Y ¹ in the above formula (2) include methylene, dimethylmethylene, 1,2-ethylene,
Dimethyl-1,2-ethylene, 1,3-trimethylene,
1,4-tetramethylene, 1,2-cyclohexylene,
Alkylene groups such as 1,4-cyclohexylene; arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene; In the formula (2), the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by Y ¹ may be a group obtained by halogenating the divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. And the like.

In the above formula (2), the divalent silicon-containing group represented by Y ¹ includes silylene, methylsilylene,
Dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-
Alkylsilylene groups such as chlorophenyl) silylene;
Alkylarylsilylene group; arylsilylene group; tetramethyl-1,2-disilylene, tetraphenyl-
Alkyldisilylene groups such as 1,2-disilylene; alkylaryldisilylene groups; aryldisilylene groups and the like. Examples of the divalent germanium-containing group represented by Y ¹ in the formula (2) include a group in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium.

Examples of the divalent tin-containing group represented by Y ¹ in the formula (2) include a group in which silicon of the divalent silicon-containing group is substituted with tin. Among the groups represented by Y ¹ in the above formula (2), dimethylsilylene,
Substituted silylene groups such as diphenylsilylene or methylphenylsilylene are particularly preferred.

Specific examples of the transition metal compound (a) represented by the formula (2) are shown below. Ethylene-bis (indenyl) dimethyl zirconium, ethylene-bis (indenyl) zirconium dichloride, ethylene-
Bis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylene-bis (indenyl) zirconiumbis (methanesulfonato), ethylene-bis (indenyl) zirconiumbis (p-toluenesulfonato), ethylene-bis (indenyl) zirconium Bis (p-chlorobenzenesulfonato), ethylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) ) (Methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (methylcyclopentadienyl) zirco Dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium bis (Trifluoromethanesulfonato), dimethylsilylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

Diphenylsilylene-bis (indenyl)
Zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl Cyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-tert-butylcyclopentadienyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3
-Tert-butylcyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (4-
Methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (4-
tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (4-tert-butylcyclopentadienyl) (3
-Tert-butylindenyl) zirconium dichloride, dimethylsilylene (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (4-tert-butylcyclopentadienyl) (3-methylindenyl ) Zirconium dichloride, dimethylsilylene (4-tert-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene (3
-Tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3
-Tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride,

Rac-dimethylsilylene-bis @ 1-
(2-methyl-4-phenylindenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-methyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene- Bis {1- (2-methyl-4- (1-anthryl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4- (2
-Anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-methyl-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-fluorophenyl) indenyl)｝ zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-methyl-4-)
(Pentafluorophenyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-methyl-4- (p-chlorophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-methyl-4-)
(O-chlorophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-Methyl-4- (o, p-dichlorophenyl) phenylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride, rac- Dimethylsilylene-bis {1- (2-methyl-4- (p-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-Methyl-4- (m-tolyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-methyl-4- (o-tolyl) indenyl)} zirconium dichloride and the like.

Further, there may be mentioned compounds in which zirconium in the above transition metal compound is replaced with titanium or hafnium. In the present invention, when polymerizing an olefin having 3 or more carbon atoms, a racemate of the transition metal compound (a) represented by the formula (2) is preferably used as a catalyst component.

In the present invention, a compound represented by the following formula (3) can be used as the transition metal compound (a). _{^{L 1 M 1 X 1 2 ...}} (3) Equation (3), M ¹ is shown a periodic table group IV transition metal atom.

In the above formula (3), L ¹ is a derivative of a delocalized π-bonded group, and imparts a constrained geometry to the metal M ¹ active site. In the above formula (3), X ¹ is They may be the same or different and are a hydrogen atom, a halogen atom, or a hydrocarbon group containing up to 20 carbon atoms, silicon atoms or germanium atoms, a silyl group or a germyl group.

Among the transition metal compounds (a) represented by the above formula (3), a transition metal compound represented by the following formula (4) is preferable.

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In the formula (4), M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, preferably titanium. In the above formula (4), Cp is π-bonded to M ¹ and the substituent Z
And a substituted cyclopentadienyl group having the formula:

In the above formula (4), Z is an oxygen atom,
Coordination involving an atom, a boron atom or an atom of group 14 of the periodic table
Indicates a child. Specifically, -Si (R¹ _Two) −, −
C (R¹ _Two)-, -Si (R¹ _Two) Si (R¹ _Two)-, -C (R¹ _Two) C
(R¹ _Two)-, -C (R¹ _Two) C (R ¹ _Two) C (R¹ _Two)-, -C (R¹)
= C (R¹)-, -C (R¹ _Two) Si (R¹ _Two)-, -Ge (R¹ _Two)
-And the like.

In the above formula (4), Y ¹ represents a ligand containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom. Specific ^{ones, -N (R 2) -,} - O -, - S-,
—P (R ² ) — and the like. In the formula (4), Z and Y ¹ may form a condensed ring.

R ¹ is a group selected from a hydrogen atom or an alkyl group having up to 20 non-hydrogen atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group, and combinations thereof. ² has 1 to 1 carbon atoms
An alkyl group of 10 or an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, or forming a condensed ring system of one or more R ¹ and up to 30 non-hydrogen atoms Is also good. In the formula (4), X ¹ is the same as X ^{1 in the} formula (3).

Hereinafter, specific examples of the transition metal compound (a) represented by the above formula (4) will be exemplified. (Tert-
Butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (tert-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl titanium dichloride , (methylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide) (tetramethyl-eta ⁵ -
(Cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -methylenetitanium dichloride, (t
tert-butylamido) dimethyl (tetramethyl-η ⁵
-Cyclopentadienyl) silane titanium dichloride,
(tert-butylamido) dimethyl (tetramethyl-
eta ⁵ - cyclopentadienyl) silane zirconium dichloride, (benzylamide) dimethyl - (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dichloride, (phenyl phosphide) dimethyl (tetramethyl -
such as cyclopentadienyl) silane zirconium dibenzyl - eta ^5.

In the present invention, the transition metal compound (a)
A transition metal imide compound represented by the following formula (5) can also be preferably used.

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In the formula (5), M represents a transition metal atom belonging to Groups 8 to 10 of the periodic table, and is preferably nickel, palladium or platinum. In the formula (5), R ^{1 to} R ⁴ may be the same or different from each other, and may be a hydrocarbon group having 1 to 50 carbon atoms;
It represents a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or a hydrocarbon group substituted with a substituent containing at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon. In the groups represented by R ^{1 to} R ⁴ , two or more of these groups, preferably adjacent groups, may be connected to each other to form a ring. In the formula (5), q represents an integer of 0 to 4.

In the above formula (5), X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
20 represents a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group, and when q is 2 or more, even if a plurality of groups represented by X are the same, May be different.

In the present invention, the transition metal compound (a)
A transition metal amide compound represented by the following formula (6) can also be preferably used.

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In the formula (6), M represents a transition metal atom belonging to Groups 3 to 6 of the periodic table, and is preferably titanium, zirconium or hafnium. In the formula (6), R ¹ and R ² may be the same or different from each other, and represent a hydrogen atom,
A hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or nitrogen,
It indicates a substituent having at least one element selected from oxygen, sulfur and silicon.

In the above formula (6), m is an integer of 0 to 2, and n is an integer of 1 to 5. In the above formula (6), A represents an atom belonging to Groups 13 to 16 of the periodic table, and specifically, boron,
Examples include carbon, nitrogen, oxygen, silicon, sulfur, germanium, selenium, tin and the like, and carbon or silicon is preferable. When n is 2 or more, a plurality of A may be the same or different from each other.

In the above formula (6), E is carbon, hydrogen, oxygen,
It is a substituent having at least one element selected from halogen, nitrogen, sulfur, phosphorus, boric acid and silicon.
When m is 2, two Es may be the same or different from each other, or may be linked to each other to form a ring.

In the above formula (6), q is an integer of 0-4. In the formula (6), X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, or nitrogen. Shows the contained groups. When q is 2 or more, a plurality of groups represented by X may be the same or different. In the formula (6), X is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group.

In the present invention, the transition metal compound (a)
Can be used alone or in combination of two or more.

<< Organic boron compound (b) and / or organoaluminum oxy compound (c) >> In the present invention, in addition to the transition metal compound (a), an organoboron compound (b) and / or an organoaluminum oxy compound as a catalyst component (C) can also be used. In particular, it is preferable to use the organic boron compound (b). Organoboron compound (b) and organoaluminum oxy compound (c)
Can use both or only one of them.

The organic boron compound (b) and the organic aluminum oxy compound (c) are preferably used in a state of being dissolved in the solvent (Y) together with the transition metal compound (a). It is preferable that the organic boron compound (b) and the organic aluminum oxy compound (c) do not dissolve in the medium (X).

Examples of the organic boron compound (b) used in the present invention include JP-A-1-501950, JP-A-1-502046, JP-A-3-179005, JP-A-3-179006, Kaihei 3-20
JP 7703, JP-A-3-207704, US
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in P-5321106. Such an organic boron compound (b) is
It is a compound which forms an ion pair by reacting with the transition metal compound (a).

As the Lewis acid used as the organic boron compound (b), BR ₃ (where R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group or fluorine) )). Specific examples of Lewis acids include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris {3,5-di (trifluoromethyl) phenyl} boron, and tris {3,5-di (Trifluoromethyl) -2,4,6-trifluorophenyl} boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p -Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound used as the organic boron compound (b) include a compound represented by the following formula (7).

Embedded image

In the formula (7), examples of R ¹ include H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

In the above formula (7), R ^{2 to} R ⁵ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation represented by R ¹ in the formula (7) include triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation. And carbonium cations.

Specific examples of the ammonium cation represented by R ¹ in the formula (7) include a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, a tributylammonium cation, and a tri (n-butyl) ammonium cation. Trialkylammonium cations such as;
N, N-dialkylanilinium cations such as N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; di (isopropyl) ammonium cation And dialkylammonium cations such as dicyclohexylammonium cation.

Specific examples of the phosphonium cation represented by R ¹ in the above formula (7) include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Cations and the like.

In the above formula (7), R ¹ is preferably a carbonium cation, an ammonium cation, or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation. .

Examples of the ionic compound used as the organic boron compound (b) include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt used as the ionic compound include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, and tri (n-
Butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o , P-dimethylphenyl) boron, tri (n-butyl) ammoniumtetra (m, m-dimethylphenyl)
Boron, tri (n-butyl) ammonium tetra (p-
Trifluoromethylphenyl) boron, tri (n-butyl) ammoniumtetra (3,5-ditrifluoromethylphenyl) boron, tri (n-butyl) ammoniumtetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt used as the ionic compound include N, N
-Dimethylanilinium tetra (phenyl) boron,
N, N-diethylaniliniumtetra (phenyl) boron, N, N-2,4,6-pentamethylaniliniumtetra (phenyl) boron and the like can be mentioned. Specific examples of the dialkylammonium salt used as the ionic compound include di (1-propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron, and the like.

Further, ionic compounds used as the organic boron compound (b) include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis {3,5-di (trifluoromethyl) phenyl} borate Triphenylcarbenium tetrakis {3,5-di (trifluoromethyl) -2,4,6-trifluorophenyl} borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis {3,5-di (trifluoromethyl) phenyl} borate, N, N-dimethylanilinium tetrakis 3,5 -Di (trifluoromethyl) -2,4,6
-Trifluorophenyl diborate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, the following formula (8) Or a boron compound represented by the formula (9).

[0068]

Embedded image (In the formula (8), Et is -CH ₂ CH _3.)

Specific examples of the borane compound used as the organic boron compound (b) include decaborane (1
4); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium Salts of anions such as dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate and bis [tri (n-butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride Metal borane anion salts such as (dodecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III).

Specific examples of the carborane compound used as the organic boron compound (b) include 4-carbanonaborane (14) and 1,3-dicarbanonaborane (1
3), 6,9-dicarbadecaborane (14), dodeca hydride-1-phenyl-1,3-dicarbanona borane, dodeca hydride-1-methyl-1,3-dicarbanona borane, undeca hydride -1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,7-dicarboundecaborane (13), undecahydride-7,8-dimethyl- 7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane,
Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1
-Trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carba Decaborate (12), tri (n-butyl) ammonium 7-carboundecaborate (1
3), tri (n-butyl) ammonium 7,8-dicarboundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-
8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8
-Ethyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8
-Butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8
-Allyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9
Salts of anions such as -trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-4,6-dibromo-7-carboundecaborate; tri (n-butyl) ammoniumbis ( Nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (III), tri ( n-butyl) ammonium bis (undecahydride-7,8
-Dicarboundecaborate) cobaltate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ) Cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (III), tri (n-butyl)
Ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (II
I), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl)
Ammonium bis (tribromooctahydride-
7,8-dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7) -Carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (II
And salts of metal carborane anions such as I) and bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV).

The organic boron compound (b) can be used alone or in combination of two or more.

The organoaluminum oxy compound (c) used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687. You may.

The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate,
An organic aluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, and adsorbed water or water of crystallization is added to the organic aluminum. A method of reacting with a compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane obtained by the above method is
It may contain a small amount of an organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in a solvent or suspended in a poor aluminoxane solvent.

As the organoaluminum compound used in preparing the aluminoxane, the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the organometallic compound (e) described later can be mentioned. As the organoaluminum compound used for preparing the aluminoxane, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. In preparing the aluminoxane, the organoaluminum compound can be used alone or in combination of two or more.

Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products can be mentioned. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these, an aromatic hydrocarbon or an aliphatic hydrocarbon is preferred.

The benzene-insoluble organoaluminum oxy compound used as the organoaluminum oxy compound (c) is such that the Al component soluble in benzene at 60 ° C. is usually 10% by weight or less, preferably 5% by weight or less in terms of Al atom.
It is particularly preferably at most 2% by weight and is insoluble or hardly soluble in benzene.

<< Dispersion Stabilizer (d) >> In the present invention, the prepolymerization can be carried out in the presence of the dispersion stabilizer (d). As the dispersion stabilizer (d), a state in which a catalyst component, a solution of the catalyst component, a monomer (M) having a polymerizable double bond, a produced polymer, and the like are stably dispersed in the medium (X) is used. Anything that can be kept can be used. Examples of such a dispersion stabilizer (d) include a surfactant. Examples of the surfactant include a compound having an affinity group for each of the medium (X) and the solvent (Y). The surfactant is used for the medium (X), the solvent (Y), the catalyst component, the monomer (M), and the like. It can be arbitrarily selected depending on the situation. By using the dispersion stabilizer (d), an olefin polymerization catalyst having excellent particle properties can be obtained.

Specific examples of the dispersion stabilizer (d) include the fourth compound of the periodic table having a fluorocarbon chain and a hydrocarbon chain.
And a Group 13 or Group 13 alkoxy compound. For example, an alkoxy metal compound of zirconium or aluminum can be mentioned.

The dispersion stabilizer (d) includes, for example, the following (d-
1) The components (d-2) and (d-3) are mixed by heating.
It can be produced by removing the generated low-boiling alcohol. (D-1): an alkoxy metal compound of Group 4 of the periodic table such as tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium or trimethoxyaluminum;
Group 13 alkoxy metal compounds such as triethoxyaluminum, triisopropoxyaluminum and tributoxyaluminum. (D-2): 1H, 1H, 2H, 2H- perfluorooctyl alcohol, 1H, 1H, 2H, 2H- perfluoro decyl alcohol, 1H, 1H, 2H, 2H- perfluoro fluorine-containing alcohols or C ₆ F dodecyl alcohol ₁₃ COOH, C ₇ F ₁₅ COOH, C ₈ F ₁₇ C
Fluorine-containing carboxylic acids such as OOH and C ₉ F ₁₉ COOH. (D-3): octyl alcohol, decyl alcohol,
Alcohols such as dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol and oleyl alcohol.

<< Organometallic Compound (e) >> In the present invention, the organometallic compound (e) can be added to the medium (X) and / or the solvent (Y) as required during the prepolymerization. . By adding the organometallic compound (e), a stable prepolymerization activity can be obtained. Specific examples of the organometallic compound (e) used as necessary in the present invention include the following organometallic compounds belonging to Groups 1, 2 and 12, and 13 of the periodic table.

(E-1) Formula: R ¹ mAl (OR ² ) n HpXq (wherein, R ¹ and R ² may be the same or different from each other and have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). X represents a halogen atom, m represents 0 <m ≦ 3, n
Is a number satisfying 0 ≦ n <3, p is a number satisfying 0 ≦ p <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0083] (e-2) formula: M ¹ AlR ¹ ₄ (wherein, M ¹ is shown a Li, Na or K, R ¹ having 1 to 15 carbon atoms, preferably a 1-4 hydrocarbon group Complex alkylated product of a Group 1 metal and aluminum.

(E-3) Formula: R ¹ R ² M ¹ (wherein R ¹ and R ² may be the same or different from each other and are a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) Wherein M ¹ is Mg, Zn or Cd.) A dialkyl compound of a Group 2 or Group 12 metal represented by the formula:

As the organoaluminum compound belonging to the above (e-1), the following compounds can be exemplified. R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² may be the same or different and each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and m is Preferably, the number is 1.5 ≦ m ≦ 3.)
An organoaluminum compound represented by the formula: R ¹ _m AlX _3-m (wherein, R ¹ represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m preferably represents 0 <m <3. )). R ¹ _m AlH _3-m (wherein, R ¹ represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m preferably satisfies 2 ≦ m <3.)
An organoaluminum compound represented by the formula: R ¹ _m Al (OR ² ) _n X _q (wherein, R ¹ and R ² may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; Represents a halogen atom, and m is 0 <m ≦ 3, n
Is 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n
+ Q = 3. The organoaluminum compound represented by).

More specifically, the organoaluminum compounds belonging to (e-1) include trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trioctylaluminum, Tri-n-alkylaluminum such as decylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-
Methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexyl Tribranched alkyl aluminum such as aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride and diisobutyl aluminum hydride; _{(i-C 4 H 9)} xAly (C 5 H 10) z ( wherein, x,
y and z are positive numbers and z ≧ 2x. Trialkenyl aluminum such as triisoprenyl aluminum; dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride; ethyl aluminum sesquichloride, butyl aluminum sesquichloride Aluminum aluminum sesquihalides such as ethyl aluminum sesquibromide; partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; diethyl aluminum hydride, dibutyl aluminum hydride and the like Dialkyl al Niumuhidorido; ethylaluminum dihydride, propyl aluminum dihydride alkylaluminum dihydride and other partially alkyl aluminum or the like which is hydrogenation and the like.

A compound similar to the above (e-1) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. As such a compound, specifically, (C
Such as _{2 H 5) 2 AlN (C} 2 H 5) Al (C 2 H 5) 2 and the like.

The compounds belonging to the above (e-2) include:
Such as _{LiAl (C 2 H 5) 4} , LiAl (C 7 H 15) 4 and the like. In addition, as the organometallic compound (e), methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, Butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can be used.

Further, a compound capable of forming the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium may be used.

<< Monomer Having a Polymerizable Double Bond (M) >> As the monomer (M) having a polymerizable double bond used in the present invention, a compound which can be polymerized to form a polymer is used. Although it can be used without limitation, α-olefins, polar group-containing compounds, aromatic vinyl compounds and polyene compounds are preferred. Of these, α-olefins are particularly preferred. The monomer (M) having a polymerizable double bond can be used alone, or
Two or more kinds can be used in combination. The monomer (M) used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

Specific examples of the α-olefin used as the monomer (M) having a polymerizable double bond include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, Carbon number 2 such as hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene ~ 20, preferably 3-8 chain α
-Olefin; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-
Examples thereof include cyclic olefins having 3 to 20 carbon atoms, preferably 5 to 12 carbon atoms, such as 1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

Specific examples of the polar group-containing compound used as the monomer (M) having a polymerizable double bond include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo. [2.2.1] α, β-unsaturated carboxylic acids such as -5-heptene-2,3-dicarboxylic acid, and their sodium, potassium, lithium, zinc, magnesium, and calcium salts Metal salts of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacrylic acid Ethyl, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate Α, β-unsaturated carboxylic esters such as -butyl, isobutyl methacrylate;
Vinyl acetate, vinyl propionate, vinyl caproate,
Vinyl esters such as vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate,
Unsaturated glycidyl such as itaconic acid monoglycidyl ester;

Specific examples of the aromatic vinyl compound used as the monomer (M) having a polymerizable double bond include styrene. Examples of the polyene compound used as the monomer (M) having a polymerizable double bond include non-conjugated dienes and polyenes. Specific examples thereof include butadiene, isoprene,
1,4-pentadiene, 1,4-hexadiene, 1,5
-Hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene -8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8, -decatriene,
And divinylbenzene.

<< Medium (X) in which the transition metal compound (a) and the produced polymer are not substantially dissolved >> In the present invention, the medium (X) used in the prepolymerization is the same as the transition metal compound (a) and the prepolymer. A medium in which the polymer produced by the polymerization is not substantially dissolved can be used without limitation. Here, "the transition metal compound (a) is not substantially dissolved" is defined as follows.

That is, first, the transition metal compound (a) used in the prepolymerization is dissolved in an organic solvent such as toluene so as to have a concentration of 0.3 mg-transition metal / ml. This organic solvent solution (for example, a toluene solution) and the medium (X) used in the prepolymerization are mixed at a volume ratio of 1: 1 and stirred for 10 minutes at the same temperature as the temperature at which the prepolymerization is performed. Next, the mixture is allowed to stand for 10 minutes while maintaining the same temperature as the temperature at which the prepolymerization is performed. Thereafter, a part of the medium (X) used in the prepolymerization or the phase mainly containing the medium (X) used in the prepolymerization is sampled. The transition metal concentration of this sample is measured by ICP (high frequency inductively coupled plasma) emission spectroscopy. As a result, the concentration of the transition metal derived from the transition metal compound (a) was 0.001 mg / ml.
The medium (X) is defined as "substantially insoluble" if:

In the case of the medium (X) determined to be “substantially insoluble” in the above method, a mixture of the medium (X) and an organic solvent solution in which the transition metal compound (a) is dissolved is usually suspended. It becomes cloudy and does not become a homogeneous solution. In addition, simply, it can be estimated that "substantially does not dissolve" because no coloring is visually observed in the sample obtained by performing the above operation.

[0097] The expression "the produced polymer does not substantially dissolve" is defined as follows. That is, after pre-polymerization is performed, solid-liquid separation is performed at the pre-polymerization temperature, and the medium (X) is withdrawn as a sample from the liquid phase. This sample was subjected to a pressure reduction at 150 ° C. under a reduced pressure of 100 mmHg or less.
After distilling off the medium (X) over 2 hours, the amount of the polymer contained in the solid is measured. As a result, when the content of the polymer is 0.1 mg / ml or less, it is defined as "the produced polymer is not substantially dissolved".

In the present invention, the medium (X) used in the prepolymerization is preferably a medium in which the catalyst component other than the transition metal compound (a) and the monomer (M) are not dissolved. Specific examples include a fluorine-containing organic compound (X-1)
Is preferred. Examples of the fluorine-containing organic compound (X-1) include a fluorine-containing organic compound in which part or all of the hydrogen of an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon is substituted with fluorine.

Fluorine-containing organic compound (X-1) in which some or all of the hydrogens of the aliphatic hydrocarbon have been replaced by fluorine
Specific preferred examples include aliphatic fluorine-containing organic compounds having 2 to 20 carbon atoms, such as perfluorohexane, perfluoroheptane, perfluorooctane, and perfluorononane. Specific examples of the fluorine-containing organic compound (X-1) in which part or all of the hydrogen of the alicyclic hydrocarbon is substituted with fluorine include perfluoromethylcyclohexane, perfluoro-1,3-
Dimethylcyclohexane, perfluorodecalin, etc.
An alicyclic fluorine-containing organic compound having 6 to 14 carbon atoms constituting a ring can be used.

Fluorine-containing organic compound (X-1) in which part or all of the hydrogen of an aromatic hydrocarbon is substituted with fluorine
Specific examples of such as perfluorotoluene,
Examples thereof include an aromatic fluorine-containing organic compound having 6 to 14 carbon atoms constituting a ring. As a medium (X) in which the transition metal compound (a) and the resulting polymer are not substantially dissolved, the fluorine-containing organic compound (X
As -1), perfluorohexane, perfluoromethylcyclohexane, perfluorooctane and the like are preferable. The medium (X) can be used alone or in combination of two or more.

<< Solvent (Y) >> In the present invention, the solvent (Y) used in the prepolymerization may be a transition metal compound (a).
Can be dissolved and a compound having no compatibility with the medium (X) can be used without limitation. Here, “not compatible” is defined as follows. That is, 1 ml of the medium (X) is added to 200 ml of the solvent (Y), mixed and stirred at the pre-polymerization temperature for 10 minutes, and then allowed to stand for 10 minutes. When the interface between the medium (X) and the solvent (Y) is visually observed after standing and is in a phase separation state, it is defined as "having no compatibility".

As the solvent (Y), those which also dissolve the catalyst component other than the transition metal compound (a) and the monomer (M) are preferable. Examples of the solvent (Y) include aromatic hydrocarbons, aliphatic saturated hydrocarbons, and halogenated hydrocarbon solvents having chlorine.

Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like. Specific examples of the aliphatic saturated hydrocarbon include:
Butane, pentane, hexane, heptane, octane, decane and the like. Specific examples of the halogenated hydrocarbon include methylene chloride, chloroform,
o-Dichlorobenzene, dichloroethane and the like can be mentioned.

As the solvent (Y), aromatic hydrocarbons and aliphatic saturated hydrocarbons are preferred, and toluene, hexane, heptane, octane and decane are particularly preferred. The solvent (Y) can be used alone or in combination of two or more.

<< Olefin Polymerization Catalyst >> The olefin polymerization catalyst of the present invention is prepared by preparing a catalyst component or a solvent of the catalyst component (X) in a medium (X) in which the transition metal compound (a) and the produced polymer are not substantially dissolved. Y) With the solution dispersed,
A solid catalyst for olefin polymerization obtained by prepolymerizing the monomer (M) having a polymerizable double bond.

When the prepolymerization is performed in a state where the catalyst component is dispersed, or when the prepolymerization is performed in a state where the solvent (Y) solution of the catalyst component is dispersed, an olefin polymerization catalyst having a high bulk specific gravity and excellent particle properties is obtained. Can be

The above-mentioned catalyst component contains at least the transition metal compound (a). Usually, in addition to the transition metal compound (a), the organic boron compound (b) and / or the organic aluminum oxy compound (c) are also contained. include. Further, other catalyst components such as the organometallic compound (e) may be contained.

The prepolymerization can be carried out by bringing the catalyst component into contact with the monomer (M) having a polymerizable double bond in the medium (X). Solvent for catalyst component (Y)
When prepolymerization is performed in a state where the solution is dispersed, the catalyst component and the monomer (M) having a polymerizable double bond are brought into contact with each other in the solvent (Y) dispersed in the medium (X). In the prepolymerization, a dispersion stabilizer (d), a small amount of an organometallic compound (e), and the like can be used as necessary.

The amount of each component used in the prepolymerization depends on the amount of the medium (X)
The transition metal compound (a) is 0.005 to 2 mmol, preferably 0.02 to 1 liter in total of the solvent and the solvent (Y).
Desirably, it is 〜1 mmol. When the organic boron compound (b) is used, the molar ratio [boron / M] of boron in the organic boron compound (b) to the transition metal atom (M) in the transition metal compound (a) is usually 0.1. 1 to 10
It is desirable to use an amount of 0, preferably 1 to 10.

When the organic aluminum oxy compound (c) is used, the aluminum atom (Al) in the organic aluminum oxy compound (c) and the transition metal compound (a)
The molar ratio (Al / M) to the transition metal atom (M) is usually 10 to 1000, preferably 30 to 300. When the organometallic compound (e) is used as a catalyst component, the molar ratio of the metal atom in the organometallic compound (e) to the transition metal atom (M) in the transition metal compound (a) [metal atom / M] is usually 10 to 100
It is desirable to use an amount of 0, preferably 30 to 300.

The amount of the solvent (Y) used is 1 lit of the medium (X).
0 to 1 liter to er, preferably 0.05 to 0.5
It is desirable to use the ratio of liter. When the dispersion stabilizer (d) is used, 0.0% is used for 1 liter of the total solvent.
It is desirably 5 to 10 mmol, preferably 0.1 to 5 mmol.

In the prepolymerization, the polymerization temperature is usually from -20 to 80.
° C, preferably 0 to 50 ° C, and the polymerization pressure is usually normal pressure to 10
0 kgf / cm ² (gauge pressure), preferably normal pressure to 50
It is desirable to carry out under the condition of kgf / cm ² (gauge pressure). The prepolymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system. Further, the prepolymerization can be carried out by two or more stages of multistage polymerization under different reaction conditions.

The amount of polymerization to be performed in the prepolymerization (hereinafter, sometimes referred to as the prepolymerization amount) is from 2 to 2000 in terms of the ratio of the number of grams of the produced polymer to 1 mmol of the transition metal compound (a).
Preferably, it is set to 10 to 1,000.

The olefin polymerization catalyst of the present invention is obtained as a slurry. After the pre-polymerization, the slurry can be used as it is for the main polymerization, or the olefin polymerization catalyst can be separated and used for the main polymerization, but it is preferable to separate and use it for the main polymerization.

A specific production method for producing the olefin polymerization catalyst of the present invention is illustrated below. 1) After mixing an aromatic hydrocarbon solution of the transition metal compound (a) and the organic boron compound (b) and / or the organic aluminum oxy compound (c) with the fluorine-containing organic compound (X-1), Prepolymerization is carried out by introducing a monomer (M) having a polymerizable double bond. 2) An aromatic hydrocarbon solution of the transition metal compound (a), an aromatic hydrocarbon solution of the organic boron compound (b) and / or the organic aluminum oxy compound (c), and a fluorine-containing organic compound (X-1) Is mixed, and a monomer (M) having a polymerizable double bond is introduced therein to perform prepolymerization.

3) An aromatic hydrocarbon solution of the transition metal compound (a) is mixed with a fluorine-containing organic compound (X-1) containing a dispersion stabilizer (d), and then mixed with an organic boron compound (b). And / or an aromatic hydrocarbon solution of the organic aluminum oxy compound (c) is added, and a monomer (M) having a polymerizable double bond is introduced therein to perform prepolymerization. 4) An aromatic hydrocarbon solution of the transition metal compound (a) containing the dispersion stabilizer (d), and a fluorine-containing organic compound (X-1)
Is added thereto, and an aromatic hydrocarbon solution of the organic boron compound (b) and / or the organic aluminum oxy compound (c) is added thereto, and a monomer (M) having a polymerizable double bond is introduced therein. To perform prepolymerization.

5) A transition metal compound (a) and an organic boron compound (b) and / or an organic aluminum oxy compound (c) and an organic aluminum are added to the fluorine-containing organic compound (X-1) containing the dispersion stabilizer (d). An aromatic hydrocarbon solution in which (e) is dissolved is added, and a monomer (M) having a polymerizable double bond is introduced therein to perform prepolymerization. Among the above production methods 1) to 5), the methods 3) to 5) are preferable, and the method 5) is more preferable.

The thus obtained olefin polymerization catalyst of the present invention is a heterogeneous catalyst,
The same performance as a homogeneous catalyst is exhibited, and the catalytic activity is high. Therefore, by polymerizing an olefin using the olefin polymerization catalyst of the present invention, an olefin polymer having a high bulk density and good particle properties can be efficiently obtained.

<< Production of Olefin Polymer >> In the production method of the olefin polymer of the present invention, an olefin is polymerized or copolymerized (hereinafter simply referred to as polymerization) in the presence of the olefin polymerization catalyst of the present invention as described above. This is a method of producing an olefin polymer (this may be referred to as main polymerization). The polymerization can be a known method, for example, a solvent phase polymerization method, a liquid phase polymerization method such as bulk polymerization,
Alternatively, a gas phase polymerization method or the like can be employed.

As the inert hydrocarbon medium used when the main polymerization is carried out by a liquid phase polymerization method, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane And alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. The olefin itself to be polymerized can also be used as a solvent.

Examples of the olefin that can be polymerized by the olefin polymerization catalyst of the present invention include an α-olefin, a polar monomer having a polar group and a polymerizable double bond, an aromatic vinyl compound, and a polyene compound. . Of these, α-olefins and polyene compounds are preferred.

Specific examples of the α-olefin that can be polymerized by the olefin polymerization catalyst of the present invention include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene and 1-hexene. , 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like. 20 chain α-olefins; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4
cyclic olefins having 3 to 20 carbon atoms such as a, 5,8,8a-octahydronaphthalene;

Specific examples of the polar monomer which can be polymerized by the olefin polymerization catalyst of the present invention include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo [2.
2.1] α, β-Unsaturated carboxylic acids such as -5-heptene-2,3-dicarboxylic acid and metal salts thereof such as sodium, potassium, lithium, zinc, magnesium and calcium salts Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-acrylate
Α, β-unsaturated carboxylic esters such as ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl acetate, vinyl propionate, caproic acid Vinyl, vinyl caprate, vinyl laurate, vinyl stearate,
Vinyl esters such as vinyl trifluoroacetate; unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate;

Further, in the olefin polymerization catalyst of the present invention, an aromatic vinyl compound such as styrene; butadiene,
Isoprene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene,
1,5-octadiene, 1,6-octadiene, 1,7
Octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6
-Octadiene, 4-ethylidene-8-methyl-1,7
-Polyene compounds such as -nonadiene, 5,9-dimethyl-1,4,8, -decatriene and divinylbenzene can also be polymerized.

When an olefin polymer is produced using the olefin polymerization catalyst of the present invention, the amount of the olefin polymerization catalyst used is usually 0.00001 to 0.1 per reaction volume liter of the transition metal compound (a). It is desirable to use the compound in an amount of mmol, preferably 0.0001 to 0.01 mmol. When an organic boron compound (b), an organic aluminum oxy compound (c), or the like is used as a catalyst component, these catalyst components are generally used in the following amounts. That is, the organoboron compound (b) has a molar ratio (boron / boron) of boron in the organoboron compound (b) to the transition metal atom (M) in the transition metal compound (a).
M) is used in an amount of usually 0.1 to 100, preferably 1 to 5. Organic aluminum oxy compound (c)
Means that the molar ratio (Al / M) of the aluminum atom (Al) in the organic aluminum oxy compound (c) to the transition metal atom (M) in the transition metal compound (a) is usually 10 to 1
0000, preferably 30 to 1,000. When the organometallic compound (e) is used for the pre-polymerization, the molar ratio of the metal atom in the organometallic compound (e) to the transition metal atom (M) in the transition metal compound (a) (metal Atom / M) is used in an amount of usually 10 to 10000, preferably 100 to 1000.

The olefin polymerization conditions using the olefin polymerization catalyst of the present invention are generally such that the temperature is -50 to 200 ° C.
Preferably 0 to 170 ° C., pressure is usually normal pressure to 100 kg
f / cm ² (gauge pressure), preferably normal pressure to 50 kgf
/ Cm ² (gauge pressure). The polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system. The polymerization is carried out under different reaction conditions.
It is also possible to carry out by multistage polymerization of more than stages.

The molecular weight of the produced olefin polymer is as follows:
It can be adjusted by a method such as the presence of hydrogen in the polymerization system or the selection of the polymerization temperature. Further, the organic boron compound (b) or the organic metal compound (e) used
It can also be adjusted by selecting the type or amount of the above.

By polymerizing an olefin in this manner, even when a heterogeneous catalyst is used, the same performance as a homogeneous catalyst is exhibited, and an olefin polymer having a high bulk density and good particle properties can be efficiently produced. Obtainable. Also,
In the olefin polymerization catalyst of the present invention, the catalyst component does not elute into the reaction medium during the olefin polymerization, and therefore, the amorphous polymer does not adhere to the polymerization vessel wall or the like.

When olefin is polymerized using the olefin polymerization catalyst of the present invention, the olefin polymerization catalyst of the present invention is a heterogeneous catalyst. An olefin polymer excellent in morphology such as the above can be easily obtained. That is, by polymerizing an olefin using the olefin polymerization catalyst of the present invention, the olefin polymer having a high bulk density and a good particle property without lowering the performance of the homogeneous catalyst, An olefin polymer excellent in morphology such as the above can be easily and efficiently obtained.

[0130]

The catalyst for olefin polymerization of the present invention is obtained by dispersing the catalyst component or a solution of the catalyst component in a medium (X) in which the transition metal compound (a) and the produced polymer are not substantially dissolved. Monomer having polymerizable double bond (M)
Is a catalyst for olefin polymerization obtained by prepolymerization of the same, so that the same performance as the homogeneous catalyst is exhibited and the catalytic activity is high despite being a heterogeneous catalyst. Moreover, by using the olefin polymerization catalyst of the present invention, it is possible to easily and efficiently obtain an olefin polymer having a high bulk density and good particle properties, and excellent in morphology such as particle size and particle shape. be able to.

The process for producing an olefin polymerization catalyst according to the present invention is characterized in that the catalyst component or a solution of the catalyst component is dispersed in a medium (X) in which the transition metal compound (a) and the produced polymer are not substantially dissolved. Since the monomer (M) having a polymerizable double bond is prepolymerized, the olefin polymerization catalyst can be efficiently obtained at low cost.

The process for producing the olefin polymer of the present invention comprises:
Since the olefin is polymerized in the presence of the olefin polymerization catalyst, without lowering the performance of the homogeneous catalyst, the bulk density is high, the olefin polymer having good particle properties, particle size, particle shape, etc. An olefin polymer having excellent morphology can be easily and efficiently produced.

[0133]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 1) Synthesis of Dispersion Stabilizer 1.50 g (5.5 mmol) of Zr (OC ₂ H ₅ ) ₄ and C ₈ F ₁₇ CH ₃ CH ₂ O were placed in a sufficiently dried Schlenk tube.
The H 4.90g (10.6mmol), and n-C ₁₆
2.37 g (10.8 mmol) of H ₃₇ OH was charged, and 1
The temperature was raised to 00 ° C. After about one hour, the temperature was lowered to room temperature, and the pressure was gradually reduced by a vacuum pump. Then 90-95
The temperature was raised to ° C and held for 1 hour. The reaction product thus obtained was dissolved in hexane, the insoluble portion was removed with a G4 glass filter, and the filtrate was obtained as a dispersion stabilizer. The Zr concentration of this Zr dispersion stabilizer is 0.197 mol.
/ L.

2) Prepolymerization In a 200-ml flask purged with nitrogen, 100 ml of perfluorooctane, 3.5 ml of toluene, and a concentration of 1.0 m
ol / l of a toluene solution of triisobutylaluminum (1.0 ml) and 1.30 ml of the Zr dispersion stabilizer synthesized in 1) above, and then propylene was added at 10 liter / liter.
After the temperature was raised to 40 ° C. while supplying at the rate of hr, the temperature was immediately returned to room temperature to prepare a fluorine-based medium. Rac in another container
-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride 17.9
mg, toluene 4.0 ml and concentration 1.0 mol /
l of triisobutylaluminum in toluene 1.0
After the addition of ml to make a homogeneous solution, the entire amount of the catalyst component solution was added to the above-mentioned fluorinated medium. 3 mmol /
1 concentration of (C ₆ H ₅ ) ₃ C [B (C ₆ F ₅ ) ₄ ] toluene solution 10
ml was added slowly. As a result, the temperature in the system becomes 3
The temperature rose to 5 ° C. After that, 10 liter /
Prepolymerization was performed at 35 ° C. for 20 minutes at normal pressure while supplying at a rate of hr. As a result, 2.8 g of a powdery catalyst obtained by prepolymerizing propylene was obtained.

3) Dissolution test of transition metal compound in perfluorooctane The rac-dimethylsilylene-bis {1-
(2-Methyl-4-phenylindenyl) zirconium dichloride was dissolved in toluene to a concentration of 0.3 mg-zirconium / ml. This toluene solution and the medium (perfluorooctane) used in the prepolymerization were mixed at a volume ratio of 1: 1 and stirred for 10 minutes at the same temperature (35 ° C) as the temperature for performing the prepolymerization. At this time, the mixture was in a suspended state and did not become a homogeneous solution. Next, this mixture was allowed to stand at 35 ° C. for 10 minutes. After standing, the mixture was separated into a perfluorooctane phase and a toluene phase. next,
A part was sampled from the perfluorooctane phase as a sample, and the zirconium concentration of this sample was measured by ICP emission spectroscopy. As a result, the zirconium concentration derived from rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride was 0.001 mg / ml or less.

4) Dissolution Test of Produced Polymer A part of the reaction solution subjected to the prepolymerization was subjected to solid-liquid separation at 35 ° C., and pentafluorooctane was sampled as a sample from the obtained liquid phase. For this sample, 10
After distilling off pentafluorooctane over 12 hours under reduced pressure of 0 mmHg or less, the amount of the polymer contained in the residue was measured. As a result, the content of the polymer was 0.1.
It was 1 mg / ml or less.

5) Polymerization In a 1 liter autoclave thoroughly dried and purged with nitrogen, 350 ml of heptane, 0.6 ml of a toluene solution of triisobutylaluminum having a concentration of 1.0 mol / l, and the heterogeneous system obtained in the above 2) The catalyst was charged at 0.01 mmol in terms of Zr atom. When propylene was supplied and pressurized to 5 kgf / cm ² (gauge pressure),
The temperature rose from 65 ° C to 80 ° C. Thereafter, the pressure was increased to 5 kgf / c by continuously supplying propylene.
While maintaining the pressure at m ² (gauge pressure), polymerization was carried out at 80 ° C. for 10 minutes. As a result, 72.0 g of polypropylene having a smooth, granular particle property, a bulk density of 0.32 g / cm ³ and a melting point of 154.2 ° C. measured by DSC was obtained. In this case, there was no adhesion of the amorphous polymer to the polymerization vessel wall or the like. In addition, this melting point was equivalent to the polypropylene obtained with the homogeneous catalyst.

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Claims (10)

[Claims] 1. A method for prepolymerizing a monomer (M) having a polymerizable double bond in a state in which a catalyst component is dispersed in a medium (X) in which a transition metal compound (a) and a produced polymer are not substantially dissolved. An olefin polymerization catalyst according to claim 1, wherein said catalyst component contains at least a transition metal compound (a). 2. A monomer (M) having a polymerizable double bond in a state in which a solution of a catalyst component is dispersed in a medium (X) in which a transition metal compound (a) and a produced polymer are not substantially dissolved. An olefin polymerization catalyst obtained by prepolymerization, wherein the solution of the catalyst component is a solution in which at least the transition metal compound (a) is dissolved in a solvent (Y) incompatible with the medium (X). Catalyst. 3. The olefin polymerization catalyst according to claim 1, wherein the transition metal compound (a) is a compound containing a transition metal belonging to Group 4 of the periodic table. 4. The catalyst component contains an organic boron compound (b) and / or an organic aluminum oxy compound (c) in addition to the transition metal compound (a).
4. The catalyst for olefin polymerization according to any one of items 1 to 3. 5. The olefin according to claim 1, wherein the medium (X) in which the transition metal compound (a) and the produced polymer are not substantially dissolved is a fluorine-containing organic compound (X-1). Catalyst for polymerization. 6. A solvent (Y) incompatible with the medium (X)
6. The catalyst for olefin polymerization according to claim 2, wherein is a hydrocarbon compound. 7. The olefin polymerization catalyst according to claim 1, which is obtained by prepolymerization in the presence of a dispersion stabilizer (d). 8. A monomer (M) having a polymerizable double bond is prepolymerized in a state where a catalyst component is dispersed in a medium (X) in which a transition metal compound (a) and a produced polymer are not substantially dissolved. A method for producing an olefin polymerization catalyst, wherein the catalyst component contains at least a transition metal compound (a). 9. A monomer (M) having a polymerizable double bond in a state in which a solution of a catalyst component is dispersed in a medium (X) in which a transition metal compound (a) and a produced polymer are not substantially dissolved. A method for producing an olefin polymerization catalyst by prepolymerization, wherein a solution of the catalyst component is a solution in which at least a transition metal compound (a) is dissolved in a solvent (Y) incompatible with a medium (X). A method for producing an olefin polymerization catalyst. 10. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 7.