JP3479582B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization. Specifically, it relates to an olefin polymerization catalyst comprising a specific transition metal compound and a specific carrier.

[0002]

2. Description of the Related Art In recent years, a transition metal compound (homogeneous catalyst) soluble in an inert organic solvent has attracted attention as a catalyst for olefin polymerization, and among them, so-called metallocene compounds are well known. A method for polymerizing an olefin using these metallocene compounds, particularly a method for stereoregularly polymerizing an α-olefin has been reported by W. Kaminsky et al. (JP-A-58-19309, Angew,
Chem., 97, 507 (1985)) Many improvements have been made.

A slurry polymerization method of polymerizing an olefin in an inert hydrocarbon using a metallocene compound and an organoaluminum oxy compound as a catalyst, a bulk polymerization method of polymerizing in a liquefied olefin monomer, or a gas phase of polymerizing in a gaseous olefin monomer. In the polymerization method, the polymer or organoaluminum oxy compound formed during the polymerization adheres to the inner wall of the reactor, causing a decrease in heat removal capacity.In addition, lumps are formed in the reactor, and stable operation of the polyolefin manufacturing equipment is possible. Interfere with. Further, there is a problem that the particle size of the produced polymer is very small, the bulk density of the polymer is low, and the productivity is remarkably reduced.

In order to solve these problems, Japanese Patent Laid-Open No.
0-35006, JP-A-61-108610, JP-A-61-296008, JP-A-63-66206,
Japanese Unexamined Patent Publication (Kokai) No. 2-173104 and the like describe a method of polymerizing an olefin using a catalyst produced by supporting an organoaluminum oxy compound on an inorganic oxide such as silica gel or alumina and contacting with a metallocene compound. .
These inorganic oxides generally have acidic surface hydroxyl groups, and when they contact an organoaluminum oxy compound or a metallocene compound, the catalyst is supported on the carrier.

However, the polyolefin synthesized by the above method using a catalyst in which a metallocene compound and / or an organoaluminumoxy compound is supported on an inorganic oxide such as silica gel or alumina is used as a carrier in the product. Relatively hard inorganic substance remains, which causes fisheye as foreign matter of the product. This not only lowers the value of the product, but also clogs the filter installed in the molding machine, the melt kneader, or the granulator, which makes industrially stable operation difficult.

Further, a polyolefin obtained by polymerizing with an olefin polymerization catalyst in which an organoaluminum oxy compound and / or a metallocene compound is supported on the above-mentioned inorganic carrier,
Especially in polypropylene, its stereoregularity is much lower than that of a polyolefin produced by a homogeneous polymerization catalyst used without being supported, and further, physical properties such as rigidity, impact resistance and heat resistance are deteriorated, and It was a big problem.

Further, there has been an attempt to improve the activity of the olefin polymerization catalyst by modifying the organoaluminum oxy compound. In JP-A-2-78687, the organoaluminum oxy compound and the active hydrogen-containing compound are contacted with each other. A method using the thus obtained benzene-insoluble organoaluminum oxy compound and a metallocene compound as a catalyst, and JP-A-7-53619 and JP-A-7-5.
Japanese Patent No. 3620 describes a method of modifying an organoaluminumoxy compound with an organic compound such as keto alcohol or β-diketone.

Further, as a method for modifying an organoaluminum oxy compound, Japanese Patent Application Laid-Open No. 7-53620 discloses a method for improving the catalytic activity and also for preventing adhesion of the produced polymer to the inner wall of the reactor. A method using a catalyst composed of an addition reaction product of an organophosphorus compound and an organoaluminumoxy compound having a specific structure and a metallocene compound is described.

However, these methods cannot sufficiently prevent the adhesion of the polymer or the like generated during the polymerization reaction to the inner wall of the reactor.

[0010]

DISCLOSURE OF THE INVENTION The present invention is to produce a polyolefin with high activity and high stereoregularity, and to prevent adhesion of the polymer or organoaluminum oxy compound formed during the polymerization reaction to the inner wall of the reactor, High bulk density,
It is an object of the present invention to provide an olefin polymerization catalyst that maintains high productivity and improves fisheye level in products.

[0011]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have conducted extensive studies on a target olefin polymerization catalyst and completed the present invention. The present invention includes the following inventions.

[0012] A and soluble organic transition metal compound in an inert organic solvent, polymerization catalyst consisting of the insoluble carrier in an inert organic solvent, carrier represented by the following general formula [1] (of 6) An olefin polymerization catalyst comprising a polyolefin containing a group having a carbonyl .

[0013]

[Chemical 6] (In the formula, Q is hydrogen, hydroxy, alkyl, aryl,
It is selected from alkoxy, aryloxy, oxycarbonyl, halogen, amino, aminocarbonyl, hydrazino or oxyanion. ) The catalyst for olefin polymerization according to [1] further containing an organometallic compound as a catalyst component.

General formula insoluble in inert organic solvents
Poly containing a group having a carbonyl represented by [1]
A catalyst component for olefin polymerization in which an organoaluminum oxy compound is brought into contact with a carrier which is an olefin.

A method for polymerizing an olefin using the catalyst described in any one of the above.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The olefin polymerization catalyst of the present invention will be specifically described below.

In the present invention, being soluble or insoluble in an inert organic solvent means that the organic transition metal compound and the carrier have the following properties.

In the present invention, the organic transition metal compound component and the carrier component are brought into contact with each other in advance in an inert organic solvent to prepare a catalyst, which is then subjected to polymerization. Soluble or insoluble in an inert organic solvent means that each component alone is soluble and insoluble in the inert organic solvent used for the preparation of this catalyst before contacting both components. Is meant to have. That is, it means that the organic transition metal compound alone has a property of being soluble in the inert organic solvent, and the carrier alone has a property of being insoluble in the inert organic solvent before the two components are brought into contact with each other.

In the present invention, the inert organic solvent is an alkane having 1 to 20 carbon atoms, an aromatic hydrocarbon compound having 6 to 20 carbon atoms, an ether having 2 to 20 carbon atoms, or a halogenated carbonization having 1 to 20 carbon atoms. It is hydrogen.

Specific examples of the alkane include methane, ethane, propane, butane, pentane, heptane, octane, isobutane, neopentane, cyclopentane or cyclohexane, decalin, and the like. Specific examples of the aromatic hydrocarbon compound include: Examples thereof include benzene, toluene, xylene, and the like, and further include ethers having 2 to 20 carbon atoms. Specific examples of ethers include diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane,
Examples of the halogenated hydrocarbon include dioxane and the like, or halogenated hydrocarbons having 1 to 20 carbon atoms, such as dichloromethane and chloroform.
Further, the inert organic solvent may be a mixture of these.

The organic transition metal compound soluble in an inert organic solvent in the present invention is a transition metal of Group 3 to Group 8 of the periodic table (Chemical Dictionary: Tokyo Kagaku Dojin, according to the periodic table on the front cover published in 1994). There is no particular limitation as long as it is an organic transition metal compound containing a compound that polymerizes an olefin by using an organoaluminum oxy compound as a cocatalyst or a catalyst activator, and particularly preferably the following general formula [4] 7) or a metallocene compound represented by the general formula [5] (Chemical formula 8).

[0022]

[Chemical 7] (In the formula, A ¹ and A ² are a cyclopentadienyl group, an indenyl group or a fluorenyl group, and A ¹ , A ²
One of the groups may be an amino group, and these groups may have substituents adjacent to each other directly bonded to each other to form the same cyclic hydrocarbon substituent. Further, some or all of the hydrogens in these groups are alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, alkoxy having 1 to 20 carbons,
It may be substituted with a substituent selected from aryloxy having 6 to 20 carbon atoms and silicon-containing alkyl having 1 to 20 carbon atoms. M is a metal selected from Group 4 of the periodic table, and X is
¹ and X ² are selected from halogen, alkyl having 1 to 20 carbon atoms or anionic ligand. ) Or, the following general formula [5]

[0023]

[Chemical 8] (In the formula, A ³ and A ⁴ are a cyclopentadienyl group, an indenyl group or a fluorenyl group, and one of A ³ and A ⁴ may be an amino group, and these groups are adjacent to each other. The substituents may directly bond to each other to form the same cyclic hydrocarbon substituent, and some or all of the hydrogen atoms in these groups may be alkyl having 1 to 20 carbons, or 6 carbons.
May be substituted with a substituent selected from aryl having 20 to 20 carbons, alkoxy having 1 to 20 carbons, aryloxy having 6 to 20 carbons, and silicon-containing alkyl having 1 to 20 carbons. A ³ and A ⁴ may be the same as or different from each other. M is a metal selected from Group 4 of the periodic table, and Y is-
^{CR 1 R 2 -, - CR} 1 R 2 -CR 3 R 4 -, or -SiR
¹ R ² — (R ¹ , R ² , R ³ or R ⁴ is hydrogen, 1 to 1 carbon atoms
20 alkyl, 6 to 20 carbon aryl, 1 carbon
˜20 alkoxy, C 6-20 aryloxy, C 1-20 silicon-containing alkyl,
R ¹ , R ² , R ³ and R ⁴ may be the same or different. ), X ¹ and X ² are halogen and have 1 to 1 carbon atoms.
20 alkyl or anionic ligands. )
In the general formulas [4] and [5], the number of carbon atoms is 1-2.
Examples of alkyl of 0 include methyl, ethyl, propyl, butyl, or isopropyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl or menthyl. Examples of the aryl having 6 to 20 carbon atoms include phenyl, tolyl, naphthyl and the like. Further, examples of the alkoxy having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, or isopropoxy, tert-butoxy, neopentoxy or cyclopentoxy, cyclohexyloxy, mentoxy and the like. Examples of the aryloxy having 6 to 20 carbon atoms include phenoxy, tolyloxy, xylyloxy and naphthyloxy.

Examples of the silicon-containing alkyl having 1 to 20 carbon atoms include trimethylsilyl, dimethylethylsilyl, diphenylmethylsilyl, cyclohexyldimethylsilyl, triphenylsilyl, 2- (methyldiphenylsilyl) ethyl and the like.

Further, adjacent substituents may be directly bonded to each other to form the same cyclic hydrocarbon substituent. Specific examples include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a benzene ring, a naphthalene ring, and derivatives thereof which are bonded to each other by a cyclic hydrocarbon substituent.

In the above general formula [5] , Y is -CR ^{1
R 2 -, - CR 1 R} 2 -CR 3 R 4 -, or -SiR ¹ R ²
-, Specifically, methylene, dimethylmethylene (or isopropylidene), diphenylmethylene or ethylene, 1,2-dimethylethylene, 1,1,2,
2-tetramethylethylene or dimethylsilylene , di
Examples include phenylsilylene .

In the above general formulas [4] and [5], M
Is a metal selected from Group 4 of the periodic table, and M includes titanium, zirconium, and hafnium. X ¹ and X ² are selected from halogen, an alkyl group or an anion ligand, halogen is selected from fluorine, chlorine, bromine and iodine, and an alkyl group is methyl,
Examples thereof include linear alkyl groups such as ethyl and propyl, branched alkyl groups such as isopropyl, and cyclic alkyl groups such as cyclopropyl.

As the anionic ligand, an organic phosphorus compound such as trimethylphosphine, triethylphosphine, triphenylphosphine or diphenylmethylphosphine, or methoxy, ethoxy, n-butoxy, sec-butoxy, tert-butoxy, phenoxy, Or, an alkoxy ligand such as naphthoxy, or an ether compound such as tetrahydrofuran, diethyl ether, dioxane, or 1,2-dimethoxyethane can be given.

Specific examples of the metallocene compounds represented by the above general formulas [4] and [5] in the present invention are shown below, but the metallocene compounds capable of polymerizing olefins are not particularly limited thereto.

Examples of the metallocene compound of the general formula [4] include bis (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride and bis (2-methylindenyl). ) Zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (4-t-butylfluorenyl) zirconium dichloride, (pentamethylcyclopentadienyl )
) (Di-t-butylamido) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (2-methylindenyl) zirconium Dimethyl, bis (fluorenyl) zirconium dimethyl, bis (4-t-butylfluorenyl) zirconium dimethyl, (pentamethylcyclopentadienyl) (di-t-
Butylamido) zirconium dimethyl and the like, and metallocene compounds in which zirconium in the above metallocene compound is replaced with titanium or hafnium.

Further, a metallocene compound represented by the general formula [5]
And thenDimethyl silyleneBis (cyclopentadiene
Le) zirconium dichloride,Dimethyl silyleneScrew
(Tetramethylcyclopentadienyl) zirconium di
Chloride,Dimethyl silyleneBis (methylcyclopenta
Dienyl) zirconium dichloride,Dimethyl silylene
Bis (dimethylcyclopentadienyl) zirconium di
Chloride, Dimethyl silylene(2,4-dimethylcyclo
Pentadienyl) (3 ', 5'-dimethylcyclopentadi)
(Enyl) zirconium dichloride,Dimethyl silylene
(2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dichloride,Dimethyl silyleneScrew (t-
Butylcyclopentadienyl) zirconium dichloride
De,Dimethyl silyleneBis (trimethylsilylcyclope
Zantadienyl) zirconium dichloride,Dimethyl sili
LenBis (2-trimethylsilyl-4-t-butylsik)
Lopentadienyl) zirconium dichloride,Dimethyl
SilyleneScrew (4,5,6,7-Tetrahydroindeni
Le) Zirconium dichloride,Dimethyl silyleneScrew
(Indenyl) zirconium dichloride,Dimethyl sili
LenBis (2-methylindenyl) zirconium dichloride
Lido,Dimethyl silyleneBis (2,4-dimethylindene
Nil) zirconium dichloride,Dimethyl silyleneScrew
(2,4,7-Trimethylindenyl) zirconium di
Chloride,Dimethyl silyleneBis (2-methyl-4-ph)
Phenylindenyl) zirconium dichloride,Dimethyl
SilyleneBis (2-ethyl-4-phenylindenyl)
Zirconium dichloride,Dimethyl silyleneBis (ben
Z [e] indenyl) zirconium dichloride,Zimechi
LuciryleneBis (2-methylbenz [e] indenyl)
Zirconium dichloride,Dimethyl silyleneScrew (3-
Methylbenz [e] indenyl) zirconium dichloride
De,Dimethyl silyleneBis (Benz [f] indenyl)
Zirconium dichloride,Dimethyl silyleneScrew (2-
Methylbenz [f] indenyl) zirconium dichloride
De,Dimethyl silyleneBis (3-methylbenz [f] a
Ndenyl) zirconium dichloride,Dimethyl silylene
Bis (cyclopenta [cd] indenyl) zirconium
Dichloride,Dimethyl silyleneBis (cyclopentadiene
Nil) zirconium dimethyl,Dimethyl sili LenScrew
(Tetramethylcyclopentadienyl) zirconium di
Methyl,Dimethyl silyleneBis (methylcyclopentadi
(Enyl) zirconium dimethyl,Dimethyl silyleneScrew
(Dimethylcyclopentadienyl) zirconium dimethyl
Le,Dimethyl silylene(2,4-dimethylcyclopenta
Dienyl) (3 ', 5'-dimethylcyclopentadienyl
Le) zirconium dimethyl,Dimethyl silylene(2,
3,5-trimethylcyclopentadienyl) (2 ',
4 ', 5'-trimethylcyclopentadienyl) zirconi
Umm dimethyl,Dimethyl seriesBis (t-butyl siku
Lopentadienyl) zirconium dimethyl,Dimethyl
RyleneBis (trimethylsilylene cyclopentadiene
Le) zirconium dimethyl,Dimethyl silyleneScrew (2
-Trimethylsilyl-4-t-butylcyclopentadiene
Nil) zirconium dimethyl,Dimethyl silyleneScrew
(4,5,6,7-Tetrahydroindenyl) Zirconi
Umm dimethyl,Dimethyl silyleneBis (indenyl) di
Ruconium dimethyl,Dimethyl silyleneBis (2-meth)
Ruindenyl) zirconium dimethyl,Dimethyl series
TheBis (2,4-dimethylindenyl) zirconium di
Methyl,Dimethyl silyleneBis (2,4,7-trimethylene
Ruindenyl) zirconium dimethyl,Dimethyl series
TheBis (2-methyl-4-phenylindenyl) zirco
N-dimethyl,Dimethyl silyleneBis (2-ethyl-
4-phenylindenyl) zirconium dimethyl,Jime
ChillillyleneBis (benz [e] indenyl) Zirconi
Umm dimethyl,Dimethyl silyleneBis (2-methylben
Z [e] indenyl) zirconium dimethyl,Dimethyl
SilyleneBis (3-methylbenz [e] indenyl) di
Ruconium dimethyl,Dimethyl silyleneBis (benz
[F] indenyl) zirconium dimethyl,Dimethyl
RyleneBis (2-methylbenz [f] indenyl) dil
Conium dimethyl,Dimethyl silyleneBis (3-methyl
Benz [f] indenyl) zirconium dimethyl,Jime
ChillillyleneBis (cyclopenta [cd] indenyl)
Zirconium dimethyl, etc. and the above-mentioned metallocene compound
Ruthenium was replaced with titanium or hafnium.
Compounds and the like.

Further, isopropylidene (cyclopenta
Dienyl) (fluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (indeni
Le) zirconium dichloride, isopropylidene (Sik
Ropentadienyl) (2,7-di-t-butylfluore
) Zirconium dichloride, isopropylidene (Shi
Clopentadienyl) (3-methylfluorenyl) zirconium dichloride, isopropylidene (cyclopenta
Dienyl) (4-methylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl)
(Octahydrofluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, isopropylidene (dimethylcyclopentadienyl) (fluorenyl
Z) Zirconium dichloride, isopropylidene (tet
Lamethylcyclopentadienyl) (fluorenyl) zirconium dichloride.

Alternatively , diphenylmethylene (cyclopen
Tadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (a
Ndenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl
Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3-methylfluorene
Nyl) zirconium dichloride, diphenylmethylene
(Cyclopentadienyl) (4-methylfluorenyl)
Zirconium dichloride, diphenylmethylene (cyclo
Pentadienyl) (octahydrofluorenyl) zirconium dichloride, diphenylmethylene (methylcyclohexane
Pentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (dimethylcyclopentadiene )
Nyl) (fluorenyl) zirconium dichloride, diphenylmethylene (tetramethylcyclopentadienyl)
(Fluorenyl) zirconium dichloride.

Or cyclohexylidene (cyclopenta
Dienyl) (fluorenyl) zirconium dichloride,
Cyclohexylidene (cyclopentadienyl) (indene
Nyl) zirconium dichloride, cyclohexylidene
(Cyclopentadienyl) (2,7-di-t-butylphenyl)
Fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3-methylfluorenyl
Le) zirconium dichloride, cyclohexylidene (Shi
Clopentadienyl ) (4- methylfluorenyl ) zirconium dichloride, cyclohexylidene (cyclopen
Tadienyl) (octahydrofluorenyl) zirconium dichloride, cyclohexylidene (methylcyclopen
Tadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (dimethylcyclopentadienyl )
R) (fluorenyl) zirconium dichloride, cyclohexylidene (tetramethylcyclopentadienyl)
(Fluorenyl) zirconium dichloride or dime
Tylsilylene (cyclopentadienyl) (fluoreni
Z) Zirconium dichloride, dimethyl silylene
Ropentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl)
(2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl )
) (3-Methylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (4-
Methylfluorenyl) zirconium dichloride, dimethy
Lucillene (cyclopentadienyl) (octahydrofuran
Ruorenyl) zirconium dichloride, dimethyl silyl
(Methylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethyl silylene (dimethyl
Clopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopen
Tadienyl) (fluorenyl) zirconium dichloride, or isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (indenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl Eni
(2)-(7-di-t-butylfluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadiene )
Nyl) (fluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) ( 2,7-di-
t-butyl fluorenyl) zirconium dimethyl, dime
Tylsilylene (cyclopentadienyl) (fluoreni
) Zirconium dimethyl, dimethylsilylene (cyclo
Pentadienyl) (indenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) (2,
Examples thereof include 7-di-t-butylfluorenyl) zirconium dimethyl and the like, and metallocene compounds in which zirconium in the above metallocene compound is replaced with titanium or hafnium.

Furthermore, ethylene bis (indenyl) zirconium dichloride, ethylene bis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride,
1,2- dimethylethylene bis (indenyl) zirconium dichloride, 1,2- dimethylethylene bis (2 '
-Methylindenyl) zirconium dichloride, 1,2
- diisopropyl ethylenebis (indenyl) zirconium dichloride, 1,2-diisopropyl-ethylenebis (2'-methyl indenyl) zirconium dichloride,
1,2- Dimethylethylene bis (3'-methylindenyl) zirconium dichloride, 1,2- dimethylethylene
Emissions bis (4'-isopropyl-indenyl) zirconium dichloride, 1,2-dimethylethylene bis (4 ', 7'
-Diisopropylindenyl) zirconium dichloride, 1,2- dimethylethylenebis (2'-methyl-4 ')
-Isopropylindenyl) zirconium dichloride,
1,2- Dimethylethylenebis (4'-cyclohexylindenyl) zirconium dichloride, 1,2- dimethyl
Ruechiren bis (2'-methyl-4'-cyclohexyl) zirconium dichloride, 1,2-dimethyl
Ethylenebis (4'-phenylindenyl) zirconium dichloride, 1,2- dimethylethylenebis (4 ',
7'-diphenylindenyl) zirconium dichloride, 1,2- dimethylethylene bis (2'-methyl-4 '
-Phenylindenyl) zirconium dichloride, 1,
2- Dimethylethylene bis (4'-naphthylindenyl) zirconium dichloride, 1,2- dimethylethylene
Emissions bis (2'-methyl-4'-naphthyl indenyl) zirconium dichloride, 1,2-dimethylethylene bis (5'-phenyl indenyl) zirconium dichloride, 1,2-dimethylethylene bis (4'-methoxy-indenyl ) Zirconium dichloride, 1,2- dimethyl
Ethylenebis (benz [e] indenyl) zirconium dichloride, 1,2- dimethylethylenebis (2'-methylbenz [e] indenyl) zirconium dichloride, 1,2- dimethylethylenebis (3'-methylbenz [e] indenyl) zirconium Dichloride, 1,2
- dimethylethylene bis (benz [f] indenyl) zirconium dichloride, 1,2-dimethylethylene bis (2'Mechirubenzu [f] indenyl) zirconium dichloride, 1,2-dimethylethylene bis (3'Mechirubenzu [f] indenyl ) Zirconium dichloride, 1,2- dimethylethylene bis (cyclopenta [c
d] indenyl) zirconium dichloride.

Or ethylenebis (indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, 1,2-
Dimethyl ethylene bis (2'-methyl-4'-isopropylindenyl) zirconium dimethyl, 1,2- dimethyl
Ruechiren bis (4', 7'-diisopropyl) zirconium dimethyl, 1,2-dimethyl ethylene <br/> bis (2'-methyl-4'-phenyl indenyl) zirconium dimethyl, 1,2-dimethyl ethylene bis (2 '
-Methyl-4'-naphthylindenyl) zirconium dimethyl, 1,2- dimethylethylenebis (benz [e]
Indenyl) zirconium dimethyl, 1,2- dimethyl
Ethylenebis (2'-methylbenz [e] indenyl)
Examples thereof include zirconium dimethyl, 1,2- dimethylethylenebis (3′-methylbenz [e] indenyl) zirconium dimethyl, and the like, and metallocene compounds in which zirconium in the above metallocene compound is replaced with titanium or hafnium.

Further, ethylene (t-butylamide)
(Cyclopentadienyl) zirconium dichloride, ethylene (t-butylamide) (tetramethylcyclopentene
Tadienyl) zirconium dichloride, dimethyl silyl
(T-butylamide) (tetramethylcyclopentadiene
(Enyl) zirconium dichloride, dimethyl silylene
(T-Butylamide) (indenyl) zirconium dichloride, dimethylsilylene (t-butylamide) (full
Orenyl) zirconium dichloride (tetrahydrofuran), dimethylsilylene (t- butylamide) ( fluor
Renyl) zirconium dichloride (diethyl ether), ethylene ( t-butylamide) (cyclopentadiene
Enyl) zirconium dimethyl, ethylene (t-butyl)
Amido) (tetramethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (t-butylami)
De) (tetramethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (t-butylamide)
( Indenyl ) zirconium dimethyl, dimethyl silyl
(T-butylamido) (fluorenyl) zirconium dimethyl (tetrahydrofuran), dimethylsilylene
Examples thereof include (t-butylamido) (fluorenyl) zirconium diphenyl and the like, and metallocene compounds in which zirconium in the metallocene compound is replaced with titanium or hafnium.

In the organic polymer compound containing a group having a carbonyl represented by the general formula [1] which is an insoluble carrier in the inert organic solvent of the present invention, Q is hydrogen, hydroxy, alkyl, aryl, alkoxy, It is selected from aryloxy, oxycarbonyl, halogen, amino, aminocarbonyl, hydrazino or oxyanion. Further, a carrier insoluble in an inert organic solvent is obtained by contacting the organic polymer compound with an organic aluminum oxy compound. Specifically, the functional group in which Q of the carbonyl-containing group represented by the general formula [1] contains hydrogen or oxygen is
Functional groups which are respectively formyl (or aldehyde) or carboxy and Q is alkyl or aryl are respectively alkyl or aryl ketones. In this case, the alkyl preferably has 1 carbon atom.
To 20 alkyl, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, or isopropyl, tert-butyl, neopentyl, or cyclopentyl, cyclohexyl, menthyl. The aryl preferably has 6 to 2 carbon atoms.
It is an aryl of 0 and includes phenyl, tolyl, xylyl, naphthyl, anthryl and the like.

Functional groups in which Q is alkyloxy or aryloxy are so-called esters, alkoxycarbonyl or aryloxycarbonyl, respectively. Here, the alkoxy is preferably an alkoxy having 1 to 20 carbon atoms, and specific examples include methoxy,
Ethoxy, propoxy, butoxy, pentoxy, hexyloxy, or isopropoxy, tert-butoxy,
Examples include neopentoxy, cyclopentoxy, cyclohexyloxy, mentoxy and the like. The aryloxy is preferably aryloxy having 6 to 20 carbon atoms, and examples thereof include phenoxy, tolyloxy, xylyloxy, naphthyloxy and anthryloxy.

The functional group in which Q is oxycarbonyl is a carboxylic acid anhydride, the functional group in which Q is a halogen is haloformyl, and the halogen is selected from fluorine, chlorine, bromine and iodine. Further, the functional group in which Q is amino, aminocarbonyl or hydrazino is amide (or carbamoyl), imide or hydrazide, respectively, and the hydrogen of these functional groups is, for example, methyl, ethyl, propyl, butyl, or isopropyl, tert- butyl or cyclopentyl, alkyl or phenyl cyclohexyl may be substituted by an aryl, such as Application Benefits Le. The functional group in which Q is an oxyanion is carbooxynium, and examples of the counter cation include ammonium, sodium, potassium, calcium, magnesium, zinc and tin.

The organic polymer compound containing a carbonyl group represented by the general formula [1] in the present invention is (I) an organic polymer obtained by (co) polymerizing a monomer containing a carbonyl group. Molecular compound. (II) An organic polymer compound obtained by grafting or graft (co) polymerizing an unsaturated compound having a carbonyl group with an organic polymer compound having no functional group.

(III) Classified as an organic polymer compound obtained by modifying with a carbonyl-containing compound or a carbonyl-containing group precursor compound.

Explaining these classifications concretely, the organic polymer compound obtained by (co) polymerizing the monomer having a group having a carbonyl of (I) is, for example, methacrylic acid or acrylic acid. , Acrylic acid esters such as methyl methacrylate, methyl acrylate, etc., acrylamides such as methacrylamide, acrylamide, crotonamide, vinyl acetate, methyl vinyl ketone, acryloyl chloride, acrylaldehyde, etc. vinyl, β- Lactones such as propiolactone, lactams such as ε-caprolactam, isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate and octamethylene diisocyanate, β-benzyl aspartic anhydride, 4-benzyl oxazolid- , 5-dione and other N-carboxyamino acid anhydrides, ε-aminocaproic acid, ω-aminoundecanoic acid and other aminocarboxylic acids, maleic anhydride, itaconic anhydride, phthalic anhydride, pyromellitic anhydride and other carboxylic acids Anhydrides, hexamethylenediamine,
Amines such as nonamethylenediamine and phenylenediamine, dicarboxylic acids such as adipic acid, maleic acid and itaconic acid, haloformyls such as adipic acid dichloride and phthalic acid dichloride, esters such as dimethyl terephthalate, or ethylene glycol, propylene glycol , Butanediol, hexamethylene glycol, alcohols such as bisphenol A, and the like, homopolymers thereof, copolymers with two or more kinds of monomers, or monomers not containing a group having a carbonyl, such as α -Copolymers with olefins, styrenes, epoxies, ethers and the like can be mentioned.

The polymerization method for synthesizing the organic polymer compound containing a group having a carbonyl is any of radical polymerization, cationic polymerization, anionic polymerization, transition metal catalyst polymerization, ring-opening polymerization, polyaddition, addition condensation or polycondensation. May be and is not particularly limited.

Further, the organic polymer compound (II) obtained by grafting or graft-polymerizing an unsaturated compound containing a carbonyl group to the organic polymer compound having no functional group is, for example, Molecular compounds such as polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, ethylene-butene copolymer,
For polymer compounds such as ethylene-propylene-butene copolymer, polyisobutene, polypentene, poly-4-methylpentene, polynorbornene, polybutadiene, polyisoprene, polystyrene, poly α-methylstyrene, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, polysiloxane , Preferably polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, ethylene-butene copolymer,
Ethylene / propylene / butene copolymer, polyisobutene, polypentene, poly-4-methylpentene, polynorbornene, polybutadiene, polyisoprene, polystyrene, poly α-methylstyrene, for example, methacrylic acid which is an unsaturated compound containing a group having a carbonyl. Acrylic acid such as acrylic acid, methyl methacrylate, 3-methacryloxypropyltrimethoxysilane,
Acrylic esters such as methyl acrylate, acrylamides such as methacrylamide, acrylamide, crotonamide, vinyl acetate, vinyl vinyl such as methyl vinyl ketone, acryloyl chloride and acryl aldehyde, and carboxylic acids such as maleic anhydride and itaconic anhydride. An organic polymer compound obtained by grafting or graft-polymerizing an anhydride, a dicarboxylic acid such as maleic acid or itaconic acid by a radical reaction can be mentioned.

The organic polymer compound obtained by modifying with a compound containing a group having a carbonyl of (III) or a precursor compound of a group having a carbonyl is, for example, polyvinyl alcohol, polyvinyl chloride, polyvinyl pyridine, Nitrated polystyrene, polyacrylonitrile,
Examples of the organic polymer compound such as cellulose include organic polymer compounds partially modified or modified by reactions such as esterification reaction, oxidation reaction, reduction reaction, and acylation reaction, or polystyrene, poly α Examples include haloformyls such as acetyl chloride, adipic acid dichloride, and phthalic acid dichloride obtained by Friedel-Crafts reaction of methylstyrene, and organic polymer compounds partially modified or modified with acetic anhydride.

Further, the method for synthesizing the organic polymer compound containing a group having a carbonyl represented by the above general formula [1] is not particularly limited, and the reaction in an organic or aqueous medium, the gas phase reaction , Gas / solid reaction, bulk reaction without solvent,
Alternatively, it may be synthesized in any reaction form such as a reaction under melt kneading. The content of the functional group in the organic polymer compound is 1 × 10 ⁻⁶ to 1 per 1 g of the polymer compound.
It is ^{x10 -2} mol, preferably 1 x 10 ^-5 to 1 x 10 ^-3 mol.

In the present invention, the carrier insoluble in an inert organic solvent is an organic polymer compound belonging to the above-mentioned category.
Organic polymers are preferred, and polyolefins which are grafted or graft polymerized with an unsaturated compound containing a group having a carbonyl group are particularly preferred. More specifically, polyethylene, polypropylene, polybutene, polyisobutene, polypentene, poly-4-methylpentene, polynorbornene, polybutadiene, polyisoprene, polystyrene, maleic anhydride, or itaconic anhydride, or a polyolefin such as poly α-methylstyrene. Organic polymers grafted with methacrylic acid, acrylic acid, or methyl methacrylate, 3-methacryloxypropyltrimethoxysilane, methyl acrylate, etc.,
Alternatively, there is an organic polymer obtained by at least partially modifying or modifying a functional group grafted to an organic polymer by a reaction such as an esterification reaction, an amidation reaction, a haloformylation, an acylation reaction after grafting these.

In the present invention, the carrier insoluble in the inert organic solvent is one in which the organoaluminum oxy compound is supported on the organic polymer by bringing the organoaluminum oxy compound into contact with the above organic polymer containing a carbonyl group. The organoaluminum oxy compound is preferably exemplified, and is held on a carrier by a chemical bond with an organic polymer. Therefore, the catalyst composed of the organic transition metal compound soluble in the inert organic solvent and the carrier insoluble in the inert organic solvent, the organic transition metal compound is an organoaluminum oxy compound supported on an organic polymer containing a group having a carbonyl. It is presumed that the organic transition metal compound is not supported on the organic polymer directly by the chemical bond with the carbonyl-containing group of the organic polymer or by impregnating the organic polymer.

In the present invention, a conventionally known aluminoxane can be used as the organoaluminum oxy compound, and the following general formula [2]

[0051]

[Chemical 9] Alternatively, the compound represented by the general formula [3] (Chemical Formula 10) is used.

[0052]

[Chemical 10] (In the formula, R ⁵ may be the same or different, is alkyl having 1 to 6 carbons, aryl having 6 to 18 or hydrogen, p 5
Is an integer of 2 to 50, preferably 10 to 35. ) Further, an organoaluminum compound may be mixed with the above organoaluminum oxy compound.

In the present invention, the method of bringing the organoaluminum oxy compound into contact with the organic polymer compound containing a group having a carbonyl which is an insoluble carrier in an inert organic solvent includes (A) heating with an inert organic solvent. A method of contacting an organic aluminum oxy compound with an organic polymer compound containing a dissolved carbonyl-containing group. (B) A method of bringing an organoaluminumoxy compound into contact with an organic polymer compound containing a group having a carbonyl, which is suspended in an inert organic solvent. (C) A method of bringing an organoaluminum oxy compound into contact with an organic polymer compound containing a carbonyl-containing group of powder.

The inert organic solvent used in the methods (A) and (B) is an alkane, aromatic hydrocarbon, ether or halogenated hydrocarbon, preferably having 1 carbon atom.
To 20 alkanes, C 6-20 aromatic hydrocarbon compounds, C 2-20 ethers or C 1-2
0 halogenated hydrocarbons. More specifically, examples of alkanes include pentane, heptane, octane, or isobutane, neopentane, cyclopentane, decalin, etc., examples of aromatic hydrocarbon compounds include benzene, toluene, xylene, etc., and examples of ethers include , Diethyl ether, tetrahydrofuran, 1,
2-dimethoxyethane and dioxane and the like,
Alternatively, examples of the halogenated hydrocarbon include dichloromethane, chloroform and the like. Further, the inert organic solvent may be a mixture of these.

In the method (A), an organic polymer compound containing a group having a carbonyl insoluble in an inert organic solvent at room temperature is heated at 40 ° C. to 250 ° C., preferably 60 ° C. to 200 ° C. in an inert organic solvent. The solution which is heated and dissolved in the contact temperature range and the organoaluminum oxy compound are mixed for 10 minutes to 24 minutes.
Mix and contact for contact time of time. Furthermore, from the solution subjected to the contact treatment, for example, an organic polymer compound supporting a powdery organoaluminum oxy compound can be obtained as follows. The solid component is precipitated by cooling. Precipitate by adding a poor solvent to the solution. The solution is sprayed on the poor solvent through a nozzle to cause precipitation. The solution is sprayed with a spray drier into an atmosphere in which the solvent is vaporized to be powdered. The solvent is removed from the solution, the mixture is dried and pulverized by a vibration mill, a ball mill or the like. ~
The operating temperature of is below the melting point temperature of the organic polymer compound.

In the method (B), the organic polymer compound is suspended in an inert organic solvent, and the organoaluminum oxy compound is contacted at a contact temperature range of -80 ° C to 200 ° C, preferably -20 ° C to 150 ° C. And mixing and contact for 10 minutes to 24 hours. Further, a poor solvent may be added to the contact-treated suspension. Alternatively, the solvent may be removed from the suspension and further pulverized by a vibration mill, a ball mill or the like.

The method (C) is the simplest method, and the organic polymer compound containing a group having a powdery carbonyl group is substantially mixed with a mixer or a mill in the absence of a solvent. -80 ° C to 200 ° C with a mixer or a crusher,
Preferably, the organoaluminum oxy compound is mixed and contacted in the contact temperature range of −20 ° C. to 150 ° C. for a contact time of 30 minutes to 24 hours. Further, the obtained powder may be suspended in a poor solvent.

The ratio of the amount of contact between the organic polymer compound containing a carbonyl group and the organoaluminum oxy compound in the above methods (A) to (C) is such that the organic polymer compound is 1 g of the organic polymer compound. 1 × 10 as the number of moles of aluminum contained in the aluminum oxy compound
^{-5 to} 0.1 mol / g, preferably 1 x 10 ^{-4 to} 0.01
Mol / g.

In the present invention, the organic polymer compound containing a group having a carbonyl carrying an organoaluminumoxy compound, which is obtained by the above-mentioned methods (A) to (C), is washed with an inert organic solvent, It is preferable to remove the unsupported organoaluminum oxy compound from the viewpoint of preventing the organoaluminum oxy compound from adhering to the inner wall of the reactor. As the washing method, an organic polymer compound carrying an organoaluminum oxy compound is suspended in an inert organic solvent, or after the inert organic solvent is rinsed with the organic polymer compound, filtration, decantation or centrifugation is performed. A method of separating and obtaining a washed product is exemplified. The inert organic solvent used here is preferably a solvent that dissolves the unsupported organic aluminum oxy compound and in which the organic polymer compound supporting the organic aluminum oxy compound is insoluble. The amount of washing solvent and the number of washings are not particularly limited. The washing temperature is not higher than the melting point temperature of the organic polymer compound.

In the method of polymerizing an olefin using a catalyst comprising an organic transition metal compound soluble in an inert organic solvent and a carrier insoluble in an inert organic solvent of the present invention, the organic transition metal compound and the organoaluminum oxy compound are used. The amount of the organic polymer compound supporting the organic transition metal compound used is the ratio of the number of moles of aluminum contained in the organic polymer compound supporting the organoaluminum oxy compound to the number of moles of the transition metal of the organic transition metal compound (aluminum / transition metal 1) to 10000, preferably 10 to 2000.

In the method of the present invention, an olefin can be polymerized with a catalyst composed of a carrier carrying an organic transition metal compound and an organic aluminum oxy compound, and when an organic metal compound is used in combination therewith, preferable results can be obtained. .

In the present invention, as the organometallic compound used in combination with the polymerization of the olefin, a metal is the first group of the periodic table.
Alkyl metal compounds selected from Group 2, Group 2, Group 12 and Group 13, specifically, lithium, sodium, potassium, or beryllium, magnesium, zinc, cadmium, or aluminum, gallium and carbon number 1 It is an organometallic compound consisting of ~ 20 alkyl. Particularly preferred is an alkylaluminum compound having 1 to 20 carbon atoms. Furthermore, specific examples of the alkylaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
Triisopropyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride,
Examples thereof include di-n-butylaluminum chloride, diisobutylaluminum chloride, and disec-butylaluminum chloride. Particularly preferred are trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum. , Tri-sec-butylaluminum.

The amount of the organic metal compound and the organic transition metal compound soluble in the inert organic solvent used is the ratio of the number of moles of the organic metal compound to the number of moles of the transition metal of the organic transition metal compound (organic metal compound / Transition metal) as 1 to 1000
It is 0, preferably 10 to 1000. The amount of the organoaluminum oxy compound supported on the organic metal compound and the organic polymer compound is the ratio of the number of moles of aluminum contained in the organic polymer compound to the number of moles of the organic metal compound (in the organic polymer compound). Aluminum / organometallic compound) of 0.01 to 100, preferably 0.1
It is -10. In the present invention, an inert organic solvent may be used for the preparation of the olefin polymerization catalyst, if necessary.

The inert organic solvent used for preparing the olefin polymerization catalyst includes propane, butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, and other alkanes, benzene, toluene, xylene, and other aromatic compounds. Hydrocarbon compounds or mixtures thereof are preferably used. Further, the catalyst preparation temperature of the organic transition metal compound and the carrier of the organic polymer compound supporting the organic aluminum oxy compound is −80 ° C. to 2
The temperature is 50 ° C., preferably −20 ° C. to 200 ° C., and the preparation time is 10 minutes to 3 days, preferably 20 minutes to 24 hours.

In the present invention, a catalyst comprising an organic transition metal compound soluble in an inert organic solvent and a carrier insoluble in the inert organic solvent may be previously polymerized or copolymerized with a small amount of olefin and used. As a result, effects such as improvement in bulk specific gravity of the produced polymer can be obtained. At this time, the amount of the olefin polymer to be contained by polymerizing or copolymerizing the olefin per 1 g of the solid catalyst is 0.1 to 300 g, preferably 0.5 to 100 g. The method of polymerizing a small amount of olefin in advance to prepare a solid catalyst includes a slurry polymerization method of polymerizing an olefin in an inert hydrocarbon, a bulk polymerization method of polymerizing in a liquefied monomer or a gas olefin monomer. Can be carried out by a gas phase polymerization method. The polymerization temperature is usually -100 to 200 ° C, preferably -20 to 100 ° C. The polymerization pressure is not particularly limited and may be normal pressure to 50 kg · f / cm ² , and may take any form of batch polymerization, semi-batch polymerization or continuous polymerization.

In the present invention, an olefin for polymerizing an olefin by using a catalyst composed of an organic transition metal compound soluble in an inert organic solvent and a carrier insoluble in the inert organic solvent is preferably α having 2 to 20 carbon atoms. -Olefins (including ethylene), more preferably 2-10 carbon atoms
Is an α-olefin. Specific examples include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane and styrene. Also,
Further, it has 4 to 20 carbon atoms such as butadiene, 1,4-pentadiene, 1,5-hexadiene, and 1,4-hexadiene.
Or a cycloolefin such as dicyclopentadiene, norbornene, methylnorbornene, tetracyclododecene, or methyltetracyclododecene, or a silicon-containing olefin such as allyltrimethylsilane or vinyltrimethylsilane. Further, these olefins may be polymerized alone or in combination of two or more kinds.

In the present invention, the polymerization of an olefin is not limited to a slurry polymerization method of polymerizing an olefin in an inert hydrocarbon, but a bulk polymerization method of polymerizing in an liquefied monomer or a gas polymerization in a gaseous olefin monomer. A phase polymerization method can also be used. Further, the catalyst of the present invention can be used for solution polymerization of olefins.

At this time, the polymerization temperature is -100 to
200 degreeC, Preferably it is -20-100 degreeC. The polymerization pressure is from normal pressure to 80 kg · f / cm ² , and any of polymerization forms such as batch polymerization, semi-batch polymerization or continuous polymerization may be adopted. It is also possible to control the molecular weight of the olefin polymer by using a molecular weight regulator such as hydrogen.

[0069]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

In the present invention, the melting point (Tm), molecular weight distribution index (PDI), intrinsic viscosity ([η]) and fisheye (FE) were measured by the following methods.

Melting point (Tm): differential scanning calorimetry (DS
The melting point (Tm) measured in C) was measured under the following conditions.
[Measuring device: Perkin Elmer DSC-4, temperature rising rate: 10 ° C / min, temperature lowering rate: -10 ° C / min, or -30 ° C / min].

Molecular weight distribution index (PDI = Mw / M
n): The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography under the following conditions. [Measuring device: Waters 15
0CVplus, column: Shodex GPC AD
-80 M / S (exclusion limit: 2 × 10 ⁷ ), mobile phase: 1,
3,5-trichlorobenzene, column temperature: 135 ° C,
Measurement flow rate: 1.0 ml / min, sample concentration: 0.2 wt
/ Vol%, injector capacity: 0.200 ml, detector: differential refractometer and viscometer, standard sample: polystyrene standard].

Intrinsic viscosity ([η]): Viscosity was measured in 135 ° C. tetralin. It is expressed in dl / g.

Fisheye or gel (FE: hereinafter simply called fisheye): 3,5-di-t-butyl-based on 100 parts by weight of polypropylene powder obtained by polymerization.
After adding 0.3 parts by weight of 4-hydroxytoluene and mixing, pelletizing was carried out at a resin temperature of 250 ° C.
A film having a thickness of 40 μm was obtained by melt-extrusion with a mmφ downward T-Die extruder at a resin temperature of 250 ° C. The film 600 cm ² 100 μm per area
The number of fish eyes and the number of fish eyes of less than 100 μm were measured.

Example 1 [Preparation of Polymer Compound Carrier (A) of Organoaluminum Oxy Compound] Maleic anhydride graft obtained by a method described in JP-B-59-14488 on a 200 ml four-necked flask which was sufficiently replaced with nitrogen. 5 g polypropylene
(Maleic anhydride content: 10 wt%, 1 mmol /
g) was suspended in 45 ml of toluene. 38 ml of a toluene solution containing 2.7 g of methylaluminoxane (manufactured by Albemarle, 8 wt%) was added to the suspension, and the mixture was heated with stirring at 80 ° C. for 6 hours, cooled to room temperature, and allowed to stand to give a pale yellow color. The solid was allowed to settle. Furthermore, the supernatant liquid was drained by decantation, 50 ml of toluene was added,
It heated at 70 degreeC for 30 minutes, and left still. This operation washing was repeated 3 times, and after removing the supernatant liquid, it was dried under reduced pressure to obtain 5.2 g of a pale yellow solid catalyst component (A). The aluminum content in this solid component was 3 mmol / g.

[Polymerization of Propylene] 480 mg of the above pale yellow solid catalyst component (A) was suspended in 20 ml of heptane in a 50 ml two-necked flask which was sufficiently replaced with nitrogen, and synthesized by the method described in JP-A-2-274703. Diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride 1.0m
g and 0.128 g of triisobutylaluminum were sequentially added to prepare a catalyst. Substantially replace with nitrogen,
Then, the prepared catalyst was charged into a 5-liter stainless autoclave substituted with propylene, 1.5 kg of propylene and 2 N liter of hydrogen were added, the temperature was raised, and polymerization was carried out at 60 ° C. for 1 hour. In this polymerization, there was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 430 g. The obtained polymer had an intrinsic viscosity [η] of 1.42 dl / g and a PDI of 2.4, and a T
m is 133 ° C., bulk density is 0.36 g / ml, FE
Has three fisheyes of 100 μm or more, 1
The number of fish eyes of less than 00 μm was 10.

Example 2 [Preparation of polymer compound carrier (B) of organoaluminum oxy compound] 20 g of maleic anhydride-grafted polypropylene (Mw: 4350) was added to 1 liter which was sufficiently replaced with nitrogen in a four flask.
0, maleic anhydride content: 6.7 wt%, 0.6 mmol / g) was suspended in 200 ml of toluene. 135 ml of a toluene solution of methylaluminoxane (manufactured by Albemarle, methylaluminoxane content 8 wt%) was added to the suspension under a nitrogen atmosphere, heated at 80 ° C for 6 hours with stirring, cooled to 40 ° C, and then the solvent was added. The mixture was distilled off under reduced pressure, and 300 ml of hexane, which was a yellow solid, was added, washed with stirring, and left to stand. 220m of supernatant by back filtration
I was drained. Further, wash with 400 ml of toluene,
350 ml was drained by the reverse filtration method. This operation washing was repeated 3 times and dried under reduced pressure to obtain 24.8 g of a pale yellow solid catalyst. The solid catalyst component (B) was manufactured by pulverizing with a ball mill . The aluminum content in this solid component is 3.6.
It was mmol / g.

[Polymerization of Propylene] Solid Catalyst Component (A)
480mg and hydrogen instead of 2N liters except that the above light-yellow solid catalyst component (B) 240 mg and hydrogen using 3N liter polymerizing Similarly propylene as in Example 1. There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 490 g. The intrinsic viscosity [η] of the obtained polymer was 1.22 dl / g, PDI
Is 2.4, Tm is 133 ° C., and bulk density is 0.36 g
The number of fish eyes of 100 μm or more was 8, and the number of fish eyes of less than 100 μm was 30.

Example 3 [Preparation of Polymer Compound Carrier (C) of Organoaluminum Oxy Compound] 1 g of maleic anhydride-grafted polypropylene (maleic anhydride content: 10 wt%, 1 mmol) was placed in a 500 ml four-necked flask which was sufficiently replaced with nitrogen. / G) was suspended in 400 ml of xylene, and then heated until boiling to completely dissolve the maleic anhydride-grafted polypropylene. To the boiling solution, using a dropping funnel, 10 ml of a toluene solution containing 0.68 g of methylaluminoxane (manufactured by Albemarle, 8% by weight of methylaluminoxane) was added, and after heating for 4 hours in a boiling state, it took 12 hours. Slowly cool to room temperature and let stand to precipitate a pale yellow solid component. Furthermore, the supernatant liquid was removed by decantation, 100 ml of toluene was added, and the temperature was 20 ° C.
The mixture was stirred for 30 minutes and left to stand. This washing operation was repeated 3 times, and the supernatant was drained to obtain a suspension containing the solid component (C). The concentration of the solid component in this suspension is 0.31
It was g / ml. Further, the aluminum content in the solid component measured by taking a predetermined amount of the suspension and drying it under reduced pressure was 6 mmol / g.

[Polymerization of Propylene] Take 0.77 ml of the obtained suspension in a 100-ml two-necked flask sufficiently replaced with nitrogen, add 20 ml of heptane,
Diphenylmethylene (cyclopentadienyl) (fluor
A catalyst was prepared by sequentially adding 1.0 mg of renyl) zirconium dichloride and 0.128 g of triisobutylaluminum. After charging the prepared catalyst into a 5 liter stainless steel autoclave which had been replaced with sufficient nitrogen and then replaced with propylene, 1.5 g of propylene was added.
Add 3N liters of kg and hydrogen, raise the temperature to 60 ° C,
Polymerization was carried out for 1 hour while maintaining the temperature. In this polymerization, there was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 490 g.

As a result of measuring the physical properties of the obtained polymer, the intrinsic viscosity [η] was 1.22 dl / g and the PDI was 2.
4, Tm is 134 ° C., bulk density is 0.36 g / ml
And FE has three fish eyes of 100 μm or more and one fish eye of less than 100 μm.
It was 0.

Example 4 [Preparation of polymer compound carrier (D) of organoaluminum oxy compound] The same procedure as in Example 3 was carried out except that the supernatant was drained and the solvent was removed to obtain a powder. 2 g of a pale yellow solid component was obtained. The aluminum content in this solid component was 6 mmol / g.

[Polymerization of Propylene] The procedure of Example 3 was repeated, except that 240 mg of a pulverized light yellow solid catalyst component (D) was used instead of the suspension.

In this polymerization, there was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The yield of the obtained polymer is 48.
It was 9.9 g. Intrinsic viscosity [η] of the obtained polymer
Is 1.12 dl / g, PDI is 2.4, and Tm is 1
34 ° C., bulk density is 0.36 g / ml, FE is 1
The number of fish eyes over 100μm is 3, 100μ
The number of fish eyes of less than m was 10.

Example 5 [Preparation of Polymer Compound Carrier (E) of Organoaluminum Oxy Compound] Maleic anhydride grafted polypropylene 4.2 was placed in a 3-liter four-necked flask which was sufficiently replaced with nitrogen.
g (Mw: 43500, maleic anhydride content: 6.7)
wt%, 0.68 mmol / g) was suspended in 1.7 liter of xylene and heated at 145 ° C. to completely dissolve it. Using a dropping funnel to the solution under reflux under a nitrogen atmosphere.
28 ml of a methylaluminoxane (manufactured by Albemarle, methylaluminoxane content 8 wt%) toluene solution was added, and the mixture was refluxed for 4 hours. Cool to 40 ℃, 200 ml
Hexane was added and the mixture was stirred for 30 minutes and allowed to stand. 1.6 liters of the supernatant liquid was drained by the reverse filtration method, 400 ml of toluene was added, and the suspension was stirred for 30 minutes and allowed to stand, 400 m
The supernatant liquid (1) was drained by reverse filtration. This toluene washing was repeated 3 times and dried under reduced pressure to obtain 6.0 g of a pale yellow solid. Further, the solid catalyst component (E) is pulverized by a vibration mill.
Was manufactured. Aluminum content in this solid component,
It was 4.7 mmol / g.

[Polymerization of Propylene] Solid Catalyst Component (B)
In the same manner as in Example 3 except that 240 mg of the above pale yellow solid catalyst component (E) was used, propylene was polymerized. There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 620 g. The intrinsic viscosity [η] of the obtained polymer was 1.29 dl / g, PDI
Is 2.1, Tm is 134 ° C., and bulk density is 0.31 g
The number of fish eyes of 100 μm or more was 12, and the number of fish eyes of less than 100 μm was 30.

Example 6 [(1R, 2R) -1,2- dimethylethylenebis (2
Synthesis of'-methylbenz [e] indenyl) zirconium dichloride] Trifluoromethanesulfonic anhydride (18.80 g)
To (2R, 3R) -2,3-butanediol (ee = 9
9.0%) (3.00 g) and pyridine (5.25 g) were added to a dichloromethane (100 ml) solution under ice cooling, and 1
Stir for hours. Furthermore, water was added, the organic phase was separated, dried over anhydrous magnesium sulfate, and the product obtained with hexane was passed through a silica gel column, concentrated and distilled to give a colorless liquid (2R, 3R) -2,3- Butyldi (triflate)
(5.31 g, 43 ° C./3 mmHg) was obtained. further,
Under a nitrogen atmosphere (2-methylbenz [e] indenyl)
Tetrahydrofuran of lithium (4.2 g) (hereinafter, T
It is written as HF. ) (50 ml) in solution (2R, 3R)-
T of 2,3-butyldi (triflate) (3.46 g)
A solution of HF (10 ml) was added dropwise at -78 ° C, and the mixture was stirred at room temperature for one day and then saturated aqueous ammonium chloride solution was added,
The organic phase was separated, dried over anhydrous magnesium sulfate, and concentrated to give an orange oil. It was then passed through a silica gel column with hexane / ethyl acetate and the solvent was removed to give a yellow solid. Further, it was recrystallized from benzene to obtain colorless crystals (2R, 3R) -2,3-bis (2-methylbenz [e] indenyl) butane (0.50 g). In addition, THF of this colorless crystal (310 mg)
(20 ml) solution with excess potassium hydride (95 mg)
Was added dropwise to a suspension of THF (30 ml) at 0 ° C., the mixture was stirred at room temperature for 24 hours, and then the suspension was filtered through Celite. This filtrate was added to zirconium tetrachloride (280 mg, 0.74 mm
ol) in THF (30 ml) at room temperature, and the mixture was stirred at room temperature for 24 hours. After removing the solvent, the obtained yellow solid was subjected to Soxhlet extraction with toluene, and the toluene was concentrated to obtain a yellow solid (200 mg). The analytical values are shown below.

¹ H-NMR (90 MHz, CDCl 3, TMS standard)
δ; 7.67-7.86 (m, 4H), 7.35-7.58 (m, 6H), 7.00
− 7.29 (m 4H), 3.48 (q, 2H), 1.26 (s, 6H), 1.24
(d, 6H) Elemental analysis; Calculated value C: 66.88, H: 4.91, Analytical value C: 66.97,
H: 4.98.

[Polymerization of Propylene] 480 mg of the solid catalyst component (A) prepared in Example 1 was added to 20 heptane in a 50 ml two-necked flask which had been sufficiently replaced with nitrogen.
(1R, 2R) -1,2- dimme
A catalyst was prepared by sequentially adding 1.0 mg of tylethylenebis (2′-methylbenz [e] indenyl) zirconium dichloride and 0.128 g of triisobutylaluminum. After thoroughly purging with 5 liters of nitrogen and then charging the prepared catalyst into a stainless steel autoclave substituted with propylene, 1.5 kg of propylene was added, the temperature was raised, and polymerization was carried out at 50 ° C. for 1 hour. With this polymerization,
There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 600 g. The obtained polymer had an intrinsic viscosity [η] of 1.58 dl / g, a PDI of 2.6, a Tm of 148 ° C., a bulk density of 0.38 g / ml, and an FE of 100 μm or more for fish eyes. The number was 3, and the number of fish eyes of less than 100 μm was 10.

Example 7 Polymerization was carried out in the same manner as in Example 6 except that 360 mg of the solid catalyst component (E) prepared in Example 5 was used and the polymerization temperature was 60 ° C. In this polymerization, there was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 680 g. The obtained polymer has an intrinsic viscosity [η] of 1.50.
dl / g, PDI is 2.3, Tm is 149 ° C., bulk density is 0.34 g / ml, FE has 16 fish eyes of 100 μm or more, and the number of fish eyes of less than 100 μm is FE. It was 40 pieces.

Example 8 [Catalyst component prepared by previously polymerizing with a small amount of propylene] 1 g of the pale yellow solid catalyst component (A) prepared in Example 1 was added to a heptane 6 mixture in a 50 ml two-necked flask sufficiently replaced with nitrogen.
A catalyst was prepared by suspending it in 0 ml and sequentially adding 3.0 mg of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride used in Example 1, and introducing propylene at 25 ° C. for 30 minutes at normal pressure. The catalyst was prepared by pouring from a tube and polymerizing 2 g of polypropylene.

[Polymerization of Propylene] Triisobutylaluminum (0.128 g) diluted with 20 ml of heptane was charged into a stainless steel autoclave which was sufficiently replaced with 5 liters of nitrogen and then replaced with propylene, and then, After charging 20 ml of the catalyst slurry prepared by previously polymerizing with propylene, 1.5 kg of propylene and 2 N liter of hydrogen were added and the temperature was raised to 60
Polymerization was carried out at ℃ for 1 hour. In this polymerization, there was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. Polymer yield is 4
It was 00 g. The polymer obtained had an intrinsic viscosity [η] of 1.40 dl / g, a PDI of 2.4 and a Tm of 13
4 ° C., bulk density is 0.36 g / ml, FE is 10
The number of fish eyes above 0μm is 3, 100μm
The number of fish eyes less than 10 was 10.

Comparative Example 1 [Preparation of Catalyst Component Consisting of Maleic Anhydride and Organoaluminum Oxy Compound] 0.37 g (3.7 mmol) of maleic anhydride was added to 30 ml of toluene in a 300 ml four-necked flask which was sufficiently replaced with nitrogen. Methylaluminoxane (manufactured by Albemarle, methylaluminoxane content 8
28% of toluene solution containing 2.0 g as wt%)
Was added, and the mixture was heated with stirring at 80 ° C. for 6 hours and cooled to room temperature. There was no solid precipitation in the yellow reaction mixture, but the interface was not clear but separated into two layers, a dark yellow part and a light yellow part. The light yellow portion of the upper layer was removed, 60 ml of toluene was added, and the mixture was stirred at room temperature for 30 minutes and allowed to stand. This operation washing was repeated 4 times. After draining the upper layer liquid,
After drying under reduced pressure, 1.7 g of a white solid catalyst component was obtained. Aluminum content in this solid component is 16 mmol / g
Met.

[Polymerization of Propylene] 240 mg of the above-mentioned white solid catalyst component was suspended in 20 ml of heptane in a 50 ml two-necked flask sufficiently replaced with nitrogen, and diphenylmethylene (cyclopentadienyl) (fluorenyl ) used in Example 1 was suspended. ) Zirconium dichloride 1.0 mg and triisobutylaluminum 0.128
A catalyst was prepared by sequentially adding g. Charge the prepared catalyst into a stainless steel autoclave that had been thoroughly replaced with 5 liters of nitrogen and then replaced with propylene,
Polymerization was carried out in the same manner as in Example 1. During this polymerization, polymer adhesion on the inner wall of the autoclave, the stirring blade and the shaft, or fouling significantly occurred. The polymer yield was 155 g. The obtained polymer had an intrinsic viscosity [η] of 1.29 dl / g, a PDI of 2.4, a Tm of 130 ° C. and a bulk density of 0.20 g / ml.

Comparative Example 2 [Preparation of Catalyst Component Consisting of Maleic Anhydride and Organoaluminum Oxy Compound] 0.55 g (5.5 mmol) of maleic anhydride was added to 30 ml of toluene in a 300 ml four-necked flask which was sufficiently replaced with nitrogen. Methylaluminoxane (manufactured by Albemarle, methylaluminoxane content 8
28% of toluene solution containing 2.0 g as wt%)
Was added, and the mixture was heated with stirring at 80 ° C. for 8 hours, cooled to room temperature, and allowed to stand. The supernatant liquid was removed from the precipitated pale yellow solid precipitate by decantation, 50 ml of toluene was added, and the mixture was heated at 70 ° C. for 30 minutes and allowed to stand. This operation washing was repeated 3 times, and after removing the supernatant liquid, it was dried under reduced pressure to 2.1.
g of a pale yellow solid catalyst component was obtained. The aluminum content in this solid component was 17 mmol / g.

[Polymerization of Propylene] 480 mg of the above pale yellow solid component was suspended in 20 ml of heptane in a 50 ml two-necked flask sufficiently replaced with nitrogen, and diphenylmethylene (cyclopentadienyl) (fluorenyl ) used in Example 1 was suspended. ) Zirconium dichloride 1.0 mg and triisobutylaluminum 0.128
A catalyst was prepared by sequentially adding g. After charging the prepared catalyst into a stainless steel autoclave sufficiently replaced with 5 liters of nitrogen and then replaced with propylene, 1.5 kg of propylene and 3.3 N liters of hydrogen were added and the temperature was raised to 60 ° C. Polymerized for 1 hour. During this polymerization, polymer adhesion on the inner wall of the autoclave, the stirring blade and the shaft, or fouling significantly occurred. The yield of polymer was 10 g. The intrinsic viscosity [η] of the obtained polymer was 0.89 dl / g, PDI
Is 3.2, Tm is 126 ° C., and bulk density is 0.26 g
/ Ml.

Comparative Example 3 [Preparation of Catalyst Component Consisting of Organoaluminum Oxy Compound and Silica] Silica (Asahi Glass Sildex) according to the method of catalyst A (preparation of catalyst) in the example described in JP-A-61-296008. H121) 5 g of toluene 25
45 ml of a toluene solution of methylaluminoxane used in Example 1 was added thereto, and silica was treated with aluminoxane to obtain 7.4 g of a solid catalyst component. The aluminum content in this solid component was 6 mmol / g.

[Polymerization of Propylene] 60 mg of the above solid catalyst component was suspended in 20 ml of heptane in a 50 ml two-necked flask sufficiently replaced with nitrogen, and diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride used in Example 1 was suspended. 1.0 m
g and 0.128 g of triisobutylaluminum were sequentially added to prepare a catalyst. The catalyst was charged in a stainless steel autoclave which was sufficiently replaced with 5 liters of nitrogen and then replaced with propylene, and then polymerization was carried out in the same manner as in Comparative Example 2. In this polymerization, there was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The yield of polymer was 500 g. The obtained polymer had an intrinsic viscosity [η] of 1.38 dl / g, a PDI of 2.6, and a T
m is 130 ° C., bulk density is 0.37 g / ml, FE
Is the number of fish eyes of 100 μm or more is 100
The number of fish eyes less than 100 μm is 6000
It was an individual.

Comparative Example 4 Toluene 1 was placed in a 50 ml two-necked flask which was sufficiently replaced with nitrogen.
1.7 g as methylaluminoxane (manufactured by Albemarle, methylaluminoxane content 8 wt%) in 0 ml
A catalyst was prepared by sequentially adding 23.8 ml of the toluene solution containing the compound and 2.0 mg of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride. The catalyst was charged into a stainless steel autoclave that was sufficiently replaced with 5 liters of nitrogen and then replaced with propylene, 1.5 kg of propylene and 3 N liters of hydrogen were added, and the temperature was raised to 60 ° C. Polymerization was continued for 1 hour. During this polymerization, polymer adhesion on the inner wall of the autoclave, the stirring blade and the shaft, or fouling significantly occurred. The yield of polymer was 495 g. The obtained polymer had an intrinsic viscosity [η] of 1.67 dl / g, a PDI of 2.1, a Tm of 140 ° C., a bulk density of 0.20 g / ml, and an FE of 100 μm or more. The number of fish eyes was 7, and the number of fish eyes of less than 100 μm was 14.

Comparative Example 5 100 mg of the solid catalyst component prepared in Comparative Example 3 was suspended in 20 ml of heptane in a 50 ml two-necked flask that had been sufficiently replaced with nitrogen, and used in Example 6 (1R, 2R) -1,2-.
A catalyst was prepared by sequentially adding 1.0 mg of dimethylethylene bis (2'-methylbenz [e] indenyl) zirconium dichloride and 0.16 g of triisobutylaluminum. Replace thoroughly with 5 liters of nitrogen,
Then, the prepared catalyst was charged into a stainless steel autoclave substituted with propylene, and then polymerized in the same manner as in Comparative Example 3. There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The yield of polymer was 467 g. The intrinsic viscosity [η] of the obtained polymer was 1.67 dl / g, P
DI is 2.5, Tm is 142 ° C, and bulk density is 0.3.
The FE was 8 g / ml, and the number of fish eyes having an FE of 100 μm or more was 300 and the number of fish eyes having an FE of less than 100 μm was 9000.

Example 9 [Isopropylidene (cyclopentadienyl) (2,7
-Synthesis of di-tert-butylfluorenyl) zirconium dichloride] It was synthesized according to JP-A-5-125112.
The analytical values are shown below. ¹ H-NMR (90 MHz, C ₆ D ₆ , TMS standard) δ; 7.93-7.50
(m, 6H), 6.16 (dd, 2H), 5.58 (dd, 2H) 2.08 (s, 6H), 1.3
4 (s, 18H) Elemental analysis; Calculated value C: 63.94, H: 6.29, Analytical value C: 64.07,
H: 6.68.

[Polymerization of Propylene] Diphenylmethylene (Cyclopentadienyl) (Fluoro
Renyl) zirconium dichloride 1.0 mg was replaced with isopropylidene (cyclopentadienyl) (2,7-di-tert- butylfluorenyl) zirconium dichloride 2.0 mg except that propylene was produced in the same manner as in Example 5. Was polymerized. There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The yield of polymer was 397 g. The obtained polymer has an intrinsic viscosity [η] of 0.70 dl.
/ G, PDI is 2.3, Tm is 137 ° C., bulk density is 0.35 g / ml, and FE has 8 fish eyes of 100 μm or more and 40 fish eyes of less than 100 μm. It was an individual.

Example 10 [Synthesis of ethylene bis (indenyl) zirconium dichloride] Scott Collins (Journal of Organometallic Ch
It was synthesized according to the method of emistry, 342 (1988) 21). The analytical values are shown below.

¹ H-NMR (90 MHz, C ₆ D ₆ , TMS standard)
δ; 7.33-6.70 (m, 8H), 6.41 (d, 2H), 5.73 (d, 2
H), 3.05 (q, 4H).

[Polymerization of Propylene] Diphenylmethylene (cyclopentadienyl) (fluor
Ethylene bis (indenyl) zirconium dichloride instead of 1.0 mg of renyl) zirconium dichloride.
Propylene was polymerized in the same manner as in Example 5 except that 0 mg was used. There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 97 g. The obtained polymer had an intrinsic viscosity [η] of 0.40 dl / g, a Tm of 133 ° C., a bulk density of 0.36 g / ml, and an FE of 14 fish eyes of 100 μm or more and 100 μm. Less than 50 fish eyes
It was an individual.

Comparative Example 6 In Comparative Example 3 using a 50 ml two-necked flask which was sufficiently replaced with nitrogen.
60 mg of the prepared solid catalyst component was suspended in 20 ml of heptane.
Turbid, diphenylmethylene (cyclopentadienyl)
(Fluorenyl)Zirconium dichloride 1.0 mg
Instead of isopropylidene(Cyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium
Comparative Example 3 except that 2.0 mg of mudic chloride was used.
Similarly, propylene was polymerized. Autoclave inner wall
Adhesion of polymer on the impeller and shaft, or
There was no howling. The polymer yield is 4
It was 17 g. The intrinsic viscosity [η] of the obtained polymer is
0.93 dl / g, Tm 132 ° C, bulk density
0.38 g / ml, FE is 100 μm or more
The number of fish eyes is 200, and the number of fish eyes is less than 100 μm.
The number of Sshu eyes was 9000.

Comparative Example 7 (1R, 2R) -1,2- dimethylethylenebis (2 ′)
-Propylene was polymerized in the same manner as in Comparative Example 5 except that 2.0 mg of ethylenebis (indenyl) zirconium dichloride was used instead of 1.0 mg of methylbenz [e] indenyl) zirconium dichloride. Adhesion of polymer on inner wall of autoclave, stirring blade and shaft,
Or there was no fouling. The yield of polymer was 105 g. The obtained polymer had an intrinsic viscosity [η] of 0.53 dl / g, a Tm of 142 ° C., a bulk density of 0.35 g / ml, and an FE of 150 fish eyes of 100 μm or more, 100 μm. The number of fish eyes below was 7,000.

Example 11 [Synthesis of rac- dimethylsilylenebis (2-methylbenz [e] indenyl) zirconium dichloride] Synthesis was carried out according to the method of Udo Stehling (Organometallics, 13, 964 (1994)). The analytical values are shown below.

¹ H-NMR (90 MHz, CDCl ₃ , TMS standard)
δ; 8.00-7.15 (m, 14H), 2.37.
(S, 6H), 1.34 (s, 6H) [Polymerization of propylene] Instead of ethylenebis (indenyl) zirconium dichloride, rac- dimethylsilylenebis (2-methylbenz [e] indenyl) zirconium dichloride 3.0 m
Propylene was polymerized in the same manner as in Example 10 except that g was used. There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 649 g. The obtained polymer has an intrinsic viscosity [η] of 1.09 dl / g, a Tm of 145 ° C., a bulk density of 0.36 g / ml, and an FE of 4 fish eyes of 100 μm or more and 100 μm. The number of fish eyes below was 35.

Example 12 [Synthesis of rac- dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride] Takaya Mise (Chemistry Letters, 1853 (1989)) ) And the like. The analytical values are shown below.

¹ H-NMR (90 MHz, CDCl ₃ , TMS standard)
δ; 6.43 (d, 2H), 5.27 (d, 2H), 2.28 (s, 6H), 2.05
(s, 6H), 0.77 (s, 6H) [Polymerization of propylene] Instead of ethylenebis (indenyl) zirconium dichloride, rac- dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethyl) Propylene was polymerized in the same manner as in Example 10 except that 2.0 mg of cyclopentadienyl) zirconium dichloride was used. There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 49 g. The obtained polymer had an intrinsic viscosity [η] of 0.77 dl / g, a Tm of 153 ° C., a bulk density of 0.35 g / ml, and an FE of
The number of fish eyes of 100 μm or more is 6, 100
The number of fish eyes of less than μm was 20.

Comparative Example 8 (1R, 2R) -1,2- dimethylethylenebis (2 ′)
-Propylene was polymerized in the same manner as in Comparative Example 5 except that 3.0 mg of rac- dimethylsilylenebis (2'-methylbenz [e] indenyl) zirconium dichloride was used in place of 1.0 mg of -methylbenz [e] indenyl) zirconium dichloride. . There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield is 58
It was 9 g. The obtained polymer had an intrinsic viscosity [η] of 1.26 dl / g, a Tm of 145 ° C., a bulk density of 0.35 g / ml, and an FE of 200 fish eyes of 100 μm or more, 100 μm. The number of fish eyes below was 6000.

Comparative Example 9 (1R, 2R) -1,2-Dimethyl ethyleneScrew (2 '
-Methylbenz [e] indenyl) zirconium dichloride
Rac-instead of 1.0 mg of lidDimethyl silylene
(2,4-dimethylcyclopentadienyl) (3 ', 5'
-Dimethylcyclopentadienyl) zirconium dichloride
Similar to Comparative Example 5 except that 2.0 mg of lid was used.
The ropylene was polymerized. Inner wall of autoclave, stirring blade and
Of polymer on the shaft and shaft, or foulin
There was no bug. The polymer yield was 30 g.
It was. The obtained polymer has an intrinsic viscosity [η] of 1.26d.
1 / g, Tm 149 ° C., bulk density 0.36 g /
ml and FE is 100 μm or more fisheye
The number of fish eyes is less than 100
The number was 9000.

Example 13 [Preparation of high molecular compound carrier (F) of organoaluminum oxy compound] 1.0 g of maleic anhydride-grafted polypropylene (Mw: 43500, maleic anhydride) was placed in a 1-liter glass autoclave which had been sufficiently replaced with nitrogen. (Content ratio: 6.7 wt%, 0.68 mmol / g) was suspended in 400 ml of xylene and heated at 130 ° C. to be completely dissolved. Under a nitrogen atmosphere, using a syringe, 7 ml of a methylaluminoxane (manufactured by Albemarle, methylaluminoxane content 8 wt%) toluene solution was added and 145
Heated at ° C for 4 hours. It was cooled to 40 ° C. and sprayed with 3 kg / cm ² of nitrogen from a spray nozzle into 3 liters of hexane through a siphon tube. The precipitate is filtered under nitrogen, 40
After rinsing with 0 ml of toluene and then with 200 ml of hexane, the residue was dried under reduced pressure to obtain 1.2 g of a pale yellow fine powdery solid. The aluminum content in this solid component is 4.
It was 3 mmol / g.

[Polymerization of Propylene] Solid Catalyst Component (E)
Polymerization of propylene was carried out in the same manner as in Example 5 except that 240 mg of the above pale yellow solid catalyst component (F) was used instead. There was no adhesion of polymer or fouling on the inner wall of the autoclave, the stirring blade and the shaft. The polymer yield was 600 g. The obtained polymer had an intrinsic viscosity [η] of 1.26 dl / g, a Tm of 134 ° C., a bulk density of 0.38 g / ml, and an FE of
The number of fish eyes of 100 μm or more is 4, 100
The number of fish eyes of less than μm was 10.

[0116]

EFFECT OF THE INVENTION By using the catalyst of the present invention, an olefin can be polymerized with high activity and a polymer having high stereoregularity can be obtained. Further, the polymer produced during the polymerization reaction, the organoaluminum oxy compound and the like are not attached to the inner wall of the reactor and are not stained, the bulk specific gravity of the polymer is high and the fisheye of the product is extremely low.

Since high productivity can be maintained and high quality products can be manufactured, the contribution to the industry is extremely large.

[Brief description of drawings]

FIG. 1 is a flow chart diagram to assist in understanding the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-9-100308 (JP, A) JP-A-7-53623 (JP, A) JP-A-63-260903 (JP, A) JP-A-8- 20606 (JP, A) JP 7-82314 (JP, A) Special table 9-509970 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/64-4 / 658

Claims (12)

(57) [Claims] 1. A polymerization catalyst comprising an organic transition metal compound soluble in an inert organic solvent and a carrier insoluble in the inert organic solvent, wherein the carrier is represented by the following general formula [1] An olefin polymerization catalyst comprising a polyolefin having a carbonyl-containing group. [Chemical 1] (In the formula, Q is hydrogen, hydroxy, alkyl, aryl,
It is selected from alkoxy, aryloxy, oxycarbonyl, halogen, amino, aminocarbonyl, hydrazino or oxyanion. ) Wherein the insoluble carrier in an inert organic solvent, containing a group having a carbonyl represented by the general formula [1] Po
Olefin polymerization catalyst according to claim 1, wherein is obtained by contacting an organic aluminum oxy compound Li olefins. Wherein the insoluble carrier in an inert organic solvent, containing a group having a carbonyl represented by the general formula [1] Po
The olefin is heated and dissolved in an inert organic solvent, and then the
Contains a group having a carbonyl represented by the general formula [1]
The catalyst for olefin polymerization according to claim 2, which is produced by contacting an organoaluminum oxy compound with a polyolefin . 4. The catalyst for olefin polymerization according to claim 2, wherein the organoaluminum oxy compound is at least one selected from the general formula [2] (formula 2) or the general formula [3] (formula 3). [Chemical 2] [Chemical 3] (In the formula, R ⁵ may be the same or different, is alkyl having 1 to 6 carbons, aryl having 6 to 18 or hydrogen, p 5
Is an integer of 2 to 50, preferably 10 to 35. ) 5. The carrier insoluble in an inert organic solvent is a polyolefin obtained by grafting or graft-polymerizing an unsaturated compound containing a group having a carbonyl represented by the general formula [1] onto a polyolefin. The catalyst for olefin polymerization described. 6. The catalyst for olefin polymerization according to claim 5, wherein the unsaturated compound containing a group having a carbonyl represented by the general formula [1] is an unsaturated organic acid anhydride. 7. The catalyst for olefin polymerization according to claim 1, which further contains an organometallic compound as a catalyst component. 8. The organometallic compound is represented by the first, second, or first periodic table.
The olefin polymerization catalyst according to claim 7, which is an organometallic compound of Group 2 or 13. 9. The catalyst for olefin polymerization according to claim 1, wherein the organic transition metal compound soluble in an inert organic solvent is a metallocene compound. 10. A metallocene compound represented by the following general formula [4]:
The catalyst for olefin polymerization according to claim 9, which is a compound selected from (Chemical Formula 4) or the general formula [5] (Chemical Formula 5). [Chemical 4] (In the formula, A ¹ and A ² are a cyclopentadienyl group, an indenyl group or a fluorenyl group, and one of A ¹ and A ² may be an amino group, and these groups are adjacent to each other. The substituents may directly bond to each other to form the same cyclic hydrocarbon substituent, and some or all of the hydrogen atoms in these groups may be alkyl having 1 to 20 carbons, or 6 carbons.
May be substituted with a substituent selected from aryl having 20 to 20 carbons, alkoxy having 1 to 20 carbons, aryloxy having 6 to 20 carbons, and silicon-containing alkyl having 1 to 20 carbons. M is a metal selected from Group 4 of the periodic table, and X ¹ ,
X ² is selected from halogen, alkyl having 1 to 20 carbons, or an anion ligand. ) [Chemical 5] (In the formula, A ³ and A ⁴ are a cyclopentadienyl group, an indenyl group or a fluorenyl group, and one of A ³ and A ⁴ may be an amino group, and these groups are adjacent to each other. The substituents may directly bond to each other to form the same cyclic hydrocarbon substituent, and some or all of the hydrogen atoms in these groups may be alkyl having 1 to 20 carbons, or 6 carbons.
May be substituted with a substituent selected from aryl having 20 to 20 carbons, alkoxy having 1 to 20 carbons, aryloxy having 6 to 20 carbons, and silicon-containing alkyl having 1 to 20 carbons, and A ³ and A ⁴ are They may be the same as or different from each other. M is a metal selected from Group 4 of the periodic table, and Y is-
^{CR 1 R 2 -, - CR} 1 R 2 -CR 3 R 4 -, or -SiR
¹ R ² — (R ¹ , R ² , R ³ or R ⁴ is hydrogen, 1 to 1 carbon atoms
20 alkyl, 6 to 20 carbon aryl, 1 carbon
˜20 alkoxy, C 6-20 aryloxy, C 1-20 silicon-containing alkyl,
R ¹ , R ² , R ³ and R ⁴ may be the same or different. ), X ¹ and X ² are halogen and have 1 to 1 carbon atoms.
20 alkyl or anionic ligands. ) 11. A poly- containing group having a carbonyl represented by the general formula [1] which is insoluble in an inert organic solvent.
A catalyst component for olefin polymerization, which comprises contacting an organoaluminum oxy compound with the carrier according to claim 1, which is an olefin. 12. A method for polymerizing an olefin using the polymerization catalyst according to claim 1.