JPH11286519A - Polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for polymerizing an olefin by which the high activity and high stereoregularity can be maintained and the molecular weight can readily be controlled. SOLUTION: The ratio of at least two kinds of organoaluminum compounds used as (C) an organoaluminum compound component is changed to control the molecular weight of a polyolefin in a method for polymerizing an olefin in the presence of a catalyst comprising (A) a compound component of a group 4 transition metal of the periodic table, (B) an organoaluminumoxy compound component and the component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for polymerizing olefins. More specifically, the present invention relates to a method for polymerizing an olefin in which the molecular weight of a polyolefin is controlled by changing the usage ratio of at least two kinds of organoaluminum compounds which are components of a polymerization catalyst.

[0002]

2. Description of the Related Art As homogeneous catalysts for olefin polymerization, so-called metallocene compounds are well known. A method of polymerizing an olefin using a normal metallocene compound, particularly a method of stereoregularly polymerizing an α-olefin,
Since reported by W. Kaminsky et al. (Angew. Chem., 9
7,507 (1985)) Many improvements have been made. As an example of these improvements, an attempt to improve the stereoregularity of a polymer obtained by a method of substituting some of the hydrogens of a cyclopentadienyl group with an alkyl group is generally made (Yamazaki et al.,
Chemistry Letters, 1853 (1989), JP-A-4-26830
No. 7). Also, many attempts have been reported to improve the stereoregularity of olefin polymers by metallocene compounds having an ethylene-bridged bisindenyl derivative as a ligand (see, for example, Organometallics, 13,
954 (1994), J. Organmet. Chem., 288, 63 (1985), etc.). The polymerization of α-olefins with these Cl-symmetric metallocene compounds is known to give isotactic polyolefins in the presence of methylaluminumoxy compounds.

[0003] It is known that polymerization of an α-olefin in the presence of a Cs-symmetric metallocene compound and a methylaluminum oxy compound of JA Ewen et al. Gives a syndiotactic polyolefin (see, for example, J. Mol.
Am. Chem. Soc. 110, 6255 (1988), JP-A-2-41303.
No.).

In these polymerizations, a method in which an organic aluminum compound is used in combination to reduce the amount of an expensive organic aluminum oxy compound and maintain the catalytic activity is disclosed in JP-A-60-260602 and JP-A-63-13060.
No. 1 and other publications. Japanese Patent Application Laid-Open No. Sho 60-35006 discloses polymerization of an olefin in the presence of a metallocene-supported catalyst on a solid organic aluminum oxy compound catalyst component obtained by contacting an organic aluminum oxy compound with an inorganic oxide such as silica gel or alumina. JP-A-61-296008, JP-A-63-66206 and JP-A-2-173104,
In these methods, it is known that an organoaluminum compound is used in combination to maintain the catalytic activity.

In the polymerization of olefins using a metallocene compound as described above, the control of the molecular weight of the polyolefin is carried out by a method of changing the polymerization temperature or a method utilizing a chain transfer reaction with hydrogen (for example, JP-A-3-41).
No. 303, JP-A-2-274703, etc.).

[0006]

However, the method of changing the polymerization temperature greatly affects the stereoregularity and the catalytic activity of the polyolefin, and the lower the polymerization temperature, the higher the stereoregularity and the molecular weight. If the polymerization temperature is lowered and conversely the polymerization temperature is raised, the catalytic activity is increased, but the stereoregularity and the molecular weight are lowered. In the method utilizing a chain transfer reaction by hydrogen, particularly in the case of a metallocene compound produced by polymerizing an isotactic polyolefin, this catalyst causes a chain transfer very sensitively to hydrogen, and a small amount of hydrogen is produced. There is a problem that the molecular weight is largely changed in response to the fluctuation. In the commercial production of polyolefins, the catalytic properties of such metallocene compounds have hindered stable production in production plants, making commercial production very difficult.

[0007]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and have succeeded in reducing the polymerization catalyst activity of olefins and the stereoregularity of polyolefins, and without impairing the controllability of molecular weight. The present inventors have made intensive studies on a method for polymerizing olefins, which enables stable control of molecular weight and enables stable commercial production, and completed the present invention.

That is, the olefin polymerization method of the present invention comprises:
In a method of polymerizing an olefin in the presence of a catalyst comprising (A) a transition metal compound of Group 4 of the periodic table, (B) an organoaluminum oxy compound, and (C) an organoaluminum compound, at least one component (C) The present invention is characterized in that the molecular weight of the polyolefin is controlled by using two kinds of organoaluminum compounds and changing the use ratio.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, (A) a transition metal compound component of Group 4 of the periodic table has the following general formula [1]:

[0010]

Embedded image (Wherein A ¹ and A ² are alkyl having 1 to 20 carbons, aryl having 6 to 20 carbons, alkoxy having 1 to 20 carbons, aryloxy having 6 to 20 carbons, silicon having 1 to 20 carbons A hydrogen selected from the group consisting of
Substituted cyclopentadienyl, 0-7 substituted indenyl, 0-9 substituted fluorenyl, or 0
It is a disubstituted amino, and these substituents may be directly bonded to adjacent substituents to form the same cyclic hydrocarbon substituent. A ¹ and A ² may be the same or different from each other. M is a metal selected from Group 4 of the periodic table; X ¹ and X ² are halogen;
Selected from alkyl or anionic ligands of )

Alternatively, the following general formula [2]

[0012]

Embedded image(Where A^Three , A^Four Is alkyl having 1 to 20 carbon atoms, charcoal
Aryl having 6 to 20 primes, alkoxy having 1 to 20 carbons
C, aryloxy having 6 to 20 carbon atoms, 1 to 20 carbon atoms
Is a substituent selected from silicon-containing alkyl of
4-substituted cyclopentadienyl group, 0-6 substituted
An indenyl group, a 0-8 substituted fluorenyl group, or
Or an amino group substituted with 0 to 1;
Are the same cyclic carbon
A hydrogen substituent may be formed. A ^Three , A^Four Are each other
They may be the same or different. M is group 4 of the periodic table
And Y is -CR¹ R^Two -, -CR
¹ R^Two -CR^Three R^Four -Or -SiR¹ R^Two − (R
¹ , R^Two , R^Three Or R^Four Is hydrogen, having 1 to 20 carbon atoms
Alkyl, aryl having 6 to 20 carbons, 1 to 20 carbons
Alkoxy, aryloxy having 6 to 20 carbon atoms, carbon
Selected from silicon-containing alkyls of Formulas 1 to 20;
¹ , R^Two , R^Three And R^Four Are the same but different
May be. ), X ¹ , X^Two Is halogen, having 1 to 1 carbon atoms
Selected from 20 alkyl or anionic ligands. )
It is.

In the general formulas [1] and [2], examples of the alkyl having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl or isopropyl, tert-butyl, neopentyl or cyclopentyl, cyclohexyl, menthyl and the like. Can be Examples of the aryl having 6 to 20 carbon atoms include phenyl, tolyl, and naphthyl. Examples of the alkoxy having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, or isopropoxy, tert-butoxy, neopentyloxy, cyclopentyloxy, cyclohexyloxy, and mentoxy. 6 to 2 carbon atoms
Examples of the aryloxy of 0 include phenoxy, toloxy, xylyloxy and naphthoxy.

Further, examples of the silicon-containing alkyl having 1 to 20 carbon atoms include trimethylsilyl, dimethylethylsilyl, diphenylmethylsilyl, cyclohexyldimethylsilyl, triphenylsilyl and 2- (methyldiphenylsilyl) ethyl. Further, adjacent substituents may be directly bonded to form the same cyclic hydrocarbon substituent, and specifically, cyclopenta, cyclohexa,
Cyclohepta, benz or naphtha groups and derivatives thereof are mentioned.

Further, Y in the general formula [2] is -CR
¹ R^Two -, -CR¹ R^Two -CR^Three R ^Four -Or -Si
R¹ R^Two -, Specifically, methylene and dimethyl
Tylene, diphenylmethylene, cyclohexylidene or
Is ethylene, 1,2-dimethylethylene, 1,1,2,2
2-tetramethylethylene or dimethylsilylene, di
Examples include phenylsilylene and methylphenylsilylene
It is.

In the general formulas [1] and [2],
M is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium.
X ¹ and X ² are selected from halogen, an alkyl group or an anionic ligand; halogen is selected from fluorine, chlorine, bromine, and iodine; and alkyl having 1 to 20 carbon atoms is methyl, ethyl, Propyl or isopropyl or cyclohexyl and the like. Further, as the anion ligand, an organic phosphorus compound such as trimethylphosphine, triethylphosphine, triphenylphosphine or diphenylmethylphosphine, or an alkoxy ligand of methoxy or tert-butoxy or phenoxy, or tetrahydrofuran, diethyl ether, dioxane or 1, Ether compounds such as 2-dimethoxyethane are exemplified.

Specific examples of the transition metal compounds of the general formulas [1] and [2] in the present invention are shown below, but are not particularly limited as long as they are transition metal compounds that polymerize olefins.

As the transition metal compound of the general formula [1],
Bis (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, 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-
Examples include t-butylfluorenyl) zirconium dimethyl, pentamethylcyclopentadienyl (di-t-butylamido) zirconium dimethyl, and metallocene compounds in which zirconium of the above transition metal compound is replaced with titanium or hafnium.

The transition metal compound of the general formula [2] includes dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (tetramethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilyl (2,4-dimethylcyclopentadienyl)
(3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilyl (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5'-trimethylcyclopentadienyl) zirconium dichloride, Dimethylsilylbis (t-butylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (trimethylsilylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2-trimethylsilyl-4-t-butylcyclopentadienyl) zirconium dichloride, dimethyl Silyl bis (4,5,6,7
-Tetrahydro-indenyl) zirconium dichloride, dimethylsilylbis (indenyl) zirconium dichloride, dimethylsilylbis (2-methylindenyl) zirconium dichloride, dimethylsilylbis (2,4-dimethylindenyl) zirconium dichloride, dimethylsilylbis (2 , 4,7-trimethylindenyl) zirconium dichloride, dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylbis (2-ethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylbis ( Benz [e] indenyl) zirconium dichloride, dimethylsilylbis (2-methylbenz [e] indenyl) zirconium dichloride, dimethylsilylbis (3-methylbenz) e] indenyl) zirconium dichloride, dimethylsilylbis (benz [f] indenyl) zirconium dichloride, dimethylsilylbis (2-methylbenz [f] indenyl) zirconium dichloride, dimethylsilylbis (3-methylbenz [f] indenyl) zirconium dichloride, Dimethylsilylbis (cyclopenta [cd] indenyl)
Zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, dimethylsilylbis (tetramethylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (methylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (dimethylcyclopentadi Enyl) zirconium dimethyl, dimethylsilyl (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilyl (2,3
5-trimethylcyclopentadienyl) (2 ′, 4 ′,
5'-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (t-butylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (trimethylsilylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (2-trimethylsilyl-4-) t-butylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7-
Tetrahydro-indenyl) zirconium dimethyl, dimethylsilylbis (indenyl) zirconium dimethyl, dimethylsilylenebis (2-methylindenyl) zirconium dimethyl, dimethylsilylbis (2,4-dimethylindenyl) zirconium dimethyl, dimethylsilylbis (2 4,7-trimethylindenyl) zirconium dimethyl, dimethylsilylbis (2-methyl-4
-Phenylindenyl) zirconium dimethyl, dimethylsilylbis (2-ethyl-4-phenylindenyl)
Zirconium dimethyl, dimethylsilylbis (benz [e] indenyl) zirconium dimethyl, dimethylsilylbis (2-methylbenz [e] indenyl) zirconium dimethyl, dimethylsilylbis (3-methylbenz [e] indenyl) zirconium dimethyl, dimethylsilylbis ( Benz [f] indenyl) zirconium dimethyl, dimethylsilylbis (2-methylbenz [f]
Indenyl) zirconium dimethyl, dimethylsilylbis (3-methylbenz [f] indenyl) zirconiumdimethyl, dimethylsilylbis (cyclopenta [cd]
Indenyl) zirconium dimethyl and the like, and transition metal compounds in which zirconium of the above transition metal compound is replaced with titanium or hafnium.

Further, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-indenyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butylfluorenyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl-3-methylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-4-methylfluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl-fluorenyl)
Zirconium dichloride, isopropylidene (dimethylcyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (tetramethylcyclopentadienyl-fluorenyl) zirconium dichloride,
Or diphenylmethylene (cyclopentadienyl-
Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-indenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-) 3-methylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-
4-methylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, diphenylmethylene (methylcyclopentadienyl-fluorenyl) zirconium dichloride, diphenylmethylene (dimethylcyclopentadienyl-) Fluorenyl) zirconium dichloride, diphenylmethylene (tetramethylcyclopentadienyl-fluorenyl) zirconium dichloride, or cyclohexylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-indenyl) zirconium dichloride, cyclohexyl Silidene (cyclopentadienyl-2,7-di-t-butylfluorenyl)
Zirconium dichloride, cyclohexylidene (cyclopentadienyl-3-methylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl-4-methylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl- (Octahydrofluorenyl) zirconium dichloride, cyclohexylidene (methylcyclopentadienyl-fluorenyl) zirconium dichloride, cyclohexylidene (dimethylcyclopentadienyl-fluorenyl) zirconium dichloride, cyclohexylidene (tetramethylcyclopentadienyl- Fluorenyl) zirconium dichloride, or dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilylene Lopentadienyl-indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-3-methylfluorenyl) zirconium dichloride, dimethyl Silylene (cyclopentadienyl-
4-methylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-octahydrofluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilylene (dimethylcyclopentadienyl- Fluorenyl) zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl-fluorenyl) zirconium dichloride, or isopropylidene (cyclopentadienyl-fluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl-indenyl) zirconium dimethyl, isopropylidene ( Cyclopentadienyl-2,7
-Di-t-butylfluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl-fluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium Dimethyl, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl-
Indenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dimethyl, and the like, and transition metal compounds in which zirconium of the above transition metal compound is replaced with titanium or hafnium, and the like. .

Further, ethylenebis (indenyl) zirconium dichloride, ethylenebis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride,
1,2-dimethylethylenediyl-1,2-bis (indenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (2'-methylindenyl) zirconium dichloride, 1,2-diisopropylethylenediyl -1,2-bis (indenyl) zirconium dichloride, 1,2-diisopropylethylenediyl-1,2-bis (2'-methylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-
1,2-bis (3'-methylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2
-Bis (4'-isopropylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2
-Bis (4 ', 7'-diisopropylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (2'-methyl-4'-isopropylindenyl) zirconium dichloride, 1,2-dimethyl Ethylenediyl-1,2-bis (4'-cyclohexylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (2'-methyl-4 '
-Cyclohexylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (4'-phenylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (4 ', 7 '-Diphenylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-
Bis (2'-methyl-4'-phenylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (4'-naphthylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-
1,2-bis (2'-methyl-4'-naphthylindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (5'-phenylindenyl)
Zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (4′-methoxyindenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (benz [e] indenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,
2-bis (2'-methylbenz [e] indenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (3'-methylbenz [e] indenyl) zirconium dichloride, 1,2-dimethylethylenediyl- 1,2-bis (benz [f] indenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (2'-methylbenz [f] indenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1 , 2-bis (3'-methylbenz [f] indenyl) zirconium dichloride, 1,2-dimethylethylenediyl-1,2-bis (cyclopenta [cd]
(Indenyl) zirconium dichloride, or ethylenebis (indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, 1,2-dimethylethylenediyl-
1,2-bis (2'-methyl-4'-isopropylindenyl) zirconium dimethyl, 1,2-dimethylethylenediyl-1,2-bis (4 ', 7'-diisopropylindenyl) zirconium dimethyl, 2-dimethylethylenediyl-1,2-bis (2'-methyl-4 '
-Phenylindenyl) zirconium dimethyl, 1,2
-Dimethylethylenediyl-1,2-bis (2'-methyl-4'-naphthylindenyl) zirconium dimethyl, 1,2-dimethylethylenediyl-1,2-bis (benz [e] indenyl) zirconium dimethyl,
1,2-dimethylethylenediyl-1,2-bis (2 ′
-Methylbenz [e] indenyl) zirconium dimethyl, 1,2-dimethylethylenediyl-1,2-bis (3'-methylbenz [e] indenyl) zirconium dimethyl and the like, and zirconium of the above transition metal compound was replaced with titanium or hafnium. Transition metal compounds and the like.

Furthermore, ethylene (t-butylamido-cyclopentadienyl) zirconium dichloride, ethylene (t-butylamido-tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (t
-Butylamide-tetramethylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene (t-butylamido-indenyl) zirconium dichloride, dimethylsilylene (t-butylamido-fluorenyl) zirconium dichloride (tetrahydrofuran), dimethylsilylene (t-butylamido-fluorenyl) zirconium dichloride (diethylether), ethylene (t-
Butylamido-cyclopentadienyl) zirconium dimethyl, ethylene (t-butylamido-tetramethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (t-butylamido-tetramethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (t-butylamido- Indenyl) zirconium dimethyl, dimethylsilylene (t-butylamido-fluorenyl) zirconium dimethyl (tetrahydrofuran), dimethylsilylene (t-butylamido-fluorenyl) zirconium diphenyl and the like, and transition metal compounds in which zirconium of the above transition metal compound is replaced by titanium or hafnium Is mentioned.

In the present invention, (B) the organoaluminum oxy compound component includes the following general formula [3]:

[0024]

Embedded image

Alternatively, a compound represented by the general formula [4] is used.

[0026]

Embedded image (In the formula, R ₅ may be the same or different and is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or hydrogen, and p is an integer of 2 to 50, preferably 10 to 35. ).

In the present invention, a solid catalyst component obtained by bringing the organic aluminum oxy compound represented by the general formulas [3] and [4] into contact with an organic polymer having a functional group can be used.

The functional group of the organic polymer compound having a functional group used in the present invention includes aldehyde, carboxy, ketone, carboxycarbonyl (dicarboxylic anhydride), ester, carbonyl halide, amide, imide and the like. No.

The organic polymer compound having a functional group used in the present invention includes (1) a polymer obtained by polymerizing a monomer containing the functional group, and (2) a polymer having no functional group. A compound obtained by grafting or graft-polymerizing a monomer having the functional group onto a compound, and (3) a compound obtained by modifying the compound with the functional group or a precursor compound of the functional group can be used.

Further, these will be specifically described.
Examples of the organic polymer compound obtained by polymerizing a monomer having a functional group of (1) include, for example,
Acrylics such as methacrylic acid and acrylic acid, acrylates such as methyl methacrylate and methyl acrylate, acrylamides such as methacrylamide, acrylamide, crotonamide, vinyl acetate, methyl vinyl ketone, acryloyl chloride, acrylaldehyde, etc. Lactones such as vinyls and β-propiolactone; lactams such as ε-caprolactam; isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate and octamethylene diisocyanate; β-benzylaspartic anhydride; 4-benzyloxazolyl N-carboxyamino acid anhydrides such as do-2,5-dione, aminocarboxylic acids such as ε-aminocaproic acid and ω-aminoundecanoic acid, maleic anhydride, itaconic anhydride, phthalic anhydride, anhydride Carboxylic anhydrides such as pyromellitic acid, hexamethylenediamine, nonamethylenediamine, amines such as phenylenediamine, adipic acid,
Dicarboxylic acids such as maleic acid and itaconic acid; haloformyls such as adipic dichloride and phthalic acid; esters such as dimethyl terephthalate; or alcohols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, and bisphenol A Monomers selected from such as alone, in combination of two or more of the above monomers, or monomers having no functional group with the above monomers, for example, α-olefins, styrenes, epoxies, ethers and the like Organic polymer compounds obtained by performing polymerization or copolymerization in combination by radical polymerization, cationic polymerization, anionic polymerization, transition metal catalyzed polymerization and ring-opening polymerization, and further by a polyaddition reaction, an addition condensation reaction or a polycondensation reaction.

The organic polymer compound obtained by grafting or graft-polymerizing the monomer having a functional group of (2) includes a polymer compound having no functional group, for example,
Polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, ethylene-butene copolymer, ethylene-propylene-butene copolymer, polyisobutene, polypentene, poly4-methylpentene, polynorbornene, polybutadiene, polyisoprene, polystyrene, poly-α-methylstyrene, poly Polymer compounds such as ethylene oxide, polypropylene oxide, polytetrahydrofuran, and polysiloxane include, for example, the above-mentioned monomers such as methacrylic acid, acrylic acids such as acrylic acid, methyl methacrylate, 3-methacryloxypropyltrimethoxysilane, and methyl acrylate Acrylates such as methacrylamide, acrylamide, crotonamide, etc., vinyl acetate, methyl vinyl ketone Vinyls such as acryloyl chloride and acrylaldehyde; haloformyls such as acetyl chloride, adipic dichloride and phthalic dichloride; carboxylic anhydrides such as acetic anhydride, maleic anhydride and itaconic anhydride; maleic acid and itaconic acid; Organic polymer compounds obtained by grafting or graft-polymerizing a dicarboxylic acid or the like by a reaction such as a radical reaction or a Friedel-Kraft reaction are exemplified.

Examples of the organic polymer compound obtained by modifying the compound (3) containing a functional group or the precursor compound of the functional group include a polymer compound to be modified, for example, polyvinyl alcohol, PVC,
Organic polymer compounds obtained by partially modifying or modifying polymer compounds such as polyvinylpyridine, nitrated polystyrene, polyacrylonitrile, and cellulose by, for example, esterification, oxidation, reduction, and acylation reactions. Is mentioned.

As the organic polymer compound containing these functional groups, preferably, polyethylene, polypropylene obtained by grafting maleic anhydride, itanconic anhydride, methacrylic acid, acrylic acid, methyl methacrylate, methyl acrylate, etc. by a radical reaction Polyolefins such as polyethylene and polypropylene grafted with maleic anhydride are particularly preferred because of their simple synthesis.

The method of bringing an organic aluminum oxy compound into contact with an organic polymer compound having a functional group used in the present invention to form a solid catalyst component includes the following methods: (I) a method comprising dissolving a functional group dissolved in a heated inert organic solvent; A method of contacting an organic aluminum oxy compound with an organic polymer compound having a group, (II) a method of contacting an organic aluminum oxy compound with an organic polymer compound having a functional group suspended in an inert organic solvent, III) A method of bringing an organic aluminum oxy compound into contact with an organic polymer compound containing a functional group of a powder.

The inert organic solvent used here is an alkane, aromatic hydrocarbon, ether or halogenated hydrocarbon, preferably an alkane having 1 to 20 carbon atoms.
C6-C20 aromatic hydrocarbon compound, C2-C2
0 ethers or 1-20 halogenated hydrocarbons. More specifically, alkanes include pentane, heptane, octane, or isobutane, neopentane,
Cyclopentane or decalin and the like, as the aromatic hydrocarbon compound, benzene, toluene, xylene and the like, and as the ether, diethyl ether,
Examples include tetrahydrofuran, 1,2-dimethoxyethane, dioxane, and the like, and examples of the halogenated hydrocarbon include dichloromethane, chloroform, and the like.
Further, the inert organic solvent may be a mixture thereof.

Further, in the method (I), an organic polymer compound having a functional group insoluble in an inert organic solvent at room temperature is treated with an inert organic solvent at 40 ° C. to 250 ° C., preferably 60 ° C.
The solution heated and dissolved at a temperature of from 0 ° C to 200 ° C is mixed with the organic aluminum oxy compound and brought into contact. further,
A poor solvent may be added to the contact-treated solution, and the precipitate may be filtered, the solvent may be removed, and the solution may be further ground by a vibration mill, a ball mill, or the like.

In the method (II), an organic polymer compound having a functional group is suspended in an inert organic solvent,
It is mixed with the organoaluminum oxy compound at a temperature of from 200C to 200C, preferably from -20C to 150C, and brought into contact.
Further, a poor solvent may be added to the suspension subjected to the contact treatment. Also, the solvent was removed from the suspension,
It may be pulverized by a ball mill or the like.

In the method (III), an organic polymer compound having a powdery functional group is substantially mixed with a mixer or a mill such as a mill or a pulverizer in the absence of a solvent.
The organoaluminum oxy compound is mixed and contacted at a temperature of 80C to 200C, preferably -20C to 150C. Further, the obtained powder may be suspended in a poor solvent.

The above (I) to (I) used in the present invention
The solid catalyst component obtained by the method (III) may be washed with an inert organic solvent, if necessary.

The above (I) to (II) used in the present invention
In the synthesis of the solid catalyst component according to the method I), the contact ratio of the organic polymer compound having a functional group and the organic aluminum oxy compound is 1 g of the organic polymer compound to aluminum contained in the organic aluminum oxy compound. Is 1 × 10 ^{−5 to} 0.1 mol / g, preferably 1 × 10 ^{−4 to} 0.01 mol / g.

Further, in the present invention, a solid catalyst component obtained by contacting an organic aluminum oxy compound represented by the general formulas [3] and [4] with an inorganic oxide can be used.

The inorganic oxide used in the present invention is S
iO_Two , Al_Two O_Three , CaO, Na _Two O, K_Two O, Mg
O, MnO, TiO_Two , ZrO_Two With various oxides such as
Objects with cavities or relatively large pores and large surface area
Can be used preferably, hollow inorganic oxides, oxidized
Gels etc. can also be used, and usually have a diameter of 1 μm to 0.1 mm
Some are preferred. Above all, silica gel
Those containing aluminum or alumina
This is preferable because the amount of the compound to be supported can be increased.

Before the inorganic oxide is brought into contact with the organoaluminum oxy compound, the inorganic oxide is calcined and dried before use, but may be anhydrous or contain up to 10% by weight of adsorbed water. Since it is considered that the organic aluminum oxy compound is fixed by reacting with the hydroxyl groups present on the surface of these inorganic oxides, firing at an excessively high temperature results in a decrease in the number of hydroxyl groups on the surface, and the amount of the organic aluminum oxy compound carried Is undesirably caused by a decrease in catalytic activity. On the other hand, if the amount of adsorbed water exceeds 10% by weight, the organoaluminum oxy compound is only insolubilized by the adsorbed water and is carried, so that it is redissolved in toluene when the organoaluminum compound coexists, which is not preferable. .

The solid catalyst component obtained by bringing the organoaluminum oxy compound used in the present invention into contact with an inorganic oxide can be used in combination with the above-mentioned inert organic solvents such as alkanes, aromatic hydrocarbons, ethers or halogenated hydrocarbons. It is obtained by suspending the inorganic oxide, mixing with an organic aluminum oxy compound at a temperature of 50 ° C to 200 ° C, and contacting the mixture.

Here, the contact amount of the organic aluminum oxy compound is at least the amount of the organic aluminum oxy compound to be supported on the inorganic oxide, and is 1.5 times or more, preferably 2.0 times or more. If the amount of the organic aluminum oxy compound is less than 1.5 times, sufficient catalytic activity cannot be obtained, which is not preferable.

After the contact between the inorganic oxide and the organic aluminum oxy compound, the unreacted organic aluminum oxy compound is separated from the solid catalyst component. The separation method is not particularly limited, but a normal filtration method or a decantation method of the supernatant after standing can be used. Further, the separated solid catalyst component may be washed with an inert organic solvent, if necessary.

In the present invention, (B) an organic aluminum oxy compound represented by the above general formulas (3) and (4), which is an organic aluminum oxy compound component, and an organic polymer compound having a functional group, The amount of the solid catalyst component obtained by contacting the organoaluminum oxy compound or the solid catalyst component obtained by contacting the organoaluminum oxy compound with the inorganic oxide is (A) a transition metal compound component of Group 4 of the periodic table. The ratio of the number of moles of aluminum contained in the organoaluminum oxy compound or the organoaluminum oxy compound in the solid catalyst component to the number of moles of the transition metal of the compound (aluminum / transition metal) is from 1 to 10,000, preferably from 10 to 2,000. .

In the present invention, at least two kinds of organoaluminum compounds are used as the (C) organoaluminum compound component, and the (C) is used for controlling the molecular weight of the polyolefin by changing the use ratio.
The component is an alkylaluminum compound having 1 to 20 carbon atoms, specifically, trimethylaluminum,
Triethyl aluminum, tripropyl aluminum,
Triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisopropylaluminum chloride, din
-Butylaluminum chloride, diisobutylaluminum chloride, disec-butylaluminum chloride and the like. In particular, a combination of a primary alkyl alkyl aluminum compound and a secondary or tertiary alkyl alkyl aluminum compound is preferred. More specifically, a combination of triethylaluminum and triisobutylaluminum is preferable.

In the present invention, the amount of at least two kinds of the organoaluminum compound and the transition metal compound used for controlling the molecular weight of the polyolefin is determined by the number of moles of the organoaluminum compound relative to the number of moles of the transition metal of the transition metal compound. (Organoaluminum compound / transition metal) from 1 to 10,000, preferably from 10 to 500
0. There is no particular limitation on the proportion of at least two kinds of organoaluminum compounds. The proportion of at least two kinds of organoaluminum compounds is such that one kind of organoaluminum compound is expressed by weight and the other at least one kind of organoaluminum compound is used. Preferably 0.5
To 99.5%, more preferably 10 to 90%, depending on the desired molecular weight of the polyolefin. Further, at least two kinds of organoaluminum compounds used for controlling the molecular weight of the polyolefin and a molecular weight regulator such as hydrogen may be used in combination.

The olefin in the present invention is an α-olefin having 2 to 20 carbon atoms (including ethylene), preferably an α-olefin having 2 to 10 carbon atoms. Specifically, ethylene, propylene, 1-butene, 3-methyl-
Examples thereof include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane, and styrene. Further, a diene having 4 to 20 carbon atoms such as butadiene, 1,4-pentadiene, 1,5-hexadiene and 1,4-hexadiene, or dicyclopentadiene, norbornene, methylnorbornene, tetracyclododecene, methyltetra Examples include cyclic olefins such as cyclododecene, and silicon-containing olefins such as allyltrimethylsilane and vinyltrimethylsilane. These olefins may be polymerized alone or in combination of two or more.

In the present invention, the polymerization can be carried out by a bulk polymerization method or a gas phase polymerization method in addition to the ordinary solvent polymerization method. The polymerization temperature is usually -100 to 200 ° C, preferably -20 to 200 ° C. 100 ° C. The polymerization pressure is not particularly limited, and is from normal pressure to 50 kgf / cm ² .

[0052]

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), intrinsic viscosity ([η]), melt flow index (MFR)
Was measured by the following method. Melting point (Tm): The melting point (Tm) measured by differential scanning calorimetry (DSC) was measured under the following conditions. [measuring device:
Perkin Elmer DSC-4, heating rate: 10 ° C / m
in, cooling rate: -10 ° C / min, or -30 ° C /
min] ・ Melt flow index (MFR): ASTM D
It is measured according to 1238E and is expressed in g / 10 min. -Intrinsic viscosity ([η]): The viscosity is measured in tetralin at 135 ° C and expressed in dl / g.

Example 1 [Solid catalyst component obtained by contacting methyl aluminum oxy compound with maleic anhydride grafted polypropylene] 3.9 g of maleic anhydride grafted polypropylene (M
w: 33630, maleic anhydride content: 12 wt%,
1.22 mmol / g) was added to 290 ml of xylene.
Heat at 20 ° C. to completely dissolve. Under a nitrogen atmosphere and under reflux, a solution of methylaluminoxane (9 wt%, manufactured by Albemarle, Inc., 9 wt%) in toluene was added to the solution using a dropping funnel.
was added and refluxed for 4 hours. Cool to room temperature, 140m
l of heptane was added and stirred for 30 minutes. The slurry was filtered under nitrogen, 90 ml of toluene and then 50 ml of heptane
The filtrate was washed with to obtain 6.4 g of a pale yellow solid. Further, the solid catalyst component was obtained by pulverizing with a vibration mill. The aluminum content in this solid component is 5.9 mmol / g
Met.

[Polymerization of Propylene] The light yellow solid catalyst component 1 was placed in a 50 ml two-necked flask sufficiently purged with nitrogen.
80 mg was suspended in 20 ml of toluene, and a catalyst was prepared by sequentially adding 0.75 mg of dimethylsilylenebis (2-methylbenz [e] indenyl) zirconium dichloride, 148 mg of triethylaluminum, and 5 mg of triisobutylaluminum. After charging the prepared catalyst in a stainless steel autoclave substituted with 5 liters of nitrogen and then propylene, 1.5 kg of propylene was added, the temperature was raised, and polymerization was carried out at 70 ° C. for 1 hour. The yield of the polymer was 600 g. The MFR of the obtained polymer was 23.0 g / 10 min, [η] was 1.27 dl / g, the Tm was 145 ° C., and the bulk density was 0.36 g / ml.

Example 2 In the polymerization of propylene in Example 1, 148 mg of triethylaluminum and 5 mg of triisobutylaluminum were used.
Was carried out in the same manner as in Example 1 except that a mixed alkyl aluminum of 147 mg of triethyl aluminum and 64 mg of triisobutyl aluminum was used instead. The yield of the polymer was 580 g. MF of the obtained polymer
R is 13.1 g / 10 min, [η] is 1.36 dl /
g, Tm is 145 ° C., and bulk density is 0.36 g / ml.
Met.

Example 3 In the polymerization of propylene in Example 1, 148 mg of triethylaluminum and 5 mg of triisobutylaluminum were used.
Was carried out in the same manner as in Example 1 except that a mixed alkylaluminum of 74 mg of triethylaluminum and 64 mg of triisobutylaluminum was used instead. The yield of the polymer was 590 g. MFR of the obtained polymer
Was 6.5 g / 10 min, [η] was 1.50 dl / g, Tm was 145 ° C., and bulk density was 0.36 g / ml.

Example 4 In the polymerization of propylene in Example 1, 148 mg of triethylaluminum and 5 mg of triisobutylaluminum were used.
Was carried out in the same manner as in Example 1 except that a mixed alkylaluminum of 5 mg of triethylaluminum and 128 mg of triisobutylaluminum was used instead. The yield of the polymer was 600 g. MFR of the obtained polymer
Was 4.0 g / 10 min, [η] was 1.69 dl / g, Tm was 145 ° C., and bulk density was 0.36 g / ml.

Example 5 In the polymerization of propylene in Example 3, hydrogen was added to 0.03 N
The same operation as in Example 3 was performed except that 1 was added. The yield of the polymer was 620 g. MFR of the obtained polymer
Is 10.5 g / 10 min, [η] is 1.38 dl / g
And the Tm was 145 ° C. and the bulk density was 0.36 g / ml.

Example 6 [Solid catalyst component obtained by contacting a methyl aluminum oxy compound with silica gel] 500 sufficiently purged with nitrogen
In a 50 ml four-necked flask, 3.0 g of silica gel (manufactured by Fuji Divison, HTG30908) was dispersed in 50 ml of toluene, and methylaluminoxane (manufactured by Albemarle, 9 g) was dispersed in 50 ml of toluene.
(wt%) 100 ml of a toluene solution was added and refluxed for 8 hours. After cooling to room temperature, the slurry was filtered under nitrogen, and the filtrate was washed with 60 ml of toluene and then 100 ml of heptane to obtain 5.5 g of a white solid catalyst component. The aluminum content in this solid component was 7.6 mmol / g.

[Polymerization of Propylene] The white solid catalyst component 15 was placed in a 50 ml two-necked flask sufficiently purged with nitrogen.
0 mg was suspended in 20 ml of toluene, and a catalyst was prepared by sequentially adding 0.75 mg of dimethylsilylenebis (2-methylbenz [e] indenyl) zirconium dichloride, 148 mg of triethylaluminum, and 5 mg of triisobutylaluminum. After charging the prepared catalyst in a stainless steel autoclave substituted with 5 liters of nitrogen and then propylene, 1.5 kg of propylene was added, the temperature was raised, and polymerization was carried out at 70 ° C. for 1 hour. The yield of the polymer was 650 g. The MFR of the obtained polymer was 30.0 g / 10 min, and [η] was 1.
18 dl / g, Tm 144 ° C., bulk density 0.4
It was 0 g / ml.

Example 7 In the polymerization of propylene in Example 6, 148 mg of triethylaluminum and 5 mg of triisobutylaluminum were used.
Was carried out in the same manner as in Example 6 except that a mixed alkyl aluminum of 147 mg of triethylaluminum and 64 mg of triisobutylaluminum was used instead. The yield of the polymer was 600 g. MF of the obtained polymer
R is 17.5 g / 10 min, [η] is 1.30 dl /
g, Tm is 144 ° C., and bulk density is 0.40 g / ml.
Met.

Example 8 In the polymerization of propylene in Example 6, 148 mg of triethylaluminum and 5 mg of triisobutylaluminum were used.
Was carried out in the same manner as in Example 6 except that a mixed alkylaluminum of 74 mg of triethylaluminum and 64 mg of triisobutylaluminum was used in place of the above. The yield of the polymer was 590 g. MFR of the obtained polymer
Was 8.7 g / 10 min, [η] was 1.46 dl / g, Tm was 145 ° C., and bulk density was 0.41 g / ml.

Example 9 In the polymerization of propylene in Example 6, 148 mg of triethylaluminum and 5 mg of triisobutylaluminum were used.
Was carried out in the same manner as in Example 6 except that a mixed alkyl aluminum of 5 mg of triethylaluminum and 128 mg of triisobutylaluminum was used instead. The yield of the polymer was 630 g. MFR of the obtained polymer
Was 5.0 g / 10 min, [η] was 1.57 dl / g, Tm was 145 ° C., and bulk density was 0.40 g / ml.

[0065]

According to the present invention, high activity and high stereoregularity can be maintained and the molecular weight can be easily controlled in the production of polyolefin, and its industrial value is extremely high.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

Claims (7)

[Claims] 1. A method of polymerizing an olefin in the presence of a catalyst comprising (A) a transition metal compound of Group 4 of the periodic table, (B) an organic aluminum oxy compound, and (C) an organic aluminum compound. C) A method for polymerizing olefins, comprising using at least two kinds of organoaluminum compounds as components and controlling the molecular weight of the polyolefin by changing the ratio. 2. The use ratio of at least two organoaluminum compounds is such that one organoaluminum compound has a desired proportion of 0.5 to 99.5% by weight with respect to the other at least one organoaluminum compound. The method for polymerizing olefins according to claim 1, wherein the method is changed according to the molecular weight of the polyolefin. 3. The olefin polymerization method according to claim 1, wherein the at least two kinds of organoaluminum compound components are triethylaluminum and triisobutylaluminum. 4. The olefin polymerization method according to claim 1, wherein the transition metal compound of Group 4 of the periodic table is a metallocene compound and the organoaluminum oxy compound is methylaluminoxane. 5. The olefin polymerization method according to claim 1, wherein the component (B) is a solid component obtained by bringing the organic aluminum oxy compound into contact with an organic polymer compound having a functional group. 6. The method according to claim 4, wherein the organic polymer compound having a functional group is a polyolefin grafted with maleic anhydride. 7. The olefin polymerization method according to claim 1, wherein the component (B) is a solid component obtained by bringing an organic aluminum oxy compound into contact with an inorganic oxide.