JP3511681B2 - Catalyst for producing olefin polymer and method for polymerizing olefin - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an olefin polymer composed of an inorganic oxide having surface hydroxyl groups partially or wholly substituted with fluorine , an organoaluminumoxy compound, a transition metal compound, an olefin, an organometallic compound and an ionized ionic compound. The present invention relates to a catalyst for combined production and a method for polymerizing olefins using this catalyst. More specifically, the present invention relates to a catalyst for producing an olefin polymer characterized by using a small amount of an organoaluminum oxy compound in combination with an ionized ionic compound, and an olefin polymerization method using this catalyst.

[0002]

2. Description of the Related Art As a method for producing a polyolefin,
It is already known to use catalyst systems which consist of a combination of transition metal compounds and organometallic compounds. Also,
It is disclosed in Kaminsky et al. That a catalyst using metallocene and methylaluminoxane exhibits high activity when producing an olefin polymer containing propylene.
It is known from Japanese Patent No. 9309.

However, in the catalyst system disclosed in the above publication, although the polymerization activity is excellent, the solution polymerization system is often used because the catalyst system is soluble in the reaction system, and the production process is limited. In addition, it is necessary to use a relatively large amount of relatively expensive methylaluminoxane in order to produce a polymer having industrially useful physical properties. Therefore, there are problems in terms of cost and a large amount of aluminum remaining in the polymer.

On the other hand, a catalyst system in which the aforementioned soluble catalyst system is supported on an inorganic oxide carrier such as silica is disclosed in JP-A-60-35.
No. 006, etc., and Japanese Patent Application Laid-Open No. 63-152608 discloses that the use of a catalyst component prepolymerized with an olefin can improve the particle properties of a polymer produced by gas phase polymerization. . However, the polymerization activity per methylaluminoxane was not sufficient even when the olefin was polymerized according to the methods described therein.

As a method for improving these, for example, JP-A-4-8704, JP-A-4-11604,
JP-A-4-213305 discloses that a gas phase polymerization using a catalyst system prepolymerized with a small amount of methylaluminoxane gives a polymer having excellent polymerization activity and good particle properties. There is. However, although the amount of methylaluminoxane used is small, the polymerization activity is still unsatisfactory, and there has been a demand for high activation of the catalyst system.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve this problem, and reduces the amount of organoaluminum oxy compound used in gas phase polymerization or suspension polymerization, and has excellent polymerization activity. And to provide a catalyst for producing an olefin polymer having a good particle shape.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a part or all of the surface hydroxyl groups are substituted with fluorine , an inorganic oxide, an organic aluminum oxy compound, or a transition compound. Metal compounds, olefins,
It was found that a polyolefin obtained with high activity, excellent physical properties and processability can be efficiently produced by using a catalyst obtained by contacting an organometallic compound and an ionized ionic compound,
The present invention has been completed.

That is, the present invention provides (a) an inorganic oxide in which a part or all of surface hydroxyl groups are substituted with fluorine , (b)
Organoaluminum oxy compound, (c) transition metal compound, (d) olefin, (e) organometallic compound, (f)
Olefin polymer for producing catalyst comprising contacting the ionizing ionic compound, off part or all of (a) a surface hydroxyl group
Inorganic oxides obtained by substituting Tsu-containing and (b) an organoaluminum oxy-compound and (c) an olefin prepolymerized catalyst formed by causing the olefin (d) a catalyst component comprising a transition metal compound is prepolymerized (e) Organometallic compounds,
(F) A catalyst for producing an olefin polymer, which comprises an ionized ionic compound, and the production of a polyolefin characterized by polymerizing or copolymerizing an olefin in the presence of the catalyst for producing an olefin polymer. Is the way.

The present invention will be described in detail below.

First, the catalyst for producing an olefin polymer of the present invention will be described.

The inorganic oxide (a) used in the present invention has an average particle size of 1 to 300 μm, particularly 10 to 200 μm.
Fine-particled porous particles in the range of 10 are preferable because they are easy to handle during catalyst preparation and polymerization processes. Specific examples of the inorganic oxide include inorganic oxides of typical elements such as silica, alumina and magnesia, inorganic oxides of transition metal elements such as titania and zirconia, and mixtures of silica-alumina, silica-magnesia and the like. These inorganic oxides usually contain Na ₂ O, K ₂ C as impurities.
It contains salts of alkali metals or alkaline earth metals such as O ₃ and BaSO ₄ . The fine-particle inorganic oxide may be used in a state of containing these impurities, but it is preferable to use an inorganic oxide that has been previously subjected to an operation of removing these impurities. The properties of such a porous fine-particle inorganic oxide differ depending on the type and production method thereof, but in the present invention, the specific surface area is 10 to 1000 m ^2.
/ G, especially 50-800 m ² / g, pore volume 0.1-
Those of 3 cc / g are preferable because many supporting components such as transition metal compounds can be supported. These inorganic oxides are used by firing at 100 to 1000 ° C. under reduced pressure or under gas flow, if necessary.

As a method of substituting the hydroxyl group of these inorganic oxides with fluorine , a method of reacting with a reactant having fluorine capable of exchanging with the surface hydroxyl group is preferable. As the reaction agent, fluorine , hydrogen fluoride, ammonium fluoride, CFC
A fluorine-containing compounds such as, but not limited thereto. These inorganic oxides are obtained by substituting some or all of the hydroxyl groups with fluorine , and then by-product H ₂ O.
May be heat-treated at 100 to 1000 ° C. under reduced pressure or under gas flow.

The inorganic oxide may be contacted with a metal compound in advance for the purpose of post-treatment of --OH residue prior to contact with other catalyst components. The metal compound used here is not particularly limited, but an organic metal compound is preferably used. The method of contacting the inorganic oxide with the above metal compound is not particularly limited, but a method of contacting in a suspension state in an organic solvent in which the oxide is insoluble and the metal compound is soluble, an organic solvent in which both are soluble Examples thereof include a method of contacting in a medium and a method of contacting with a ball mill or the like in a substantially solvent-free state.

The organoaluminum oxy compound (b) used in the present invention is a conventionally known aluminoxane or an aluminoxane further reacted with water, and may be used as a mixture of two or more kinds. The aluminum substituent of aluminoxane is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, and preferably a methyl group. The degree of oligomer is 4 to 60. The production method of this kind of compound is known, for example, salts containing water of crystallization (copper sulfate hydrate,
An example is a method in which an aluminum compound is added to a hydrocarbon medium suspension of aluminum sulfate hydrate or the like) and reacted.

The transition metal compound (c) used in the present invention is represented by the following general formula (1)

[0016]

[Chemical 11]

[0017]

[In the formula, M1 is a titanium atom, a zirconium atom or a hafnium atom, and Y is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
It is an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group, and R1 and R2 are each independently the following general formula (3), (4), (5) or (6).

[0019]

[Chemical 13]

(In the formula, each of R6 is a hydrogen atom.) And the ligand forms a sandwich structure together with M1 . ] It is suitable that it is a transition metal compound of the periodic table group 4 represented by these.

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

Examples of the compound represented by the general formula (1) include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride and bis. Dichloro compounds such as (indenyl) titanium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) hafnium dichloride, etc., and dimethyl compounds, diethyl compounds, dihydro compounds, diphenyl compounds of the Group 4 transition metal compounds of the periodic table , A dibenzyl body etc. can be illustrated.

[0034]

The olefin (d) used as a constituent component of the catalyst of the present invention is ethylene, propylene, butene-
1, α-olefins such as pentene-1,4-methyl-1-pentene, hexene-1, and octene-1, cyclic olefins such as norbornene and norbornadiene, and the like, but a mixture of two or more kinds of these components is polymerized. You can also

Further, the organometallic compound (e) used in the present invention is represented by the following general formula (27)

[0037]

[Chemical 20]

[In the formula, M5 is aluminum. R1
8 is each independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
An aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group or an alkylaryloxy group, wherein at least one R18 is a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. n is equal to the oxidation number of M5. ] It is an organometallic compound represented by.

Examples of the compound represented by the general formula (27) include trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n.
-Propyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, triamyl aluminum, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum ethoxide, di-n-propyl aluminum ethoxide, diisobutyl aluminum ethoxide, di-
n-Butyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, diisopropyl aluminum hydride, di-n
-Propyl aluminum hydride, diisobutyl aluminum hydride, di-n-butyl aluminum hydride, etc. can be illustrated.

Next, the ionized ionic compound (f) used as a constituent component of the catalyst of the present invention will be described.

[0041]

[0042]

[0043]

Specific examples of the ionized ionic compound include tri (n-butyl) ammonium tetrakis (p-tolyl) borate, tri (n-butyl) ammonium tetrakis (m-tolyl) borate and tri (n-butyl). ) Ammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N- Dimethylanilinium tetrakis (p-tolyl) borate, N, N-Dimethylanilinium tetrakis (m-tolyl) borate, N,
N-dimethylanilinium tetrakis (2,4-dimethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-dimethylphenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (p-tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4-dimethyl) Phenyl) borate, triphenylcarbenium tetrakis (3,5-dimethylphenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tropylium tetrakis (p-tolyl) borate, tropylium tetrakis (m-tolyl) borate ,
Tropylium tetrakis (2,4-dimethylphenyl)
Borate, tropylium tetrakis (3,5-dimethylphenyl) borate, tropylium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, lithium tetrakis (phenyl) borate, lithium tetrakis (p-tolyl) borate, Lithium tetrakis (m-tolyl) borate, lithium tetrakis (2,4-dimethylphenyl) borate, lithium tetrakis (3,5-dimethylphenyl) borate, lithium tetrafluoroborate, sodium tetrakis (pentafluorophenyl)
Borate, sodium tetrakis (phenyl) borate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-tolyl) borate, lithium tetrakis (2,4-dimethylphenyl) borate, sodium tetrakis (3,5-dimethylphenyl) borate , Sodium tetrafluoroborate, potassium tetrakis (pentafluorophenyl) borate, potassium tetrakis (phenyl) borate, potassium tetrakis (p-tolyl) borate, sodium tetrakis (m)
-Tolyl) borate, potassium tetrakis (2,4-dimethylphenyl) borate, potassium tetrakis (3,3)
5- dimethylphenyl) borate, potassium tetrafluoroborate, and the like, but not limited thereto.

In the olefin polymerization catalyst of the present invention, the amount of the transition metal compound (c) with respect to 1 g of the inorganic oxide (a) in which some or all of the surface hydroxyl groups are substituted with fluorine is not particularly limited, but the transition metal atom 0.005-1mmo in quantity
1, preferably 0.05 to 0.5 mmol, and the amount of Al atoms contained in the organoaluminum oxy compound (b) with respect to the transition metal compound (c) is 10 to 200 mol based on 1 mol of the transition metal atom in the transition metal compound. It is preferable to use it in a ratio of 10 to obtain a better polymerization activity. The olefin (d) is added to 1 g of the inorganic oxide (a) in which some or all of the surface hydroxyl groups are substituted with fluorine.
If the amount of 0.01 to 100 g is used, a better polymerization activity can be obtained, which is preferable.

The molar ratio of the transition metal compound (c) and the ionized ionic compound (f) used in the present invention is not particularly limited, but a transition metal compound (a): ionized ionic compound (f) molar ratio is preferable. Is from 0.01 to 1: 1
000, particularly preferably 1: 0.2 to 1:
The range is 200. By using this range, a better polymerization activity can be obtained. The amount of the organometallic compound (e) used here is not particularly limited.

In the present invention, the method for contacting the catalyst component is not particularly limited, but as a preferred contact method for obtaining a catalyst having good polymerization activity, a part or all of the surface hydroxyl groups are fluorinated.
An olefin prepolymerization catalyst formed by prepolymerizing an olefin (d) with a catalyst component composed of an element- substituted inorganic oxide (a), an organoaluminum oxy compound (b), and a transition metal compound (c), and an organic compound. Examples thereof include a method of bringing the metal compound (e) and the ionized ionic compound (f) into contact with each other. The conditions for contacting the olefin (d) in this prepolymerization are not particularly limited, but the prepolymerization is carried out without solvent or under an inert hydrocarbon solvent. Generally, this contact treatment is -50 to 100 ° C, preferably -20 to 60.
C., more preferably in the temperature range of 0 to 50.degree. C., and can be carried out under normal pressure or under increased pressure. When the treatment is carried out in the gas phase, it is carried out under the flow condition, and when the treatment is carried out in the liquid phase. It is preferable to make sufficient contact under stirring. The monomers used in the prepolymerization may be used alone or in combination of two or more kinds, and when prepolymerizing two or more kinds, the prepolymerization may be carried out sequentially or simultaneously.

The catalyst for producing an olefin polymer of the present invention is obtained as described above, and a Lewis base compound may be added thereto. Specific Lewis base compounds include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate. , Hexyl acetate, cyclohexyl acetate, benzyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 3-
Ethylhexyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl isovalerate, isokichi Isobutyl herbate, butyl stearate, pentyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate, ethyl cinnamate, diethyl oxalate, dibutyl oxalate, oxalic acid Esters such as dipentyl, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate and triacetin, methylacetate Amine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, diisopropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, allylamine, aniline, N -Methylaniline, N, N-dimethylaniline, N, N-diethylaniline, toluidine, cyclohexylamine, dicyclohexylamine, pyrrole, piperidine, pyridine, picoline, 2,4-lutidine, 2,6-lutidine, 2,6- Amines such as di (t-butyl) pyridine, quinoline and isoquinoline, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether Ether, anisole, phenetole, butyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, veratrole, 1,2-epoxypropane, dioxane, trioxane, furan,
Ethers such as 2,5-dimethylfuran, tetrahydrofuran, tetrahydropyran, 1,2-diethoxyethane, 1,2-dibutoxyethane and crown ether, acetone, methyl ethyl ketone, methyl propyl ketone,
Diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, dipropyl ketone,
Diisobutyl ketone, cyclohexanone, methylcyclohexanone, ketones such as acetophenone, dimethyl sulfide, diethyl sulfide, thioethers such as thiophene, tetrahydrothiophene, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, Tetraisopentoxysilane, tetrahexoxysilane, tetraphenoxysilane, tetrakis (2-ethylhexoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-methoxyethoxy) silane, methyltrimethoxysilane, ethyltrimethoxysilane , Propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane , Sec-butyltrimethoxysilane, t-butyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, norbonyltrimethoxysilane, cyclohexyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-chlorotrimethoxysilane, triethoxysilane, methyltriethoxysilane,
Ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, ethyltriisopropoxysilane, isopentyltributoxysilane, methyltrihexoxysilane , Methyldimethoxysilane, dimethyldimethoxysilane, propylmethyldimethoxysilane, propylethyldimethoxysilane, dipropyldimethoxysilane, isopropylmethyldimethoxysilane, diisopropyldimethoxysilane, propylisopropyldimethoxysilane, butylmethyldimethoxysilane, butylethyldimethoxysilane, butylpropyl Dimethoxysilane, butylisopropyldimethoxysilane, dibutyldimethoxysilane, Seo-butyl methyl dimethoxy silane,
Diisobutyldimethoxysilane, sec-butylethyldimethoxysilane, di (sec-butyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylpropyldimethoxysilane, di (t-butyl) dimethoxysilane, t-butylhexyldimethoxysilane, Diisoamyldimethoxysilane, hexylpropyldimethoxysilane, decylmethyldimethoxysilane, norbonylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, Diisopropyldiethoxysilane, sec-butylmethyldiethoxysilane, t-butylmethyldiethoxysilane, dime Distearate butoxy silane, trimethyl methoxy silane, trimethyl ethoxy silane, trimethyl tetraisopropoxysilane, trimethylpropoxysilane,
Silyl ethers such as trimethyl-t-butoxysilane, trimethylisobutoxysilane, trimethylbutoxysilane, trimethylpentoxysilane, and trimethylphenoxysilane, methylphosphine, ethylphosphine, phenylphosphine, benzylphosphine, dimethylphosphine, Diethylphosphine, diphenylphosphine, methylphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, tributylphosphine, ethylbenzylphenylphosphine, ethylbenzylbutylphosphine, trimethoxyphosphine, diethylethoxyphosphine Phosphines such as fins, triphenylphosphine oxide, dimethylethoxyphosphine oxide, trieth Phosphine oxides such as cyphosphine oxide, nitriles such as acrylonitrile, cyclohexanedinitrile and benzonitrile, nitro compounds such as nitrobenzene, nitrotoluene and dinitrobenzene, acetone dimethyl acetal, acetophenone dimethyl acetal, benzophenone dimethyl acetal, cyclohexanone dimethyl acetal Examples thereof include acetals such as diethyl carbonate, diphenyl carbonate, carbonates such as ethylene carbonate, thioacetals such as 1-ethoxy-1- (methylthio) cyclopentane, and thioketones such as cyclohexanethione. It is not limited.

When a Lewis base compound is added to obtain a catalyst, the transition metal compound (c) and the Lewis base compound are in mols.
The ratio is not particularly limited, but the molar ratio of the transition metal compound (c): Lewis base compound is preferably 1: 0.01 to.
It is in the range of 1: 1000, particularly preferably 1: 0.1
˜1: 100.

In addition, in preparing the catalyst, the method of adding the Lewis base compound is not limited, but it is preferable to add the Lewis base compound after contacting (a) to (f).

In the present invention, in the presence of the catalyst for producing an olefin polymer prepared by the above method, the α-olefin or the cyclic olefin is in a solution state, a suspension state or a gas phase state at a temperature of -60 to 280 ° C. , 0.05-20
A polyolefin can be produced by polymerization or copolymerization under a pressure of 0 MPa .

As these olefins, ethylene,
Propylene, butene-1, pentene-1,4-methyl-
Examples thereof include α-olefins such as 1-pentene, hexene-1, and octene-1, and cyclic olefins such as norbornene and norbornadiene, but it is also possible to polymerize a mixed component of two or more kinds thereof.

When the polymerization is carried out in a solution state or a suspension state, the catalyst for producing an olefin polymer obtained by the above method may be used as it is or may be diluted with a polymerization solvent. The polymerization solvent may be any organic solvent commonly used, and specifically, halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride, and fats such as pentane, hexane, heptane, octane, nonane and decane. Examples thereof include aromatic hydrocarbons such as group hydrocarbons, benzene, toluene and xylene, or the olefin itself can be used as a solvent.

[0054]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The polymerization operation, reaction and solvent purification were all carried out under an inert gas atmosphere. Further, as the solvent and the like used in the reaction, those which were previously purified, dried and deoxidized by a known method were used. The compounds used in the reaction were those synthesized and identified by known methods. The melting index (MI) described in the examples was measured by a method according to ASTM D1238 condition E.

Example 1 [Preparation of prepolymerization catalyst] A 500 ml glass flask was subjected to fluorination treatment with NH ₄ F (200
1.01 g and 15 ml of decane were added to make a suspension. To this was added 5.6 ml of a toluene solution of methylaluminoxane (2.98 mol / l), and the mixture was stirred at room temperature for 1 hour.
Stir for hours. Then, a toluene solution of bis (indenyl) zirconium dichloride (0.0024 mol /
l) 70 ml was added, and the mixture was stirred at room temperature for 1 hour. Then
Add 35 ml of decane, introduce ethylene at atmospheric pressure, and
The mixture was stirred at 0 ° C. for 3 hours under an ethylene gas atmosphere. After the completion of prepolymerization, remove the solvent with a bridge filter,
Washing was performed 4 times with 200 ml of hexane. As a result, zirconium was 0.084 per 1 g of the ash content of the prepolymerization catalyst.
A prepolymerization catalyst containing 1 mmol of polyethylene and 10 g of polyethylene was obtained.

[Polymerization] The interior of the stainless steel magnetic stirring type autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Then, a mixture of the prepolymerized catalyst prepared above (corresponding to 2.4 μmol of zirconium), 1.5 mmol of triisobutylaluminum and 5 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was inserted into an autoclave. Immediately, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 30 minutes while continuously adding ethylene gas so that the internal pressure of the autoclave became 8 kg / cm ² G. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI is 1.1g
/ 10 minutes, the polymer having a bulk density of 0.30 g / cm ³ is 82
g was obtained.

Example 2 [Preparation of pre-polymerization catalyst] 1.0 g of silica magnetically treated with NH ₄ F (calcined at 200 ° C. for 5 hours) and 30 ml of hexane were placed in a 1 l glass electromagnetic stirring autoclave.
Was added to make a suspension. 7.0 ml of a toluene solution of methylaluminoxane (2.39 mol / l) was added thereto,
Stirred at room temperature for 1 hour. Then, a toluene solution of bis (indenyl) zirconium dichloride (0.0024
(mol / l) 70 ml was added, and the mixture was stirred at room temperature for 1 hour.
Then, 40 ml of hexane was added, and prepolymerization was carried out at 30 ° C. for 3 hours while continuously adding ethylene gas so that the internal pressure of the autoclave became 0.5 kg / cm ² G. After the completion of the preliminary polymerization, the solvent was removed, and the mixture was washed with 200 ml of hexane four times. As a result, 1 g of silica as a prepolymerization catalyst
Thus, a prepolymerization catalyst containing 0.052 mmol of zirconium and 8 g of polyethylene was obtained.

[Polymerization] The interior of the stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Then, a mixture of the prepolymerized catalyst prepared above (corresponding to 2.5 μmol of zirconium), 1.5 mmol of triisobutylaluminum and 5 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was inserted into an autoclave. Immediately, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 35 minutes while continuously adding ethylene gas so that the internal pressure of the autoclave became 8 kg / cm ² G. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI is 1.6g
/ 10 minutes, the polymer having a bulk density of 0.38 g / cm ³ is 10
1 g was obtained.

Example 3 [Polymerization] The interior of a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Next, the prepolymerized catalyst obtained in Example 2 (corresponding to zirconium 2.5 μmol), triisobutylaluminum 1.5 mmol, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 5 μmol
Then, a mixture of 1.25 μmol of diphenyldimethoxysilane and 1.25 μmol of diphenyldimethoxysilane was inserted into the autoclave. Immediately introduce ethylene gas and the internal pressure of the autoclave is 8 kg / cm
8 while continuously adding ethylene gas to ² G
Polymerization was carried out at 0 ° C. for 35 minutes. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI was 1.9 g / 10 minutes, and 110 g of a polymer having a bulk density of 0.36 g / cm ³ was obtained.

Example 4 [Polymerization] The interior of a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 150 g of sodium chloride was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Then, the prepolymerized catalyst obtained in Example 2 (corresponding to 2.5 μmol of zirconium), 1.5 mmol of triisobutylaluminum and 5 μm of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
The mixture of ol was inserted into the autoclave. Immediately mixed gas of ethylene / butene-1 (butene-1 content 2
9 mol%) was introduced, and the internal pressure of the autoclave was 8 kg /
8 while continuously adding the mixed gas so as to obtain cm ² G
Polymerization was carried out at 0 ° C. for 35 minutes. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. This mixture was washed with pure water, dissolved in sodium chloride, and then dried. As a result, MI was 40 g / 10 minutes and melting point was 1.
73 g of polymer with a bulk density of 0.41 g / cm ³ at 26 ° C.
Was obtained.

Example 5 [Polymerization] 500 ml of hexane and 0.5 mmol of triisobutylaluminum were added to a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l, and the mixture was stirred for 10 minutes. An autoclave was prepared by mixing the solution with the prepolymerized catalyst obtained in Example 2 (corresponding to 1.0 μmol of zirconium), 0.3 mmol of triisobutylaluminum and 2 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Inserted into. 4 kg / cm ² inside the autoclave with ethylene
While maintaining at G, polymerization was carried out at 80 ° C for 30 minutes. As a result, MI was 0.83 g / 10 minutes and bulk density was 0.06 g / c.
29 g of m ³ polymer was obtained.

Comparative Example 1 [Preparation of Preliminary Polymerization Catalyst] In [Preparation of Prepolymerization Catalyst] of Example 2, untreated silica (calcined at 200 ° C. for 5 hours) was used instead of silica treated with fluorine by NH ₄ F. A catalyst was prepared in the same manner as in Example 2 except that was used. As a result, a prepolymerized catalyst containing 0.087 mmol of zirconium and 10 g of polyethylene per 1 g of silica of the prepolymerized catalyst was obtained.

[Polymerization] 500 ml of hexane and 0.5 mmol of triisobutylaluminum were added to a stainless steel magnetic stirring type autoclave having an internal volume of 2 liters, and 1
Stir for 0 minutes. This solution was mixed with the prepolymerized catalyst prepared above (corresponding to 1.0 μmol of zirconium), 0.3 mmol of triisobutylaluminum and 2 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and inserted into an autoclave. did. 4 inside the autoclave with ethylene
Polymerization was carried out at 80 ° C. for 30 minutes while keeping it at kg / cm ² G. As a result, 13 g of a polymer having an MI of 0.76 g / 10 minutes and a bulk density of 0.04 g / cm ³ was obtained.

[0065]

EFFECT OF THE INVENTION By using the catalyst for producing an olefin polymer of the present invention, an olefin polymer having an excellent polymerization activity and a good particle shape can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-32830 (JP, A) JP-A-6-25343 (JP, A) JP-A-1-292008 (JP, A) JP-A-1- 292010 (JP, A) JP-A-6-345806 (JP, A) JP-A-8-48714 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/64-4 / 658

Claims (3)

(57) [Claims] 1. An inorganic oxide in which part or all of surface hydroxyl groups are substituted with fluorine, (b) an organoaluminum oxy compound, (c) the following general formula (1): [In the formula, M1 is a titanium atom, a zirconium atom or a hafnium atom, and Y is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 to 2 carbon atoms.
0 is an aryl group, an arylalkyl group or an alkylaryl group, and R 1 and R 2 are each independently the following general formula (3), (4), (5) or (6) (In the formula, each of R6 is a hydrogen atom.), And the ligand forms a sandwich structure together with M1. ] A transition metal compound of Group 4 of the periodic table represented by: (d) an olefin; (e) the following general formula (27): [In formula, M5 is aluminum. R18 is independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group or an alkylaryloxy group. And at least one R18 is a hydrogen atom and has 1 to 2 carbon atoms.
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. n is M
Equivalent to an oxidation number of 5. ] An organometallic compound represented by the formula (f) tri (n-butyl) ammonium tetrakis (p
-Tolyl) borate, tri (n-butyl) ammonium
Tetrakis (m-tolyl) borate, tri (n-butyl)
Lu) ammonium tetrakis (2,4-dimethylphenyl)
Ru) borate, tri (n-butyl) ammonium tetra
Kiss (3,5-dimethylphenyl) borate, tri (n)
-Butyl) ammonium tetrakis (pentafluorophenyl)
Phenyl) borate, N, N-dimethylanilinium tet
Lakis (p-tolyl) borate, N, N-dimethylani
Rinium tetrakis (m-tolyl) borate, N, N-
Dimethylanilinium tetrakis (2,4-dimethylphenylene)
Phenyl) borate, N, N-dimethylanilinium tet
Lakis (3,5-dimethylphenyl) borate, N, N
-Dimethylanilinium tetrakis
Phenyl) borate, triphenylcarbenium tetraki
Su (p-tolyl) borate, triphenylcarbenium
Tetrakis (m-tolyl) borate, triphenyl carb
Benium tetrakis (2,4-dimethylphenyl) bore
, Triphenylcarbenium tetrakis (3,5-
Dimethylphenyl) borate, triphenylcarbenium
Mutetrakis (pentafluorophenyl) borate,
Ropyrium tetrakis (p-tolyl) borate, tropi
Lithium tetrakis (m-tolyl) borate, tropiliu
Mutetrakis (2,4-dimethylphenyl) borate,
Tropylium tetrakis (3,5-dimethylphenyl)
Borate, tropylium tetrakis (pentafluorofuran
Phenyl) borate, lithium tetrakis (pentafluor)
Rophenyl) borate, lithium tetrakis (phenyl)
B) borate, lithium tetrakis (p-tolyl) bore
, Lithium tetrakis (m-tolyl) borate, lithium
Titanium tetrakis (2,4-dimethylphenyl) volley
G, lithium tetrakis (3,5-dimethylphenyl)
Borate, lithium tetrafluoroborate, natriu
Mutetrakis (pentafluorophenyl) borate, na
Thorium tetrakis (phenyl) borate, sodium
Tetrakis (p-tolyl) borate, sodium tetra
Kiss (m-tolyl) borate, lithium tetrakis
(2,4-dimethylphenyl) borate, sodium te
Trakis (3,5-dimethylphenyl) borate, nato
Lithium tetrafluoroborate, potassium tetrakis
(Pentafluorophenyl) borate, potassium tetra
Kiss (phenyl) borate, potassium tetrakis (p-
Trilyl) borate, sodium tetrakis (m-tri)
Le) borate, potassium tetrakis (2,4-dimethyl)
Phenyl) borate, potassium tetrakis (3,5-di)
Methylphenyl) borate, potassium tetrafluoroborate
A catalyst for producing an olefin polymer, which is obtained by contacting an ionized ionic compound selected from rates . 2. (a) An inorganic oxide in which a part or all of surface hydroxyl groups are substituted with fluorine, (b) an organoaluminum oxy compound, and (c) the following general formula (1): [In the formula, M1 is a titanium atom, a zirconium atom or a hafnium atom, and Y is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 to 2 carbon atoms.
0 is an aryl group, an arylalkyl group or an alkylaryl group, and R1 and R2 are each independently the following general formula (3), (4), (5) or (6): (In the formula, each of R6 is a hydrogen atom.), And the ligand forms a sandwich structure together with M1. ] An olefin prepolymerization catalyst formed by prepolymerizing an olefin (d) with a catalyst component consisting of a transition metal compound of Group 4 of the periodic table represented by the following general formula (27) ] [In formula, M5 is aluminum. R18 is independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group or an alkylaryloxy group. And at least one R18 is a hydrogen atom and has 1 to 2 carbon atoms.
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. n is M
Equivalent to an oxidation number of 5. ] An organometallic compound represented by the formula (f) tri (n-butyl) ammonium tetrakis (p
-Tolyl) borate, tri (n-butyl) ammonium
Tetrakis (m-tolyl) borate, tri (n-butyl)
Lu) ammonium tetrakis (2,4-dimethylphenyl)
Ru) borate, tri (n-butyl) ammonium tetra
Kiss (3,5-dimethylphenyl) borate, tri (n)
-Butyl) ammonium tetrakis (pentafluorophenyl)
Phenyl) borate, N, N-dimethylanilinium tet
Lakis (p-tolyl) borate, N, N-dimethylani
Rinium tetrakis (m-tolyl) borate, N, N-
Dimethylanilinium tetrakis (2,4-dimethylphenylene)
Phenyl) borate, N, N-dimethylanilinium tet
Lakis (3,5-dimethylphenyl) borate, N, N
-Dimethylanilinium tetrakis
Phenyl) borate, triphenylcarbenium tetraki
Su (p-tolyl) borate, triphenylcarbenium
Tetrakis (m-tolyl) borate, triphenyl carb
Benium tetrakis (2,4-dimethylphenyl) bore
, Triphenylcarbenium tetrakis (3,5-
Dimethylphenyl) borate, triphenylcarbenium
Mutetrakis (pentafluorophenyl) borate,
Ropyrium tetrakis (p-tolyl) borate, tropi
Lithium tetrakis (m-tolyl) borate, tropiliu
Mutetrakis (2,4-dimethylphenyl) borate,
Tropylium tetrakis (3,5-dimethylphenyl)
Borate, tropylium tetrakis (pentafluorofuran
Phenyl) borate, lithium tetrakis (pentafluor)
Rophenyl) borate, lithium tetrakis (phenyl)
B) borate, lithium tetrakis (p-tolyl) bore
, Lithium tetrakis (m-tolyl) borate, lithium
Titanium tetrakis (2,4-dimethylphenyl) volley
G, lithium tetrakis (3,5-dimethylphenyl)
Borate, lithium tetrafluoroborate, natriu
Mutetrakis (pentafluorophenyl) borate, na
Thorium tetrakis (phenyl) borate, sodium
Tetrakis (p-tolyl) borate, sodium tetra
Kiss (m-tolyl) borate, lithium tetrakis
(2,4-dimethylphenyl) borate, sodium te
Trakis (3,5-dimethylphenyl) borate, nato
Lithium tetrafluoroborate, potassium tetrakis
(Pentafluorophenyl) borate, potassium tetra
Kiss (phenyl) borate, potassium tetrakis (p-
Trilyl) borate, sodium tetrakis (m-tri)
Le) borate, potassium tetrakis (2,4-dimethyl)
Phenyl) borate, potassium tetrakis (3,5-di)
Methylphenyl) borate, potassium tetrafluoroborate
A catalyst for producing an olefin polymer, which comprises an ionized ionic compound selected from a rate . 3. In the presence of the catalyst for producing an olefin polymer according to any one of claims 1 to 2 , an α-olefin or a cyclic olefin in a solution state, a suspension state or a gas phase state is -60 to 2
A method for producing an olefin polymer, which comprises polymerizing or copolymerizing at a temperature of 80 ° C. and a pressure of 0.05 to 200 MPa.