JPH05255437A - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Abstract

(57) [Summary] [Structure] A particulate carrier containing 1.0% by weight or more of water, an organoaluminum oxy compound, and at least 2
A solid catalyst for olefin polymerization formed from a group IVB transition metal compound having a cyclopentadienyl skeleton, an organoaluminum compound if desired, and an olefin polymer formed by prepolymerization. A method for polymerizing an olefin using the above catalyst. [Effect] A solid for olefin polymerization capable of producing an olefin polymer having high polymerization activity and excellent melt tension, and providing a copolymer having a narrow composition distribution when two or more kinds of monomers are copolymerized. A catalyst can be provided.
To polymerize olefins using catalysts with good properties. The obtained polymer has a wide molecular weight distribution and is excellent in melt tension, and therefore is excellent in moldability.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid catalyst for olefin polymerization and a method for polymerizing olefins using this catalyst. More specifically, an olefin polymer having excellent melt tension, broad molecular weight distribution and excellent moldability is obtained. The
Moreover, the present invention relates to a solid catalyst for olefin polymerization capable of producing an olefin polymer with high polymerization activity, and an olefin polymerization method using this catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, α-olefin polymers,
For example, as a catalyst for producing an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst composed of a titanium compound and an organoaluminum compound or a vanadium-based catalyst composed of a vanadium compound and an organoaluminum compound is known. There is.

In recent years, a new Ziegler type olefin polymerization catalyst composed of a zirconium compound and an organoaluminum oxy compound has been developed as a catalyst capable of producing an ethylene / α-olefin copolymer with high polymerization activity, and such a catalyst is also available. Ethylene / α-using a new catalyst
A method for producing an olefin copolymer is described, for example, in JP-A-58-58.
19309, JP-A-60-35005, JP-A-60-35006, and JP-A-60-35007.
Japanese Patent Laid-Open Publication No. 60-35008 and the like.

The catalyst formed from a transition metal compound and an organoaluminum oxy compound proposed in these prior arts is a catalyst formed from a transition metal compound and an organoaluminum compound which are known before the appearance of this catalyst. Polymerization activity, especially ethylene polymerization activity is better than that of, but most of them are soluble in the reaction system, and in most cases, the production process is limited to the solution polymerization system, and a polymer with a high molecular weight should be produced. In that case, there is a problem that the viscosity of the solution containing the polymer is significantly increased and the productivity is lowered, or it is difficult to produce a spherical olefin polymer having excellent particle properties.

On the other hand, using a catalyst in which at least one component of a transition metal compound and an organoaluminum oxy compound is supported on a porous inorganic oxide carrier such as silica, alumina or silica-alumina, a suspension polymerization system or a gas phase system is used. Attempts have also been made to polymerize olefins in polymerization systems.

For example, JP-A-60-35006, JP-A-60-35007 and JP-A-60-
Japanese Patent No. 35008 describes that a catalyst in which a transition metal compound and an organoaluminum oxy compound are supported on silica, alumina, silica-alumina or the like can be used.

In JP-A-60-106808 and JP-A-60-106809, a highly active catalyst component containing a titanium compound and / or a zirconium compound soluble in a hydrocarbon solvent is contacted with a filler in advance. A composition comprising a polyethylene-based polymer and a filler obtained by copolymerizing ethylene or ethylene and an α-olefin in the presence of a product obtained by the treatment, an organoaluminum compound, and a filler having affinity for polyolefin. A method of making an article is described.

JP-A-61-31404 discloses that a product obtained by reacting a trialkylaluminum with water in the presence of silicon dioxide or aluminum oxide and a transition metal compound in the presence of a mixed catalyst. , Ethylene or a method of polymerizing or copolymerizing ethylene and an α-olefin.

Japanese Patent Laid-Open No. 61-276805 discloses that a reaction mixture obtained by reacting a zirconium compound with an aluminoxane and a trialkylaluminum is further reacted with an inorganic oxide having a surface hydroxyl group such as silica. It is described to polymerize olefins in the presence of a catalyst consisting of a mixture.

JP-A-61-108610 and JP-A-61-296008 disclose that an olefin is present in the presence of a catalyst in which a transition metal compound such as metallocene and aluminoxane are supported on a carrier such as an inorganic oxide. A method for polymerizing is described.

However, when the olefins are polymerized or copolymerized in the suspension polymerization system or the gas phase polymerization system using the solid catalyst component supported on the carrier described above, the polymerization activity is higher than that in the solution polymerization system. It was remarkably reduced, and the bulk specific gravity of the produced polymer was not sufficiently satisfactory.

By the way, the produced polymer is required to have various properties depending on the molding method and application. For example, when an inflation film is to be molded at high speed, there is no bubble fluctuation or breakage, and in order to perform stable high speed molding, a polymer with a high melt tension relative to the molecular weight must be selected. .. With similar characteristics
It is necessary to prevent sagging or tearing in hollow molding, or to suppress the width reduction in T-die molding to a minimum. In addition, the copolymer is required to have a narrow composition distribution in order to prevent stickiness when it is formed into a film or the like. Further, if the polymer has a narrow molecular weight distribution, molding conditions may be limited, and an olefin polymer having a wide molecular weight distribution is required for some applications. The conventionally proposed solid catalyst component supported on a carrier has not satisfied such requirements.

[0013]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and it is possible to obtain an olefin polymer having excellent melt tension, broad molecular weight distribution and excellent moldability, and having high polymerization activity. To provide a solid catalyst for olefin polymerization capable of producing a spherical olefin polymer having excellent particle properties and providing a copolymer having a narrow composition distribution when two or more kinds of monomers are copolymerized. Has a purpose.

Another object of the present invention is to provide a method for polymerizing olefins using a catalyst having good properties as described above.

[0015]

SUMMARY OF THE INVENTION A solid catalyst for olefin polymerization according to the present invention comprises [A] (i) an oxide of at least one element selected from Group II, Group III and Group IV, and (ii) 1.0 A fine particle carrier containing water in an amount of at least wt%; [B] an organoaluminum oxy compound;
Containing a ligand having a certain [C] cyclopentadienyl skeleton
It is characterized in that it is formed from a Group IVB transition metal compound and an olefin polymer produced by prepolymerization.

In the present invention, the fine particle carrier [A] is
After drying, it adsorbs water and the amount of adsorbed water is 1.0% by weight.
The above may be sufficient. Further, the [C] transition metal compound is preferably a Group IVB transition metal compound containing a ligand having an alkyl-substituted cyclopentadienyl group.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized or copolymerized in the presence of the above solid catalyst. In the present invention, in addition to the above [A] to [C] during the prepolymerization, [D] may be added if desired.
An organoaluminum compound may be used, and an organoaluminum compound may be optionally used during the polymerization.

In the present invention, since the specific fine particle carrier and at least two kinds of transition metal compounds are used, the obtained olefin polymer has excellent melt tension, wide molecular weight distribution and excellent moldability.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization solid catalyst according to the present invention and the olefin polymerization method using the catalyst will be specifically described below.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may be used not only as a homopolymer but also as a copolymer. May be used to mean coalesce.

The fine particle carrier [A] used in the present invention (hereinafter sometimes referred to as "component [A]") is at least one element selected from the group II, the group III and the group IV. A fine particle inorganic compound made of an oxide is used.

There are many such fine particle inorganic compounds.
Porous oxides are preferred, specifically SiO 2₂, Al
₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO, Z
nO, BaO, ThO₂Or a mixture containing these,
For example, SiO₂-MgO, SiO₂-Al₂O ₃, SiO₂-TiO
₂, SiO₂-V₂O_Five, SiO₂-Cr₂O₃, SiO₂-TiO₂
-MgO etc. can be illustrated. Among these
₂, Al₂O₃And a small amount selected from the group consisting of MgO
It is preferred to have at least one component as the main component.

The fine particle carrier [A] has an average particle size of usually 1 to 300 μm, preferably 10 to 200 μm, and a specific surface area of 50 to 1000 m ^2.
/ G, preferably in the range of 100 to 700 m ² / g, and the pore volume is preferably in the range of 0.3 to 2.5 cm ³ / g.

Such a fine particle carrier [A] generally contains water in an amount of 1.0% by weight or more, preferably 1.2 to 20% by weight, more preferably 1.4 to 15% by weight. Is desirable. The water contained in the fine particle carrier [A] means adsorbed water adsorbed on the surface of the fine particle carrier.

As a method for obtaining a fine particle carrier containing a specific amount of water, for example, the following method can be mentioned. (1) A method in which a carrier is stored in air containing water and allowed to stand until the water content of the carrier reaches a specific amount.

(2) Store the carrier in air containing water,
A method of adsorbing water to the carrier and then drying the carrier until the water content reaches a specific amount. (3) A method of adsorbing water after drying the carrier. Specifically, a predetermined amount of water, water vapor, solution, on a sufficiently dried carrier,
A method of adding a suspension or the like and stirring. At this time, when a temperature of about 200 ° C. or higher is adopted as the drying temperature, it is usually accompanied by desorption of adsorbed water and dehydration by condensation of surface hydroxyl groups.

The heat loss method can be used to quantify the water contained in the particulate carrier. In the present invention, the amount of adsorbed water is the weight loss when dried at 200 ° C. for 4 hours under the flow of dry gas such as air or nitrogen.

By using such a particulate carrier containing a specific amount of water, it is possible to obtain a solid catalyst component for olefin polymerization capable of producing an olefin excellent in melt tension with high polymerization activity.

The [B] organoaluminum oxy compound (hereinafter sometimes referred to as "component [B]") used in the present invention may be a conventionally known aluminoxane, or JP-A-2- It may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent No. 78687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and ceric chloride hydrate A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same.

(2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as a hydrocarbon solution.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and trialuminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum Dialkyl aluminum halides such as chloride, diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; diethyl aluminum Examples thereof include dialkylaluminum aryloxides such as aluminum phenoxide.

Of these, trialkylaluminum is particularly preferable. Further, as the organoaluminum compound, isoprenylaluminum represented by the following general formula [I] can also be used.

(I-C ₄ H ₉ ) x Aly (C ₅ H ₁₀ ) z ... [I] (In the formula, x, y, and z are positive numbers, and z ≧ 2x.) The above organic The aluminum compounds are used alone or in combination.

As the solvent used in the production of the aluminoxane as described above, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane,
Hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons, cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or The above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides, and particularly hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The transition metal compound of Group IVB containing a ligand having a [C] cyclopentadienyl skeleton (hereinafter sometimes referred to as component [C]) used in the present invention has the following general formula. The compound represented by [II] can be illustrated. In the present invention, this component [C] is at least 2
Used in combination of species.

ML _X [II] In the above general formula [II], M is a transition metal of Group IVB, specifically, zirconium, titanium or hafnium, and L is a coordination metal coordinated with the transition metal. Is a ligand, at least one L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, Alkoxy group, aryloxy group, halogen atom, trialkylsilyl group, SO ₃ R (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) or a hydrogen atom. And x is the valence of the transition metal.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula [II] contains two or more groups having a cyclopentadienyl skeleton, the two groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene, It may be bonded via a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Examples of the ligand other than the ligand having a cyclopentadienyl skeleton include the following. Specifically as a hydrocarbon group having 1 to 12 carbon atoms,
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and pentyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; benzyl group, neofil group etc. An aralkyl group is exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group. A phenoxy group etc. are illustrated as an aryloxy group.

Halogen includes fluorine, chlorine, bromine,
Examples thereof include iodine. Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

Examples of the compound represented by the above general formula [IV] include
For example, when the valence of the transition metal is 4, more specifically,
It is represented by the following general formula [II ′]. R¹ _aR² _bR³ _cR^Four _dM ... [II '] (In the formula [II'], M is zirconium, titanium or huff.
N, R¹Has a cyclopentadienyl skeleton
R group², R³And R^FourIs cyclopentadier
A group having a nyl skeleton, an alkyl group, a cycloalkyl group,
Aryl group, aralkyl group, alkoxy group, aryloxy
Si group, halogen atom, trialkylsilyl group, SO₃R
Or a hydrogen atom, a is an integer of 1 or more, and a +
b + c + d = 4. ) In the present invention, R in the above general formula [II ′] is², R³And
And R^FourOne of them has cyclopentadienyl skeleton
A group of transition metal compounds such as R¹And R ²Siku
A transition metal compound having a lopentadienyl skeleton
Is preferably used. These cyclopentadienyl
The group having a skeleton is an alkylene such as ethylene or propylene.
Group, a substituted alkylene group such as diphenylmethylene,
Alkylidene group such as Sopropylidene, silylene group or
Is dimethylsilylene, diphenylsilylene, methylphen
Linked via a substituted silylene group such as nylsilylene
It may be. Also, R³And R^FourIs cyclopenta
Group having dienyl skeleton, alkyl group, cycloalkyl
Group, aryl group, aralkyl group, alkoxy group, aryl
Roxy group, halogen atom, trialkylsilyl group, SO
₃R or a hydrogen atom.

Specific examples of transition metal compounds in which M is zirconium will be shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride,

Ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) ) Zirconium bis (methane sulfonate), ethylene bis (indenyl) zirconium bis (p-toluene sulfonate),
Ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl
-Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) ) Zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (indenyl)
Zirconium bis (trifluoromethane sulfonate),
Dimethyl silylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenyl silylene bis (indenyl) zirconium dichloride, methylphenyl silylene bis (indenyl) zirconium dichloride ,

Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis ( Cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclo Pentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bi (Cyclopentadienyl) dibenzyl zirconium, bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methane sulfonato),
Bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato),

Bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethane) Sulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, Bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutane) Le cyclopentadienyl) zirconium bis (methane sulfonato), bis (trimethyl cyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl)
Zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product is 1,2,3- and 1,2,4-. Including substitutes. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

Further, in the present invention, in the above zirconium compound, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.

In the present invention, the component [C] as described above is
Used in combination of two or more. In this case, at least one selected from the following (i) and (ii),
It is preferable to use in combination with at least one selected from (iii) and (iv).

(I) It has two ligands having a cyclopentadienyl skeleton, and the ligand having this cyclopentadienyl skeleton has a (substituted) alkylene group, a (substituted) silylene group or the like. A transition metal compound (hereinafter referred to as "bridge type transition metal compound") that is bonded together.

(Ii) A transition metal compound having two ligands having a cyclopentadienyl skeleton, and the ligands having a cyclopentadienyl skeleton being not bonded to each other (hereinafter referred to as "non-bridge Type transition metal compound "), wherein the ligand having a cyclopentadienyl skeleton has 2 to 5 substituents, (iii) a ligand having a cyclopentadienyl skeleton Is a non-bridge type transition metal compound having no substituent.

(Iv) A non-bridge type transition metal compound in which the ligand having a cyclopentadienyl skeleton has one substituent. Among the above combinations, in particular, the ligand having a cyclopentadienyl skeleton has 2 to 3 substituents (ii)
It is preferable to use the transition metal compound of (iv) and the transition metal compound of (iv) in combination.

When two kinds of components [C] are combined, one of them is 5 to 95 mol%, preferably 10 to 90.
It is desirable to be in the range of mol%, more preferably 20-80 mol%. When combining three or more kinds, the mixing ratio of the component [C] is arbitrary, but one component is not used in excess of 95 mol% and is not used in less than 5 mol%.

By using at least two kinds of transition metal compounds as the olefin polymerization catalyst, an olefin polymer having a wide molecular weight distribution and excellent moldability can be obtained.

Examples of the [D] organoaluminum compound (hereinafter sometimes referred to as “component [D]”) used in the present invention include organoaluminum compounds represented by the following general formula [III]. be able to.

R ⁵ _n AlX _3-n [III] (In the formula, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, and X 5
Is halogen or hydrogen, and n is 1 to 3. In the above formula [III], R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-
Examples thereof include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

As such an organoaluminum compound, the following compounds are specifically used. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, Dialkyl aluminum halides such as diisobutyl aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethylaluminium sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; methylaluminium Mujikurorido, ethylaluminum dichloride, isopropyl aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dibromide; Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organic aluminum compound [D], a compound represented by the following general formula [IV] can be used. R ⁵ _n AlY _3-n ... [IV] (wherein R ⁵ is the same as above, Y is an —OR ⁶ group,
OSiR ⁷ ₃ group, -OAlR ⁸ ₂ group, -NR ⁹ ₂ group, -Si
R ¹⁰ ₃ group or —N (R ¹¹ ) AlR ¹² ₂ group, and n is 1
A ^{~2, R 6, R 7,} R 8 and R ¹² are methyl groups,
An ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁹ is hydrogen, a methyl group,
It is an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group or the like, and R ¹⁰ and R ¹¹ are a methyl group, an ethyl group or the like. ) As such an organoaluminum compound, the following compounds are specifically used.

(I) Compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like.

(Ii) compounds represented by R ⁵ _n Al (OSiR ⁷ ₃ ) _3-n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al
(OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc.

(Iii) a compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ Al
OAl (iso-Bu) ₂ etc.

(Iv) compounds represented by R ⁵ _n Al (NR ⁹ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ A
1NHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (S
iMe ₃ ) ₂ etc.

(V) A compound represented by R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , for example, (iso-Bu) ₂ AlSiMe _{3 and the} like.

[0069]

[Chemical 1]

Among the organoaluminum compounds represented by the above general formulas [III] and [IV], R ⁵ ₃ Al and R ⁵ _n Al (O
R ⁶⁾ _3-n, it can be mentioned organoaluminum compounds represented by _{^{R 5 n Al (OAlR 8 2}} ) 3-n Suitable examples, R
Those in which ⁵ is an isoalkyl group and n = 2 are particularly preferred. These organoaluminum compounds may be used as a mixture of two or more kinds.

The solid catalyst for olefin polymerization in the present invention is [A] a fine particle carrier, [B] an organoaluminum oxy compound and a group IVB transition metal compound having at least two [C] cyclopentadienyl skeletons. Can be prepared by further mixing [D] an organoaluminum compound in an inert solvent, introducing an olefin into the mixture, and performing prepolymerization.

At this time, the order of mixing and contacting the above-mentioned respective components is arbitrarily selected, but it is preferable that the component [A] and the component [B] are mixed and contacted, and then the component [C] is mixed and contacted. [A] and component [B] are mixed and contacted, then component [C] and then component [D] are mixed and contacted in this order, or component [A] and component [B] are mixed and contacted, and then Component [D] and then component [C] are mixed and contacted in this order, or component [A] and component [B] are mixed and contacted, and then component [D] and component [C] are simultaneously or, It is selected that the components [D] and the components [C] are mixed and contacted in advance and then mixed and contacted. The component [C] is preferably mixed and used in advance, and the mixing and contact are preferably performed with stirring.

FIG. 1 shows the steps for preparing the solid catalyst for olefin polymerization according to the present invention. Examples of the inert hydrocarbon medium used in the preparation of the solid catalyst for olefin polymerization according to the present invention include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Cyclopentane, cyclohexane,
Alicyclic hydrocarbons such as methylcyclopentane; benzene,
Examples thereof include aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

The mixing temperature for mixing and contacting the component [A], the component [B], the component [C] and the component [D] is usually −
It is desirable that the temperature is in the range of 100 to 200 ° C, preferably -70 to 100 ° C. The order of mixing the component [A] and the component [B] is arbitrary, but it is desirable to add the components to be added later over 5 minutes to 2 hours. The components [A] and [B] are mixed and contacted under the above-mentioned conditions, and then further -30 to 30
At a temperature of 200 ° C, preferably 0-120 ° C, 1
Mixing and contacting for 0 minutes to 10 hours, preferably 1 to 6 hours,
After that, it is desirable that the component [C] is mixed and brought into contact with it, and if desired, the component [D] is brought into mixed and contact with it.

When the component [A], the component [B], the component [C] and, if desired, the component [D] are mixed and brought into contact with each other, water (H ₂ O) contained in the component [A] and the component [B].
Molar ratio of aluminum to aluminum (Al) (H ₂ O / Al)
Is usually in the range of 0.02 to 0.8, preferably 0.05 to 0.5.

Component [C] is usually 1 per 1 g of component [A].
0 ^{−5 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ⁻⁵ to 10 ⁻³
Used in amounts in the molar range, the concentration of component [C] is about 1
0 ^{−4 to} 2 × 10 ⁻² mol / liter, preferably 2 × 10
It is in the range of ^-4 to 10 ^-2 mol / liter.

Component [B] aluminum and component [C]
The atomic ratio with the transition metal (Al / transition metal) is usually 1
It is in the range of 0 to 3000, preferably 20 to 2000. The aluminum atom (Al _D ) of the component [ _D ] and the aluminum atom (A of the component [B] that are used as necessary.
The atomic ratio (Al _D / Al _B ) of l _B ) is usually 0.02 to
3, preferably in the range of 0.05 to 1.5.

In the present invention, an olefin is prepolymerized in the presence of the above-mentioned component [A], component [B], component [C], and optionally component [D]. In the prepolymerization, the transition metal compound is usually 10 ⁻⁵ to 2 × 10 ⁻² mol /
It is used in an amount of 1 liter, preferably 5 × 10 ^-5 to 10 ^-2 mol / liter, and the prepolymerization temperature is -20 to 80.
C., preferably 0 to 50.degree. C., and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

The olefin used in the prepolymerization is selected from the olefins used in the polymerization,
Preferred is ethylene or a mixture of ethylene and an α-olefin.

The o'clock according to the present invention obtained as described above
The reffin polymerization catalyst contains at least two components [C]
It is supported on the catalyst component [A] together with the catalyst component [B].
It Such an olefin polymerization solid catalyst of the present invention,
About 5 x 10 per gram of ingredient [A] ^-6-10^-3Gram atom,
Preferably 10^-Five~ 3 x 10^-FourTransitions in the range of gram atoms
About 10 metal atoms are supported^-3-10^-1Gram atom, good
2x10 is better^-3~ 5 x 10^-2Range of gram atom
It carries a luminium atom.

Further, it is desirable that the amount of the polymer produced by the prepolymerization is in the range of about 0.1 to 500 g, preferably 0.3 to 300 g, and particularly preferably 1 to 100 g per 1 g of the component [A].

When the olefin polymerization is carried out using the solid catalyst for olefin polymerization in which the olefin is prepolymerized as described above, the transition metal compound of the component [C] is converted into transition metal atoms per liter of the polymerization volume. Usually 10
It is desirable to use an amount in the range of ^-8 to 10 ^-3 gram atom, preferably 10 ^-7 to 10 ^-4 gram atom. At this time, an organoaluminum compound or aluminoxane may be used if necessary. Examples of the organoaluminum compound used at this time include the same compounds as the above-mentioned component [D]. The amount used is 0 to 500 mol, preferably 5 to 20 per gram atom of transition metal atom.
It is preferably in the range of 0 mol.

In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components. Examples of olefins that can be polymerized by such an olefin polymerization catalyst include ethylene, and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-
Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene , 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, etc. You can Further, styrene, vinylcyclohexane, diene and the like can be used.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method. In the liquid phase polymerization method, the same inert hydrocarbon solvent used in the catalyst preparation method can be used, and the olefin itself can also be used as the solvent.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually in the range of -50 to 150 ° C, preferably 0 to 100 ° C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² .
The conditions are in the range of cm ² , and the polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the polymerization in two or more stages under different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.

The olefin polymer obtained by the catalyst for olefin polymerization according to the present invention is according to ASTM D1238-65T,
MF measured at 190 ° C under a load of 2.16 kg
R is usually in the range of 0.001 to 100 g / 10 minutes.

Further, the melt tension (MT) and the MFR are
Normally, the relationship represented by log MT ≧ −0.66 log MFR + 0.5 is satisfied.

As described above, the ethylene polymer produced according to the present invention has excellent melt tension and good moldability.
The melt tension is determined by measuring the stress when the melted polymer is stretched at a constant rate. That is, the generated polymer powder or the powder is once melted in decane, and then the polymer precipitated in a methanol / acetone (1/1) solution in an amount of 5 times or more the amount of decane is used as a measurement sample, manufactured by Toyo Seiki Seisakusho, Using MT measuring machine, resin temperature 190 ° C, extrusion speed 10 mm / min, winding speed 1
The measurement was performed under the conditions of 0 to 20 m / min, nozzle diameter 2.09 mmφ, and nozzle length 8 mm. When measuring the melt tension, the ethylene-based copolymer was preliminarily supplemented with 2,6-
0.1% by weight of di-t-butylparacresol was added.

[0089]

The solid catalyst for olefin polymerization according to the present invention comprises a fine particle carrier [A] containing at least 1.0% by weight of water, an organoaluminum oxy compound [B], and at least two kinds of cyclopenta. IVB having a dienyl skeleton
It is formed by prepolymerizing an olefin of a group transition metal compound [C] and optionally an organoaluminum compound [D].

Such a solid catalyst for olefin polymerization is
An olefin polymer having an excellent melt tension can be obtained, and a spherical olefin polymer having a high polymerization activity and an excellent particle property can be produced, and when two or more kinds of monomers are copolymerized, a composition distribution of A narrow copolymer can be obtained. Further, when such an olefin polymerization catalyst is used, an olefin polymer having a larger average molecular weight can be obtained as compared with the case where an olefin is polymerized under the same conditions using a conventional catalyst. Further, the polymer obtained by the present invention has a wide molecular weight distribution and is excellent in melt tension, and therefore is excellent in moldability.

[0091]

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

[0092]

Example 1 [Preparation of water adsorption carrier] 150 g of silica (F-94 manufactured by Fuji Devison Co., Ltd.) was placed in a quartz tube having an inner diameter of 45 mm loaded in an electric furnace.
8), and under nitrogen flow at 200 ° C for 4 hours, then 7
It was dried at 00 ° C. for 7 hours.

Next, 30 g of the dried silica obtained above was placed in a 500 ml eggplant-shaped flask, and 1.6 m was placed under a nitrogen atmosphere.
1 l of water was added, and the mixture was rotated for 1 hour and stirred. In this way, water adsorbed silica was obtained.

When 20 g of the water-adsorbed silica was taken and dried at 200 ° C. for 4 hours under a nitrogen stream, a weight loss of 1.00 g was recognized. Therefore, the amount of water in the water-adsorbed silica is 5.00% by weight.

[Preparation of solid catalyst component (A-1)] To a glass flask (400 ml) purged with nitrogen was added 85 m of toluene.
l, Organoaluminum oxy compound (methyl aluminoxane manufactured by Schering Co., dried and redissolved in toluene, Al concentration; 1.15 g atom / liter)
65.2 ml was added, and the system was brought to 0 ° C. with stirring. To this, 9.0 g of the water-adsorbed silica obtained above was added over 30 minutes under a nitrogen atmosphere. Then, the mixture was reacted at 20 to 25 ° C for 1 hour and at 80 ° C for 3 hours. Thus, the solid catalyst component (A-1) was obtained.

[Preparation of Solid Catalyst (C-1)] 150 ml of hexane was placed in a 400 ml glass flask purged with nitrogen, and the solid catalyst component (A-1) obtained above was mixed with Al while stirring.
15 mg of atom, bis (n-propylcyclopentadienyl) zirconium dichloride was converted into 0.
02 mmol and 0.04 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
1.5 mmol of triisobutylaluminum was added,
Ethylene gas (normal pressure) was continuously introduced, and prepolymerization was performed at 30 ° C. for 2 hours. By this operation, 0.033 milligram atom of zirconium, 9.0 milligram atom of aluminum and 6.
A solid catalyst (C-1) containing 9 g was obtained.

[Ethylene under normal pressure suspension polymerization] Purified n-decane (1 liter) and triisobutylaluminum (0.5 mmol) were placed in a nitrogen-substituted glass polymerization vessel having an internal volume of 1 liter, and ethylene was added at 250 liter / hr. 0 hydrogen
The temperature was raised to 70 ° C. while circulating 15 liter / hr.
Next, 0.02 mmol of the solid catalyst (C-1) obtained above was added in terms of zirconium atom, and the system was kept at 75 ° C. to carry out normal-pressure suspension polymerization of ethylene for 2 hours. The amount of the polymer obtained was 72.2 g. Polymerization activity is 3610g-PE /
Corresponds to mmol-Zr.

The polymer thus obtained had an MFR of 0.65 g / 10 min., An Mw / Mn of 4.2 and a melt tension of 7 g.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (12)

[Claims] 1. [A] (i) An oxide of at least one element selected from Group II, Group III and Group IV, wherein (i)
i) A fine particle carrier containing 1.0% by weight or more of water, [B] an organoaluminum oxy compound, and at least two [C] ligands having a cyclopentadienyl skeleton.
A solid catalyst for olefin polymerization, which is formed from a Group IVB transition metal compound and an olefin polymer produced by prepolymerization. 2. [A] (i) An oxide of at least one element selected from Group II, Group III and Group IV, wherein (i
i) A fine particle carrier containing 1.0% by weight or more of water, [B] an organoaluminumoxy compound, and at least two [C] ligands having a cyclopentadienyl skeleton.
A solid catalyst for olefin polymerization formed from a Group IVB transition metal compound, [D] an organoaluminum compound, and an olefin polymer produced by prepolymerization. 3. The olefin polymerization according to claim 1 or 2, wherein the [A] fine-particle carrier is a carrier that is adsorbed with water after being dried so that the amount of adsorbed water is 1.0% by weight or more. For solid catalyst. 4. The catalyst for olefin polymerization according to claim 1, wherein the [C] transition metal compound is a Group IVB transition metal compound having an alkyl-substituted cyclopentadienyl group. 5. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 1. 6. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 2. 7. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 3. 8. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 4. 9. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 1 and an organoaluminum compound. 10. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 2 and an organoaluminum compound. 11. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 3 and an organoaluminum compound. 12. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 4 and an organoaluminum compound.