JP2975409B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a solid catalyst for olefin polymerization and a method for polymerizing olefin using the catalyst. In detail, the present invention is capable of producing a spherical olefin polymer having an excellent bulk specific gravity when a slurry polymerization method or a gas phase polymerization method, particularly, a gas phase polymerization method is employed, and has a narrow molecular weight distribution. In addition, the present invention relates to a solid catalyst for olefin polymerization capable of providing an olefin polymer having a narrow molecular weight distribution and a narrow composition distribution when applied to copolymerization of two or more olefins, and a method for polymerizing olefins using the catalyst.

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION Conventionally, as a catalyst for producing an α-olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and organoaluminum or vanadium has been used. Vanadium-based catalysts comprising a compound and an organoaluminum compound are known.

Further, as a new Ziegler-type olefin polymerization catalyst, a method for producing an ethylene / α-olefin copolymer using a catalyst comprising a zirconium compound and an aluminoxane has been recently proposed.

The catalyst formed from the transition metal compound and the aluminoxane proposed in these prior arts has remarkably superior polymerization activity as compared with a catalyst system formed from a conventionally known transition metal compound and an organoaluminum compound. However, most of the catalyst systems proposed in these are soluble in the reaction system, and often employ a solution polymerization system, which not only limits the production process, but also produces a high molecular weight polymer. However, the solution viscosity of the polymer system was remarkably increased, the bulk specific gravity of the polymer obtained by the post-treatment of these solution systems was small, and it was difficult to obtain a polymer having excellent powder properties.

On the other hand, using a catalyst in which one or both components of the above-mentioned transition metal compound and aluminoxane are supported on a porous inorganic oxide carrier such as silica, silica / alumina, and alumina, a suspension polymerization system or a gaseous Attempts have also been made to carry out olefin polymerization in a phase polymerization system.

For example, JP-A-60-35006, JP-A-60-35007
And JP-A-60-35008 describe that a catalyst in which a transition metal compound and an aluminoxane are supported on silica, silica-alumina, alumina or the like can be used.

JP-A-61-276805 discloses a reaction mixture obtained by reacting a trialkylaluminum with a zirconium compound and an aluminoxane, and further reacting the reaction mixture with an inorganic oxide having a surface hydroxyl group such as silica. A method for polymerizing an olefin in the presence of a catalyst comprising:

Further, JP-A-61-108610 and JP-A-61-29
No. 6008 proposes a method of polymerizing an olefin in the presence of a catalyst in which a transition metal compound such as a metallocene and an aluminoxane are supported on a support such as an inorganic oxide.

In the method proposed in the above prior art, an aluminoxane component had to be separately synthesized and used.

On the other hand, JP-A-61-31404 discloses that in the presence of a mixed catalyst comprising a product obtained by reacting a trialkylaluminum with water in the presence of silicon dioxide or aluminum oxide and a transition metal compound, A method of polymerizing or copolymerizing ethylene or ethylene and an α-olefin has been proposed. According to this method, a step of separately synthesizing aluminoxane can be omitted. However, the bulk density of the obtained polymer was as low as 0.2 g / cm ³ or less.

JP-A-1-207303 discloses a gas phase polymerization by adding metallocene to a reaction mixture obtained by reacting undehydrated silica gel and trialkylaluminum in a solvent, and then removing the solvent and drying the mixture. A method for obtaining a catalyst for use is taught. However, according to this method, although a separate synthesis step of aluminoxane can be omitted, many catalyst synthesis steps such as a solvent removal step and a drying step are required.

Object of the Invention The present invention has been made in view of the prior art as described above, and there is no need to separately synthesize aluminoxane, the catalyst synthesis step is simple, and further, the powder properties are excellent. It is an object of the present invention to provide a solid catalyst for olefin polymerization capable of providing an olefin polymer and a method for polymerizing olefin using the catalyst.

SUMMARY OF THE INVENTION The solid catalyst for olefin polymerization according to the present invention comprises: [A] an inorganic oxide containing water and chloride or sulfate of a metal selected from the group consisting of magnesium, aluminum, iron and nickel [A-1]. And (B) a transition metal compound represented by the following formula (I): ML ₄ ... (I) (wherein M is zirconium , Hafnium and titanium, L is a ligand coordinated to the transition metal, at least one L is a ligand having a cycloalkadienyl skeleton, When at least two or more ligands having a dienyl skeleton are included, the ligand having at least two cycloalkadienyl skeletons may be an alkylene group or a substituted alkylene group. , A silylene group, may be bonded via a substituted silylene group, L other than a ligand having a cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a silyloxy group, Halogen or hydrogen) and, if necessary, [C] an organoaluminum compound.

Further, the solid catalyst for olefin polymerization according to the present invention,
It is formed by prepolymerizing an olefin in a suspension containing [A] and [B].

Furthermore, the method for polymerizing an olefin according to the present invention comprises:
The olefin is polymerized or copolymerized in the presence of the solid catalyst for olefin polymerization as described above.

The solid catalyst for olefin polymerization according to the present invention has excellent powder properties and a narrow molecular weight distribution, and when applied to copolymerization of two or more olefins, the molecular weight distribution and the composition distribution are particularly narrow in olefin copolymers. An ethylene-based copolymer can be provided.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the solid catalyst for olefin polymerization according to the present invention and a method for polymerizing olefins using the catalyst will be specifically described.

In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. Sometimes used in

FIG. 1 shows an explanatory view of the solid catalyst for olefin polymerization according to the present invention.

The catalyst for olefin polymerization according to the present invention comprises: [A] a component obtained by contacting a specific inorganic oxide [A-1] with an organoaluminum compound [A-2]; and [B] a cycloalkadienyl. It is formed from a transition metal compound containing a ligand having a skeleton and, if necessary, [C] an organoaluminum compound.

In the present invention, as the inorganic oxide [A-1], a particulate inorganic oxide having an average particle size of usually 1 to 300 µm, preferably 10 to 200 µm is used. Specific examples of the particulate inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ and TiO ₂
Alternatively, a mixture thereof is used. Among these, Si
An oxide containing at least one component selected from the group consisting of O ₂ , Al ₂ O ₃ and MgO as a main component is preferred.

The inorganic oxide as described above contains a metal chloride or sulfate selected from the group consisting of magnesium, aluminum, iron and nickel, and water. Specific examples of chlorides or sulfates of metals selected from the group consisting of magnesium, aluminum, iron and nickel include magnesium chloride, aluminum chloride, calcium chloride, zinc chloride, ferric chloride, nickel chloride, and magnesium sulfate. , Aluminum sulfate, copper sulfate, ferric sulfate,
Nickel sulfate and the like can be mentioned.

In 1 g of the inorganic oxide, usually, a salt of the above metal is 0.1 to 10 milligram atoms in terms of metal atom, preferably 0.2 to 10 mg atom.
5 milligram atoms, 1-30 millimoles of water, preferably 2
It is contained in an amount of ~ 20 mmol.

In the present invention, specific examples of the organoaluminum compound [A-2] include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, and trialuminum. tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tricyclohexyl aluminum, trialkyl aluminum such as tricyclooctyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride Such as dialkyl aluminum halide, diethyl aluminum hydration And dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide, and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkyl aluminum is particularly preferred.

Further, as the organoaluminum compound, isoform represented by the general formula (iC ₄ H ₉ ) _x A _y (C ₅ H ₁₀ ) _z (x, y, z are positive numbers and z ≧ 2x) Prenyl aluminum can also be used.

The above-mentioned organoaluminum compounds are used alone or in combination.

The [B] transition metal compound used in the present invention has the formula ML
_x (wherein, M is a transition metal selected from the group consisting of zirconium, hafnium and titanium, L is a ligand coordinated to the transition metal, and at least one L has a cycloalkadienyl skeleton A ligand having at least two ligands having a cycloalkadienyl skeleton, the ligand having at least two cycloalkadienyl skeletons is an alkylene group, a substituted alkylene group,
L other than a ligand having a cycloalkadienyl skeleton may be bonded through a silylene group or a substituted silylene group, and L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a silyloxy group, or a halogen atom. Or x, and x is the valence of the transition metal. ).

In the above formula, M is a transition metal selected from the group consisting of zirconium, hafnium and titanium,
Of these, zirconium and hafnium are particularly preferred.

As the ligand having a cycloalkadienyl skeleton,
For example, alkyl-substituted cyclopentane such as cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, dimethylcyclopentadienyl group and pentamethylcyclopentadienyl group Dienyl group, indenyl group, 4,
Examples thereof include a 5,6,7-tetrahydroindenyl group and a fluorenyl group.

The ligand having a cycloalkadienyl skeleton as described above may be coordinated to two or more transition metals. In this case, the ligand having at least two cycloalkadienyl skeletons is They may be bonded via an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group. Examples of the alkylene group include a methylene group, an ethylene group,
Examples of the substituted alkylene group include a propylene group and the like. Examples of the substituted alkylene group include an isopropylidene group and a diphenylmethylene group. Examples of the substituted silylene group include a dimethylsilylene group and a diphenylsilylene group.

The ligand other than the ligand having a cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen or hydrogen.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Specifically, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group, and the like.Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.Examples of the aryl group include a phenyl group, a tolyl group, and the like, and an aralkyl group includes a benzyl group, A neofil group is exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the silyloxy group include a trimethylsilyloxy group and a triphenylsilyloxy group.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

Hereinafter, specific examples of the transition metal compound containing a ligand having a cycloalkadienyl skeleton in which M is zirconium will be described.

Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride, bis ( Cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride hydride, bis (indenyl) zirconium Monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium Monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride bis (Indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, (Lopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (methylcyclopentadienyl) zirconium ethoxycyclolide Bis (cyclopentadienyl) zirconium phenoxycyclolide, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium triphenylsilyloxychloride, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diethylzirconium, ethylenebis (Indenyl) diphenyl zirconium monochloride, ethylene bis (indenyl) methyl zirconium mono Chloride, ethylenebis (indenyl) ethylzirconium monochloride, ethylenebis (indenyl) methylzirconium monobromide, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (4,5,6,7- Tetrahydro-1-indenyl) dimethyl zirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide, ethylene bis (4-methyl-1-indenyl) zirconium dichloride, ethylene bis (5-methyl-1-indenyl) zirconium dichloride Ethylene bis (6-methyl-1-indenyl) zirconium dichloride, ethylene bis (7-methyl-1-indenyl) zirconium dichloride, ethylene bis (5-methoxy-1-indenyl) zirconium dichloride, ethylene bis (2,3- Dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethoxy-1-indenyl)
Zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (indenyl) zirconium dichloride, isopropylidene (cyclo) (Pentadienyl-fluorenyl) zirconium dichloride.

Further, in the above-mentioned zirconium compound, a transition metal compound in which zirconium metal is replaced by titanium metal or hafnium metal can also be used.

Next, the second olefin polymerization catalyst according to the present invention will be described.

This olefin polymerization catalyst is formed from an olefin polymerization catalyst [C] organoaluminum compound comprising the above component [A] and the above transition metal compound [B].

Examples of the [C] organoaluminum compound used in the present invention include R _n ⁶ AX _3-n (where R ⁶ is a hydrocarbon group having 1 to 12 carbons, X is halogen or hydrogen, and n is
Is 1 to 3).

In the above formula, R ⁶ 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, an n-propyl group, an isopropyl group, an isobutyl group. Group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds.

Trimethyl aluminum, triethyl aluminum,
Trialkylaluminums such as triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide.

Alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, ethyl aluminium sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide;

Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide;

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum ^{_{compound, R 6 n AY 3-n}} ( wherein R ⁶ is as defined above, Y is -OR ⁷ group, -OSiR ⁸ ₃ group,
-OAr ⁹ ₂ group, -NR ¹⁰ ₂ group, -SiR ¹¹ ₃ group or Wherein n is 1-2, R ⁷ , R ⁸ , R ⁹ and R ¹³ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ¹⁰ is hydrogen,
Examples include a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group, and R ¹¹ and R ¹² are a methyl group, an ethyl group, and the like. ) Can also be used.

As such an organoaluminum compound, specifically, the following compounds are used.

_{^{(I) R 6 n A (}} OR 7) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R 6 n A}} (OSiR 8 3) 3-n Et 2 A (OSiMe ₃₎ (such as _{iso-Bu) 2 A (OSiMe} 3) (iso-Bu) 2 A (OSiEt 3), (iii) R 6 n A (OAR 9 2) 3-n Et 2 AOAEt 2 (iso-Bu) ₂ AOA (iso-Bu) ₂ etc., (iv) R ⁶ _n A (NR ¹⁰ ₂ ) _3-n Me ₂ ANEt ₂ Et ₂ ANHMe Me ₂ ANHEt Et ₂ AN (Me ₃ Si) ₂ (iso-Bu) ₂ such as AN (Me _{3 Si) 2,} etc. _{^{(v) R 6 n A (}} SiR 11 3) 3-n (iso-Bu) 2 ASiMe 3, Organoaluminum compounds mentioned above, R ⁶ ₃ A
^{_{, R 6 n A (OR 7}} ) 3-n, can be mentioned organoaluminum compounds represented by _{^{R 6 nA (OAR 9 2)}} 3-n suitable examples, in particular R ⁶ is isoalkyl group, Those having n = 2 are preferred. These organoaluminum compounds can be used as a mixture of two or more kinds.

Next, the third solid catalyst for olefin polymerization according to the present invention will be described.

The olefin polymerization solid catalyst is formed by prepolymerizing an olefin in a suspension containing the olefin polymerization catalyst composed of the component [A] and the transition metal compound [B].

The fourth olefin polymerization catalyst according to the present invention is formed by prepolymerizing an olefin in a suspension containing the component [A] and the olefin polymerization catalyst comprising the transition metal compound [B]. It is formed from a prepolymerization catalyst component and [C] an organoaluminum compound.

The catalyst for olefin polymerization in the present invention can be specifically prepared as follows.

First, the component [A] is composed of an inorganic oxide [A-1] containing a salt of a metal belonging to the third and fourth periods of the periodic table and water in an inert hydrocarbon medium and an organoaluminum compound [A- 2] and mixed contact.

At this time, the amount of the organoaluminum compound [A-2] is usually 10 ^-3 to 10 ^-1 mol, preferably 2 × 10 ^{-3 to} 5 × 10 ^-2 mol per 1 g of the inorganic oxide [A-1]. Used.

The concentration of the organic aluminum compound [A-2] is about 0.1 to 5 mol /, preferably 0.3 to 3 mol /.
It is desirable to use within the range. The reaction temperature is usually -100 to 120C, preferably -70 to 100C, and the reaction time varies depending on the reaction temperature, but is usually about 1 to 200 hours, preferably about 2 to 100 hours.

After the reaction, the entire suspension may be used as the component [A], the inert hydrocarbon solvent may be removed by filtration, and the remaining solid component may be used as the component [A]. A solid component obtained by evaporating the inert hydrocarbon solvent from the liquid may be used as the component [A].

At this time, about 1 × 10 ⁻³ to 1 × 10 ⁻¹ gram atom, preferably 2 × 10 ⁻³ to 1 × 10 ⁻¹ gram atom per 1 g of the inorganic oxide is present on the solid component [A].
5 × 10 ^-2 gram atoms of aluminum atoms are carried.

 Next, a method for preparing the prepolymerized catalyst component will be described.

The component [A] and the transition metal compound [B] obtained as described above are mixed in an inert hydrocarbon solvent, the olefin is introduced therein, and prepolymerization is performed, whereby the olefin according to the present invention is obtained. A solid catalyst for polymerization is obtained.

When mixing the component [A] with the transition metal compound [B], the transition metal compound [B] is usually added per 1 g of the inorganic oxide.
It is used in an amount of 10 ^{-5 to} 5 × 10 ^-3 mol, preferably 5 × 10 ^-5 to 10 ^-3 mol, and the concentration of the transition metal compound [B] is about 2 ×
10 ^{-4 to} 5 × 10 ^-2 mol /, preferably 5 × 10 ^-4 to 2 × 10
^-2 mol / range. The atomic ratio between aluminum and the transition metal (A / transition metal) in the component [A] is usually 10 to 500, preferably 20 to 200. The mixing temperature of the components [A] and [B] is usually -20 to 80 ° C, preferably 0 ° C.
6060 ° C. and the contact time is 1200200 min, preferably 5 min.
~ 120 minutes.

The olefin is prepolymerized in the presence of the component [A], the component [B] and, if necessary, the component [C] as described above. In the prepolymerization, the transition metal compound is usually 10 ^-4
５5 × 10 ^-2 mol /, preferably 5 × 10 ^-4 to 10 ^-2 mol /
The prepolymerization temperature is -20 to 80C, preferably 0 to 50C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

The olefin used for the prepolymerization is selected from olefins used for the polymerization, and is preferably ethylene.

The solid catalyst for olefin polymerization of the present invention obtained as described above has an amount of about 5 × 10 ^-6 to 10 ^-3 gram atoms, preferably 10 ^{-5 to} 5 × 10 ^-4 gram atoms per gram of inorganic oxide. Transition metal atoms are carried, and about 10 ^-3 to 10 ^-1 gram atoms, preferably 2 x 10 ^{-3 to} 5 x 10 ^-2 gram atoms of aluminum atoms are carried.

Further, the amount of the polymer formed by the prepolymerization is desirably in the range of about 0.1 to 500 g, preferably 0.3 to 300 g, and particularly preferably 1 to 100 g per gram of the inorganic oxide.

As the inert hydrocarbon medium used for preparing the olefin polymerization catalyst according to the present invention, specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; and mixtures thereof. it can.

When performing olefin polymerization using the olefin polymerization catalyst as described above, the [B] transition metal compound
Usually 10 ^-8 ~
It is desirable that it be used in an amount of 10 ^-3 gram atoms, preferably 10 ^-7 to 10 ^-4 gram atoms. At this time, an organic aluminum compound [C] is used as necessary. At this time, the amount used is generally in the range of 0 to 200 mol, preferably 5 to 150 mol, per 1 gram atom of the transition metal atom.

Examples of the olefin that can be polymerized with such an olefin polymerization catalyst include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene and 1-olefin.
Butene, 1-hexene, 4-methyl-1-pentene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl- 1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene and the like can be mentioned.

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 as used in the catalyst preparation method can be used, or the olefin itself can be used as the solvent.

The polymerization temperature of the olefin using such an olefin polymerization catalyst is usually -50 to 120 ° C, preferably 0 to 100 ° C.
It is in the range of ° C. The polymerization pressure is usually from normal pressure to 100 kg / c.
m ² , preferably normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages under different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

In the present invention, the catalyst for olefin polymerization can contain other components useful for olefin polymerization in addition to the above components.

Effect of the Invention The solid catalyst for olefin polymerization according to the present invention has excellent particle properties, has a narrow molecular weight distribution and, when applied to copolymerization of two or more olefins, has a narrow molecular weight distribution and a narrow composition distribution. Can be given.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of Catalyst Component [A] To about 18.1 g of silica (F-948) dried at 800 ° C., about 100 ml of an aqueous solution of magnesium chloride (MG 1 mmol /) was added, and the mixture was stirred at room temperature for 10 minutes. And filtered. Thereafter, drying was performed for 16 hours under reduced pressure while flowing nitrogen through the silica remaining on the glass filter. As a result, for 1 g of silica, magnesium chloride
A catalyst component [A-1] containing 80 mg and 135 mg of water was obtained.

Trimethylaluminum 50 diluted with 100 ml of toluene
The mmol was cooled to 0 to -5 ° C, and 9.7 g of the catalyst component [A-1] prepared above was added dropwise thereto over 35 minutes. At this time, the temperature in the system was maintained at 0 to -5C.

Thereafter, the temperature was raised to 25 ° C., and the mixture was stirred at that temperature for 1 hour. The temperature was further raised to 80 ° C., and the mixture was stirred at that temperature for 6 hours to obtain a catalyst component [A].

Preparation of Prepolymerized Catalyst Toluene was added to the catalyst component [A] obtained above,
The volume was adjusted to 0 ml, of which 60 ml was transferred to a 400 ml glass flask. Thereto, 35.7 ml of toluene and 4.3 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr 0.0465 mol /) were further added, followed by stirring at room temperature for 30 minutes. Thereafter, 100 ml of hexane was further added, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was performed at 30 ° C. for 80 minutes. After the completion of the pre-polymerization, the mixture was filtered through a glass filter and then washed with hexane to obtain silica.
A prepolymerized catalyst containing 4.0 mg of zirconium, 78 mg of aluminum and 4 g of polyethylene per 1 g was obtained.

Polymerization 150 g of sodium chloride (special grade of Wako Pure Chemical Industries, Ltd.) was charged into a stainless steel autoclave having an internal volume of 2 which had been sufficiently purged with nitrogen, and dried under reduced pressure at 90 ° C. for 1 hour. Thereafter, the pressure in the system was returned to normal pressure by introducing ethylene gas, and the system was heated to 80 ° C. Subsequently, the prepolymerized catalyst prepared above was converted to zirconium atoms.
The polymerization was initiated by adding 0.02 milligram atoms and further introducing ethylene. The polymerization was carried out for 1 hour at a total pressure of 8 kg / cm ² -G and a temperature of 85 ° C. while continuously supplying ethylene. After completion of the polymerization, the polymer was recovered by dissolving sodium chloride in water, washed with methanol, and dried under reduced pressure at 80 ° C. for 12 hours. As a result, the bulk specific gravity is 0.
Was 49 g / cm ^3, it MFR measured under 2.16kg load at 190 ° C.
36 g of polymer, 0.07 g / 10 min, were obtained.

Example 2 Preparation of Prepolymerized Catalyst The preparation of the prepolymerized catalyst of Example 1 was repeated except that 1.5 mmol of triisobutylaluminum was added before adding bis (methylcyclopentadienyl) zirconium dichloride. A prepolymerized catalyst containing 3.8 mg of zirconium, 80 mg of aluminum, and 4.5 g of polyethylene was obtained based on 1 g of silica.

Polymerization Using the prepolymerized catalyst prepared above, polymerization was carried out in the same manner as in Example 1. As a result, the bulk specific gravity was 0.47 g / cm ³ ,
Of the polymer was 0.05 g / 10 min.

Example 3 Polymerization The prepolymerized catalyst prepared in Example 1 was slurried with 0.01 ml of zirconium atom in 10 ml of hexane, and 0.25 mmol of triisobutylaluminum was added thereto and stirred for 10 minutes. The whole amount was added to an autoclave, and polymerization was carried out in the same manner as in Example 1. As a result, polymer 25 having a bulk specific gravity of 0.45 g / cm ³ and an MFR of 0.06 g / 10 min was obtained.
g was obtained.

Comparative Example 1 In the preparation of the catalyst component [A] of Example 1, a prepolymerization was carried out in the same manner as in Example 1 using a catalyst component prepared without using magnesium chloride. As a result, 3.7 g of zirconium was added to 1 g of silica. A prepolymerized catalyst containing milligrams, 82 milligrams of aluminum and 3.8 g of polyethylene was obtained.

Using this prepolymerized catalyst, polymerization was carried out in the same manner as in Example 1. As a result, the bulk specific gravity was 0.45 g / cm ³ , and the MFR was 0.08 g / 10
27 g of polymer were obtained.

[Brief description of the drawings]

FIG. 1 is an illustration of an olefin polymerization catalyst according to the present invention.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (6)

(57) [Claims] 1. An inorganic oxide [A-1] containing [A] a chloride or sulfate of a metal selected from the group consisting of magnesium, aluminum, iron and nickel, and water;
A component obtained by contacting with an organoaluminum compound [A-2], and [B] a transition metal compound represented by the following formula (I): ML ₄ ... (I) (where M is zirconium, A transition metal selected from the group consisting of hafnium and titanium, L is a ligand coordinated to the transition metal, at least one L is a ligand having a cycloalkadienyl skeleton, When at least two ligands having an enyl skeleton are included, the ligands having at least two cycloalkadienyl skeletons are bonded via an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group. L other than a ligand having a cycloalkadienyl skeleton may be a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a silyloxy group, a halo group. Olefin polymerization catalyst comprising a a) emissions or hydrogen. 2. An olefin polymerization catalyst comprising the component [A] according to claim 1, and the transition metal compound [B] and [C] an organoaluminum compound according to claim 1. 3. A solid catalyst for olefin polymerization formed by prepolymerizing an olefin in a suspension containing the component [A] according to claim 1 and the transition metal compound [B] according to claim 1. . 4. An olefin polymerization catalyst comprising the olefin polymerization solid catalyst according to claim 3 and [C] an organoaluminum compound. 5. A polymerization of an olefin, wherein the olefin is polymerized or copolymerized in the presence of the catalyst for olefin polymerization or the solid catalyst for olefin polymerization according to any one of claims 1 to 4. Method. 6. Chloride or sulfate of a metal selected from the group consisting of magnesium, aluminum, iron and nickel is 0.1 to 10 mg atom in terms of metal atom per 1 g of the inorganic oxide [A-1]. The catalyst for olefin polymerization according to claim 1, wherein the amount of water is 1 to 30 mmol.