JP2530624B2 - Olefin Polymerization Method - Google Patents

Description

The present invention relates to a method for polymerizing olefins. More specifically, in the present invention, a slurry polymerization method or a gas phase polymerization method,
In particular, the present invention relates to a method for polymerizing olefin, which has a good particle size distribution, is capable of producing a spherical polymer, and has an excellent bulk specific gravity when a gas phase polymerization method is adopted. Also, the molecular weight distribution is narrow,
Moreover, it relates to a method for polymerizing an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution with excellent polymerization activity when applied to the copolymerization of two or more kinds of olefins.

[Conventional technology]

Conventionally, as a method for producing an α-olefin polymer, particularly 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 used. A method of copolymerizing ethylene or ethylene and α-olefin in the presence thereof is known. In general, the ethylene / α-olefin copolymer obtained with a titanium catalyst generally has a wide molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. In addition, the ethylene / α-olefin copolymer obtained with the vanadium catalyst has a narrower molecular weight distribution and composition distribution than those obtained with the titanium catalyst, and the transparency, surface non-adhesiveness, and mechanical properties are significantly improved. However, α-olefin polymers having improved performances, particularly ethylene / α-olefin copolymers, are still inadequate for applications requiring these properties.

On the other hand, a catalyst comprising a zirconium compound and aluminoxane has recently been proposed as a new Ziegler type olefin polymerization catalyst.

JP-A-58-19309 discloses that the following formula (cyclopentadienyl) ₂ MeRHal [wherein R is cyclopentadienyl, C ₁ -C ₈ -alkyl, halogen, Me is a transition metal , Hal is halogen], and a transition metal-containing compound represented by the following formula: Al ₂ OR ₄ (Al (R) -O) _n [wherein R is methyl or ethyl and n is a number of 4 to 20]. Is a linear aluminoxane represented by In the presence of a catalyst consisting of a cyclic aluminoxane represented by [wherein R and n are the same as defined above],
A method of polymerizing ethylene and one or more of C _{3 to} C ₁₂ α-olefins at a temperature of −50 ° C. to 200 ° C. is described. The same publication discloses that in order to control the density of the resulting polyethylene, small amounts of somewhat long-chain α up to 10% by weight can be used.
It is stated that the polymerization of ethylene should be carried out in the presence of olefins or mixtures.

JP-A-59-95292 discloses the following formula [Wherein n is 2 to 40 and R is C _{1 to} C ₈ alkyl] and a linear aluminoxane represented by the following formula An invention relating to a process for producing a cyclic aluminoxane represented by [wherein n and R are the same as defined above] is described. In the same publication, for example, methylaluminoxane and a bis (cyclopentadienyl) compound of titanium or zirconium produced by the same production method are mixed, and olefin polymerization is carried out. It is stated that 25 million g or more of polyethylene can be obtained.

JP-A-60-35005 discloses the following formula [Wherein R ¹ is C ₁ -C ₁₀ alkyl, R ⁰ is R ¹ or is bonded to represent -O-], and the aluminoxane compound is first reacted with a magnesium compound, and then the reaction product is formed. There is disclosed a method for producing a polymerization catalyst for olefin by chlorinating the product and further treating it with a compound of Ti, V, Zr or Cr. The publication describes that the catalyst is particularly suitable for the copolymerization of a mixture of ethylene and C ₃ -C ₁₂ α-olefin.

JP-A-60-35006 discloses a catalyst system for producing a reactor blend polymer, which comprises mono-, di- or tri-cyclopentadienyl of two or more different transition metals or its derivative (a) and alumoxane ( Aluminoxane) (b)
Are disclosed. In Example 1 of the publication, ethylene and propylene are polymerized using bis (pentamethylcyclopentadienyl) zirconium dimethyl and alumoxane as catalysts to contain a number average molecular weight of 15,300, a weight average molecular weight of 36,400 and a propylene component of 3.4%. It is disclosed that polyethylene is obtained. Further, in Example 2, bis (pentamethylcyclopentadienyl)
Polymerization of ethylene and propylene using zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and alumoxane as catalysts, and a number average molecular weight of 2,200, a weight average molecular weight of 11,900 and a toluene soluble part containing a propylene component of 30 mol% and a number average. Molecular weight 3,
000, a weight average molecular weight of 7,400 and a number average molecular weight of 2,000 composed of a toluene insoluble portion containing 4.8 mol% of a propylene component.
A blend of polyethylene and an ethylene-propylene copolymer containing 0, a weight average molecular weight of 8,300 and a propylene component of 7.1 mol% is obtained. Similarly, in Example 3, the molecular weight distribution (w / n) was 4.57 and the propylene component was 20.6 mol%.
Soluble part and molecular weight distribution of 3.04 and propylene component 2.9
Blends of LLDPE and ethylene-propylene copolymers consisting of mol% insoluble moieties are described.

JP-A-60-35007 discloses ethylene alone or together with α-olefin having 3 or more carbon atoms and metallocene and the following formula. [Wherein, R is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to about 20] or a cyclic alumoxane represented by the following formula: A method of polymerizing in the presence of a catalyst system comprising a linear alumoxane represented by [wherein R and n are the same as defined above] is described. According to the description of the publication, the polymer obtained by the same method has a weight average molecular weight of about 500 to about 1.4 million and a molecular weight distribution of 1.5 to 4.0.

Further, in JP-A-60-35008, by using a catalyst system containing at least two kinds of metallocene and alumoxane, polyethylene having a broad molecular weight distribution or ethylene and a C ₃ -C ₁₀ α-olefin compound can be used. It is described that a polymer is produced. The publication describes that the above copolymer has a molecular weight distribution (w / n) of 2 to 50.

The catalysts formed from these transition metal compounds and aluminoxane have significantly higher polymerization activity than conventionally known catalyst systems, but these catalyst systems are soluble in the reaction system and It was difficult to obtain a polymer having a low bulk specific gravity and excellent powder properties.

On the other hand, a method of using a catalyst formed of aluminoxane and a solid catalyst component in which the transition metal compound is supported on a porous inorganic oxide carrier such as silica, silica-alumina, or alumina is also disclosed in JP-A-60-35006. Publication, JP-A-60-3
It is also proposed in Japanese Patent Laid-Open No. 5007, Japanese Patent Laid-Open No. 60-35008, and the like, and further, Japanese Patent Laid-Open No. 61-31404, Japanese Patent Laid-Open No. 61-10861.
No. 0, JP-A-60-106808 and the like also propose a method of using a solid catalyst component supported on a similar porous inorganic oxide carrier. In the methods described in these prior arts, by employing a supported solid component, there were many cases where the polymerization activity was lowered and the powder properties such as bulk specific gravity of the obtained polymer were insufficient.

[Problems to be solved by the invention]

The present inventors have found that olefin copolymers having excellent powder properties, a narrow molecular weight distribution, and a narrow molecular weight distribution and a narrow composition distribution when applied to the copolymerization of two or more kinds of olefins,
In particular, as a result of examining a method for producing an ethylene polymer or an ethylene / α-olefin copolymer having an excellent powder property and a narrow molecular weight distribution and / or composition distribution with excellent polymerization activity, a specific carrier-supported solid catalyst component was used. By doing so, they have found that the above-mentioned objects can be achieved, and have reached the present invention.

[Means for Solving Problems] and [Action] According to the present invention, [A] a porous inorganic material treated with an organometallic compound selected from organoaluminum, organoboron, organomagnesium, organozinc and organolithium. A solid catalyst in which a zirconium compound having a [B] cycloalkadienyl group is supported on an oxide carrier, wherein 3 x 10 ^-3 to 3 milligrams of zirconium are supported on 1 gram of a porous inorganic oxide carrier. And a solid catalyst component, and a catalyst formed from [C] aluminoxane, in the presence of a catalyst formed by olefin polymerization or copolymerization.

 The present invention will be described in detail 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 to mean not only homopolymer but also copolymer. .

The catalyst used in the present invention is formed from three catalyst components [A], [B] and [C].

The catalyst component [A] is organic aluminum, organic boron,
It is a porous inorganic oxide support treated with an organometallic compound selected from organomagnesium, organozinc and organolithium. Specific examples of the carrier include SiO ₂ , Al ₂ O ₃ , and Mg.
O, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or
These mixtures for _{example, SiO 2 -MgO, SiO 2 -Al} 2 O 3, SiO 2
_{-TiO 2, SiO 2 -V 2 O} 5, SiO 2 -Cr 2 O 3, can be exemplified SiO ₂ -TiO ₂ -MgO and the like. Among these, SiO ₂ and Al ₂ O
A carrier containing as a main component at least one component selected from the group consisting of ₃ is preferable. The inorganic oxide contains a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ S.
_{O 4, Al 2 (SO 4} ) 3, BaSO 4, KNO 3, Mg (NO 3) 2, Al (NO 3) 3, Na
_It does not matter even if it contains carbonate, sulfate, nitrate, or oxide components such as ₂ O, K ₂ O and Li ₂ O. The carrier has different properties depending on its type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 μm.
To 200μ, specific surface area 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, pore volume 0.3 to 3.0 cm ³ / g,
It is preferably 0.5 to 2.5 cm ³ / g. The carrier is usually 1
It is used by baking at 50 to 1000 ° C, preferably 200 to 800 ° C.

In the catalyst component [A], the above-mentioned carrier is previously treated with an organometallic compound before supporting the catalyst component [B]. Examples of the organic metal compound include organic aluminum, organic boron, organic magnesium, organic zinc, and organic lithium. Among these, organoaluminum compounds are preferable, and specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, and tributylaluminum, alkenylaluminum such as isoprenylaluminum, dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide. In addition to alkyl aluminum sesquialkoxides such as dialkyl aluminum alkoxides such as methyl aluminum sesquimethoxide and ethyl aluminum sesquiethoxide, R ¹ _2.5 Al (OR ² )
Partially alkoxylated alkylaluminum having an average composition represented by _0.5, etc., dialkylaluminum halides such as dimethylaluminium chloride, diethylaluminum chloride, dimethylaluminum bromide, alkyl such as methylaluminum sesquichloride, ethylaluminum sesquichloride. Partially halogenated alkylaluminum such as alkylaluminum dihalide such as aluminum sesquihalide, methylaluminum dichloride and ethylaluminum dichloride can be exemplified.

As the organoaluminum compound, trialkylaluminum and dialkylaluminum dichloride are preferable, and trimethylaluminum, triethylaluminum, dimethylaluminum chloride and diethylaluminum chloride are particularly preferable.

The mixing ratio of the organoaluminum compound and the carrier in the above treatment is 0.5 to 50, preferably 1 to 3 in terms of mmol of organoaluminum compound / gram of carrier.
The range is 0, more preferably 1.5 to 20.

In the catalyst component [A], the treatment of the porous inorganic oxide carrier with an organoaluminum compound is carried out by dispersing the carrier in an inert solvent, adding one or more of the above organoaluminum compounds, and adding 0 to 120 ° C. Treatment at a temperature of preferably 10 to 100 ° C, more preferably 20 to 90 ° C for 10 minutes to 10 hours, preferably 20 minutes to 5 hours, more preferably 30 minutes to 3 hours under normal pressure, reduced pressure or pressure. Can be done by.

Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane and isooctane, and alicyclic hydrocarbons such as cyclohexane.

The zirconium compound having a cycloalkadienyl group in the catalyst component [B] has, for example, the following formula (I) R ¹ _k R ² _l R ³ _m R ⁴ _n Zr (I) [wherein R ¹ is a cycloalkadienyl group] , R ² , R ³
And R ⁴ is a cycloalkadienyl group, an aryl group, an alkyl group, an aralkyl group, an alkoxy group, a halogen atom or hydrogen, and k ≧ 1, k + l + m + n = 4]
Is a compound represented by.

The cycloalkadienyl group is, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group,
Examples thereof include an indenyl group and a tetrahydroindenyl group.
Examples of the alkyl group of R ² , R ³ and R ⁴ include a methyl group,
Examples thereof include an ethyl group, propyl group, isopropyl group and butyl group, examples of the aryl group include phenyl group and tolyl group, and examples of the aralkyl group include benzyl group and neophyl group. Examples of the alkoxy group include a methoxy group, ethoxy group, propoxy group, butoxy group, 2-ethylhexoxy group, and the like, and examples of the halogen atom include fluorine, chlorine, bromine, and the like. . The following compounds can be illustrated as this zirconium compound.

Bis (cyclopentadienyl) zirconium monochloride monohydride, Bis (cyclopentadienyl) zirconium monobromide monohydride, Bis (cyclopentadienyl) methylzirconium hydride, Bis (cyclopentadienyl) ethylzirconium hydride, Bis ( Cyclopentadienyl) cyclohexyl zirconium hydride, Bis (cyclopentadienyl) phenyl zirconium hydride, Bis (cyclopentadienyl) benzyl zirconium hydride, Bis (cyclopentadienyl) neopentyl zirconium hydride, Bis (methylcyclopentadi) (Enyl) zirconium monochloride monohydride, bis (indenyl) zirconium monochloride monohydride, bis (indene) Clopentadienyl) 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 (methylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis ( Indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium phenyl, bis (cyclo Lopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) methoxyzirconium chloride, bis (cyclopentadienyl) ethoxyzirconium chloride, bis (cyclopentadienyl) butoxyzirconium chloride, bis (cyclopentadienyl) 2-ethylhexyl Soxy zirconium chloride, bis (cyclopentadienyl) methyl zirconium ethoxide, bis (cyclopentadienyl) methyl zirconium butoxide, bis (cyclopentadienyl) ethyl zirconium ethoxide, bis (cyclopentadienyl) phenyl zirconium ethoxy Bis (cyclopentadienyl) benzyl zirconium ethoxide, bis (methylcyclopentadienyl) ethoxy zirconium chloride, bis (indenyl ) Ethoxyzirconium chloride, bis (cyclopentadienyl) ethoxyzirconium, bis (cyclopentadienyl) butoxyzirconium, bis (cyclopentadienyl) 2-ethylhexoxyzirconium.

In the method of the present invention, the catalyst component [B] is supported on the catalyst component [A].

In the supporting reaction, 1 g of the catalyst component [A], which is a porous inorganic oxide carrier treated with an organometallic compound selected from organoaluminum, organoboron, organomagnesium, organozinc, and organolithium, is used for cycloalkadienyl. The catalyst component [B], which is a zirconium compound having a group, is 3 × 10 ⁻³ to 3 in terms of zirconium atom.
It is carried by milligram atoms, preferably 5 × 10 ⁻³ to 2 milligram atoms, more preferably 1 × 10 ⁻² to 1 milligram atoms. When the supported amount is lower than 3 × 10 ^-3 mg atom, a large amount of the carrier remains in the produced polymer, which causes a fish eye when formed into a film, and when it is higher than 3 mg atom, the unit is It is not preferable because the activity per zirconium atom is reduced.

The loading method is as follows: catalyst component [A] in an inert hydrocarbon medium.
Is added, and the catalyst component [B] is added thereto. The reaction temperature is generally 0 to 100 ° C., preferably 20 to 90 ° C., and the reaction time is generally 5 minutes to 5 hours, preferably 10 minutes to 2 hours. After the supporting reaction, the solid hydrocarbon component can be obtained by removing the inert hydrocarbon medium by excess or by evaporating it under normal pressure or reduced pressure.

 The catalyst component [C] is aluminoxane.

General formula (II) and general formula (III) as aluminoxane used as the catalyst component [C] The organoaluminum compound represented by can be exemplified. In the aluminoxane, R is a methyl group,
It is a hydrocarbon group such as an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group, and m is an integer of 2 or more, preferably 5 or more. Examples of the method for producing the aluminoxane include the following methods.

(1) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, chloride first
A method in which a trialkylaluminum is added to a hydrocarbon medium suspension such as cerium hydrate and reacted.

(2) A method in which water is allowed to act directly on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of organic metal component.

INDUSTRIAL APPLICABILITY The present invention is effective for producing olefin polymers, particularly ethylene polymers and copolymers of ethylene and α-olefin.

Examples of α-olefins that can be used in the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene. , 1-
Examples thereof include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In the method of the present invention, the polymerization of olefin is usually
It is carried out in a gas phase or a liquid phase, for example, in the form of a slurry, but a gas phase polymerization method is particularly preferable. When carrying out by gas phase polymerization, the polymerization temperature is usually 0 to 120 ° C., preferably 20.
To 100 ° C.

The use ratio of the zirconium compound when carrying out the method of the present invention by a gas phase polymerization method is usually 10 ^-8 to 10 ^-2 g atom / l, preferably the concentration of zirconium metal atom in the polymerization reaction system. It is in the range of 10 ^-7 to 10 ^-3 gram atom / l.

The proportion of aluminoxane used is usually 10 ^-4 to 10 ^-1 gram atom / l, preferably 10 ^-3 to 5 × 10 ^-2 gram atom as the concentration of aluminum atoms in the polymerization reaction system.
/ l range, and is usually 25 as the ratio of aluminum metal atoms to zirconium metal atoms in the polymerization reaction system.
To 10 ⁵ preferably in the range of 10 ² to 10 ⁴ . Aluminoxane may be added at the time of polymerization, or may be used in the form of being supported on a carrier supporting zirconium prior to the polymerization.

The molecular weight of the polymer can be adjusted by hydrogen and / or the polymerization temperature.

The polymerization pressure is usually atmospheric pressure to 100 kg / cm ² , preferably 2 to 50 kg / cm ² under pressure. The polymerization can be carried out by any of batch method, semi-continuous method and continuous method. In addition, polymerization is performed under different reaction conditions 2
It is also possible to divide into more than one step.

〔The invention's effect〕

Olefin polymerization in the present invention, especially ethylene polymerization or copolymerization of ethylene and α-olefin is a slurry polymerization method or gas phase polymerization method, especially when the gas phase polymerization method is adopted, there is no adhesion of the polymer in the reactor, powder When applied to the copolymerization of two or more kinds of olefins, which has excellent properties and a narrow molecular weight distribution, an olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution can be obtained.

〔Example〕

Next, the method of the present invention will be specifically described with reference to examples. In the examples and comparative examples, the MFR has a temperature of 190
The measurement is performed under the conditions of ℃ and load of 2.16 kg, and the w / n value is measured according to “Gel Permeation Chromatography” published by Maruzen by Takeuchi.

(1) Using a standard polystyrene of known molecular weight (Toyo Soda (manufactured by Toyo Soda) monodisperse polystyrene), the molecular weight M and its GPC (Gel Permeation Chromatograph) count are measured, and the correlation diagram calibration between the molecular weight M and EV (Elution Volume) is performed. Create a curve. The concentration at this time is 0.02 wt%.

(2) Take a GPC chromatograph of the sample by GPC measurement,
The number average molecular weight n and the weight average molecular weight w in terms of polystyrene are calculated by the above (1) to obtain the w / n value.
The sample preparation conditions and GPC measurement conditions in that case are as follows.

[Sample preparation]

(A) The sample is dispensed into an Erlenmeyer flask together with an o-dichlorobenzene solvent so as to have a concentration of 0.1 wt%.

(B) Heat the Erlenmeyer flask to 140 ° C. and stir for about 30 minutes to dissolve.

(C) Pour the liquid on GPC.

[GPC measurement conditions]

 It carried out on the following conditions.

(B) Equipment Waters (150C-ALC / GPC) (b) Column Toyo Soda (GMH type) (c) Sample volume 400 μl (d) Temperature 140 ° C (v) Flow rate 1 ml / min n in copolymer -The amount of decane soluble part (the smaller the amount of soluble part, the narrower the composition distribution) is about 3 g of copolymer.
It was added to 450 ml of decane, dissolved at 145 ° C., then gradually cooled to 23 ° C. to remove the insoluble part of n-decane and recover the soluble part of n-decane from the liquid.

Example 1 [Preparation of catalyst component [C]] Al ₂ (SO ₄ ) ₃
Charge 14H ₂ O 37g and toluene 125ml, cool to 0 ℃, dilute with toluene 125ml trimethylaluminum 500mmol.
Was dripped. Next, the temperature was raised to 40 ° C., and the reaction was continued at that temperature for 10 hours. After the reaction, solid-liquid separation is performed due to excess,
Further, toluene was removed from the liquid to obtain 13 g of a white solid aluminoxane. The molecular weight determined by freezing point depression in benzene was 930, and the m value shown in the catalyst component (B) was 14.

[Preparation of solid catalyst component (zirconium catalyst)]

Silica (average particle size 70μ, specific surface area 260m ² / g, pore volume 1.65cm ³ / g) 70 in a 200ml flask thoroughly replaced with nitrogen.
5.2 g of the product baked at 0 ° C. for 5 hours, 26 ml of a toluene solution of dimethyl aluminum monochloride (A 1 mol / l) and 50 ml of toluene were added, and the mixture was heated at 80 ° C. for 2 hours. Then, solid-liquid separation was performed by filtration to obtain a catalyst component [A].
The catalyst component [A] was transferred to 50 ml of toluene, and the catalyst component [B], bis (cyclopentadienyl), was added thereto.
Toluene solution of zirconium dichloride (Zr0.04mol /
l) 43 ml was added and heated at 80 ° C. for 1 hour. Again, solid-liquid separation was carried out by filtration to obtain a solid component in which 0.012 mg of Zr and 1.12 mg of Al were supported on 1 g of silica. This solid component is 0.015 in terms of zirconium atom.
Milligram atom, 4.9 ml of toluene solution of aluminoxane as catalyst component [C] (A1.03 mol / l) and toluene
20 ml was added and the mixture was stirred at room temperature for 30 minutes. After that, Zr was removed by removing toluene with an evaporator at room temperature.
A solid component of 0.08 wt% and A10 wt% was obtained.

〔polymerization〕

250 g of sodium chloride (Wako Pure Chemical Industries, Ltd.) was charged into a stainless steel autoclave having an internal volume of 2 l which had been sufficiently replaced with nitrogen, and dried under reduced pressure at 90 ° C for 1 hour. Then, the system was replaced with ethylene and the temperature was raised to 75 ° C. Subsequently, the total amount of the catalyst prepared above was charged, and ethylene was further introduced to bring the total pressure to 8 kg / cm ^2.
Polymerization was started as a gauge. Then, only ethylene was replenished and the total pressure was maintained at 8 kg / cm ² · gauge, and polymerization was carried out at 80 ° C. for 1 hour. After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with hexane and then at 80 ° C for 1 hour.
It was dried under reduced pressure at night. 72 g of a polymer having an MFR of 0.07 g / 10 min, w / n 2.64 and a bulk specific gravity of 0.36 g / cm ³ was obtained.

No adhesion of the polymer to the autoclave wall was observed.

Example 2 [Preparation of solid catalyst component (zirconium catalyst)] A 200 ml flask, which had been sufficiently purged with nitrogen, was charged with alumina (average particle diameter 60 μ, specific surface area 270 m ² / g, pore volume 1.05 ml / g) in an amount of 5
5.8 g of the product baked at 00 ° C. for 5 hours, 17 ml of a toluene solution of dimethyl aluminum monochloride (A 1 mol / l) and 50 ml of toluene were added, and the mixture was heated at 80 ° C. for 2 hours. After that, solid-liquid separation was performed by filtration, and the solid portion was transferred to 50 ml of toluene, and 32 ml of a toluene solution of bis (cyclopentadienyl) zirconium dichloride (Zr0.036 mol / l) was added thereto, and the mixture was heated at 80 ° C for 1 hour. . Again, solid-liquid separation was performed by filtration to obtain a solid component of Zr 0.25 wt%. The reaction between this solid component and aluminoxane was carried out in the same manner as in Example 1, and Zr0.16
wt% solid catalyst component was obtained.

〔polymerization〕

Polymerization was performed in exactly the same manner as in Example 1 using 0.015 mg of zirconium atom as the solid catalyst, and 42 g of a polymer having MFR of 0.09 g / 10 min, w / n 2.77 and bulk specific gravity of 0.35 g / cm ³ was obtained. Was given.

No adhesion of the polymer to the autoclave wall was observed.

Example 3 [Preparation of solid catalyst component (zirconium catalyst)] 30 ml of silica (average particle diameter 70 μ, specific surface area 260 m ² / g, pore volume 1.65 cm ³ / g) was placed in a 200 ml flask that had been sufficiently replaced with nitrogen.
2.3 g of the product baked at 0 ° C. for 4 hours, 15 ml of a toluene solution of dimethyl aluminum monochloride (A 1 mol / l) and 50 ml of toluene were added, and the mixture was heated at 80 ° C. for 2 hours. After that, solid-liquid separation is performed by filtration, and the solid part is transferred to 50 ml of toluene, and 6.4 ml of a solution of bis (cyclopentadienyl) zirconium dichloride in toluene (Zr0.01 mol / l) is added to it.
Was added and the mixture was stirred at room temperature for 2 hours. Next, a toluene solution of aluminoxane synthesized in Example 1 (A1.03 mol / l) 31 m
l was added, and the mixture was stirred at room temperature for 30 minutes. Subsequent operations were performed in the same manner as in Example 1 to obtain a solid catalyst component of Zr 0.14 wt% and Al 22 wt%.

〔polymerization〕

Polymerization was carried out in the same manner as in Example 1 using 0.015 mg of zirconium atom as the solid catalyst, and the result was MFR.
70 g of a polymer having 0.12 g / 10 min, w / n 2.67 and a bulk specific gravity of 0.38 g / cm ³ was obtained. No adhesion of the polymer to the autoclave wall was observed.

Comparative Example 1 Catalyst preparation and polymerization were carried out in the same manner as in Example 1 except that silica was not treated with dimethylaluminum monochloride, and MFR 0.02g / 10min, w / n2.89, bulk specific gravity 0.15g / cm. 21 g of polymer ³ was obtained.

The solid catalyst component used for the polymerization was Zr 0.35 wt%, Al
It contained 35 wt%.

Example 4 [Preparation of solid catalyst component (zirconium catalyst)] 6 g of triethylaluminum instead of dimethylaluminum monochloride was added to 1 g of silica calcined at 800 ° C for 12 hours in Example 1 and reacted at 50 ° C for 2 hours. 6.7 × 10 ^-3 mg of zirconium per 1 g of silica except that 0.042 mmol of biscyclopentadienyl zirconium dichloride was added to 1 g of silica and reacted at room temperature for 2 hours. An atom-supported solid catalyst component was obtained.

〔polymerization〕

The same procedure as in Example 1 was carried out except that aluminoxane was charged in Example 1 in an amount of 15 mg of aluminum atom, the solid catalyst component prepared above was charged in an amount of 0.015 mg in terms of zirconium atom, and further 50 ml of hydrogen was introduced. 69 g of a polymer having an MFR of 24 g / 10 min, w / n of 2.70 and a bulk specific gravity of 0.31 g / cm ³ was obtained.

Almost no adhesion of the polymer to the wall of the autoclave was observed.

Example 5 [Preparation of solid catalyst component (zirconium catalyst)] The same procedure as in Example 4 was repeated except that diethylaluminum monochloride was used in place of triethylaluminum, and 1 g of silica contained 5.7 zirconium.
A solid catalyst component carrying x10 ^-3 mg of atoms was obtained.

〔polymerization〕

Same as Example 4, MFR9.5g / 10min, w / n2.59,
71 g of a polymer having a bulk specific gravity of 0.34 g / cm ³ was obtained. Almost no adhesion of the polymer to the wall of the autoclave was observed.

Example 6 [Polymerization] In Example 1, 10 ml of hexene-1 was added, and the temperature was changed to 70 ° C.
Was carried out in the same manner as in Example 1 except that the polymerization was carried out for 0.5 hours.
FR2.05g / 10min, w / n2.84, bulk specific gravity 0.31g / cm ³ , density
As a result, 42 g of a polymer having a room temperature decane-soluble part weight fraction of 0.15 wt% at 0.926 g / cm ³ was obtained.

Almost no adhesion of the polymer to the autoclave wall was obtained.

[Brief description of drawings]

FIG. 1 is a flow chart showing one example of the preparation of a catalyst in the polymerization of olefin of the present invention.

Claims (3)

(57) [Claims] 1. A porous inorganic oxide support treated with an organometallic compound selected from [A] organoaluminum, organoboron, organomagnesium, organozinc and organolithium, and having [B] cycloalkadienyl group. A solid catalyst supporting a zirconium compound, which is formed from a solid catalyst component in which 3 × 10 ⁻³ to 3 mg of zirconium atoms are supported per 1 gram of a porous inorganic oxide support, and [C] aluminoxane. A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of a prepared catalyst. 2. The polymerization method according to claim 1, wherein the organometallic compound [A] is an organoaluminum compound. 3. A zirconium compound having a cycloalkadienyl group is represented by the following formula (I): [Wherein R ¹ represents a cycloalkadienyl group, R ² and R ³
And R ⁴ is a cycloalkadienyl group, an aryl group, an alkyl group, an aralkyl group, an alkoxy group, a halogen atom or hydrogen, k ≧ 1, k + 1 + m + n = 4, and a cycloalkadienyl group is cyclopentadienyl. Base,
A methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group or a tetrahydroindenyl group.] The compound according to claim 1 characterized in that The described polymerization method.