JPH0832733B2 - Olefin Polymerization Method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for polymerizing olefin, which has excellent polymerization activity. Furthermore, in particular, it relates to a method of polymerizing an olefin copolymer having a narrow molecular weight distribution and a narrow molecular weight distribution and composition distribution when applied to the copolymerization of two or more kinds of olefins with excellent polymerization activity, particularly the molecular weight distribution. And a method for producing an ethylene / α-olefin copolymer having a narrow composition distribution as polymer particles having high bulk density and excellent powder properties and excellent polymerization activity.

[Conventional technology]

Conventionally, as a method for producing an α-olefin polymer, particularly an ethylene polymer or an ethylene / α-olefin copolymer, ethylene or ethylene and α are used in the presence of a titanium catalyst composed of a titanium compound and an organoaluminum compound.
-Methods of copolymerizing olefins are known. In general, the ethylene / α-olefin copolymer obtained with a titanium-based catalyst has a wide molecular weight distribution and composition distribution, and therefore the transparency and surface non-adhesiveness of the molded film are inferior. Especially, when trying to increase the content of α-olefin, these problems were largely manifested. On the other hand, the ethylene / α-olefin copolymer obtained with a vanadium catalyst has a higher molecular weight distribution and composition distribution when it is used to produce a copolymer with a higher α-olefin content than that obtained with a titanium catalyst. Although it tends to become narrower, it is difficult to make a copolymer for film with excellent transparency and surface non-adhesiveness, for example, when manufacturing so-called LLDPE with a comonomer content of around 10% by weight. At the same time, since the polymerization activity is extremely low, α-
There is a demand for olefin polymers, especially ethylene / α-olefin copolymers.

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, and 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 method for producing a cyclic aluminoxane represented by [wherein n and R are the same as defined above] is described. In the publication, for example, a mixture of methylaluminoxane and a bis (cyclopentadienyl) compound of titanium or zirconium produced by the same production method is used to polymerize olefin, and 1 g of transition metal and It is stated that more than 25 million g of polyethylene can be obtained per hour.

Japanese Unexamined Patent Publication No. 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—], the aminoxane 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. In the same publication, the catalyst is ethylene and
It is described as being particularly suitable for the copolymerization of mixtures of C _{3 to} C ₁₂ α-olefins.

JP-A-60-35006 discloses, as a catalyst system for producing a reactor blend polymer, two or more different transition metal monomers, di- or tri-cyclopentadienyl or its derivative (a) and alumoxane (aluminoxane).
The combination of (b) is disclosed. In the above-mentioned 1 of the publication, ethylene and propylene are polymerized by using bis (pentamethylcyclopentadienyl) zirconium dimethyl and alumoxane as catalysts, and polyethylene having a number average molecular weight of 15.300, a weight average molecular weight of 36,400 and a propylene component of 3.4% is contained. What has been obtained is disclosed. Also,
In Example 2, ethylene and propylene were polymerized using bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and alumoxane as catalysts,
Number-average molecular weight 2,000 consisting of a number-average molecular weight of 2,200, a weight-average molecular weight of 11,900 and a toluene-soluble portion containing 30 mol% of a propylene component and a number-average molecular weight of 3,000, a weight-average molecular weight of 7,400 and a toluene-insoluble portion containing a propylene component of 4.8 mol%. A blend of polyethylene and an ethylene / propylene copolymer containing a propylene component having a weight average molecular weight of 8,300 and 7.1 mol% is obtained. Similarly, in Example 3, the molecular weight distribution () w / n) 4.57 and the propylene component 2
Blends of LLDPE and ethylene-propylene copolymers are described which consist of 0.6 mol% soluble part and 3.04 molecular weight distribution and 2.9 mol% propylene component insoluble part.

JP-A-60-35007 discloses that ethylene alone or 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. The polymer obtained by this 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, according to the description of the publication.

Further, JP-A-60-35008 discloses the use of a catalyst system containing at least two kinds of metallocene and alumoxane to obtain polyethylene or ethylene having a broad molecular weight distribution and C ₃ -C ₁₀ α-olefin. It is described that a copolymer 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 better polymerization activity than conventionally known catalyst systems, but in many cases these catalyst systems are soluble in the reaction system. Alternatively, when vapor phase polymerization is attempted, it is difficult to adopt the above-mentioned polymerization method because the resulting polymer has a very low bulk density and is inferior in powder property.

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 or silica-alumina is also disclosed in JP-A-60-35006. , JP-A-60-35007, JP-A-60-35008, etc., have also been proposed,
Further, in JP-A-61-31404, JP-A-61-108610 and JP-A-60-106808, a method using a fixed catalyst component supported on a similar porous inorganic oxide carrier is also disclosed. Proposed. By adopting a supported solid component in the methods described in these prior arts, the polymerization activity is greatly reduced, and many fine powders and coarse particles are found in the obtained polymer, and the bulk density is low. Many of the powder properties were insufficient.

[Problems to be solved by the invention]

The present inventors have found that the molecular weight distribution is narrow, and when it is applied to the copolymerization of two or more kinds of olefins, the molecular weight distribution is narrow, and the olefin copolymer having excellent powder properties, particularly the molecular weight distribution and the composition distribution are narrow. Moreover, as a result of investigating a method for producing an ethylene / α-olefin copolymer having an excellent powder property with an excellent polymerization activity, [A] a specific carrier-supported solid catalyst component and [B] an aluminoxane or an aluminum halide. The inventors have found that the above object can be achieved by using a catalyst formed from nooxane, and have reached the present invention.

[Means for Solving Problems] and [Action] The above-mentioned object is to provide a porous inorganic oxide support treated with [A] aluminoxane in accordance with the present invention with a group having a conjugated π electron as a ligand. Polymerization or copolymerization of olefin in the presence of a catalyst formed from a solid catalyst component carrying the zirconium compound and [B] aluminoxane or halogenated aluminoxane. Can be achieved by

The olefin polymer or copolymer obtained by the method of the present invention has a feature that the molecular weight distribution is narrow and the composition distribution is narrow, and at the same time, there are few fine powdery or coarse polymer particles and high bulk density. .

 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. is there.

The catalyst used in the present invention is formed from one catalyst component [A] and [B].

The catalyst component [A] is a solid catalyst component in which a zirconium compound having a group having a conjugated π electron as a ligand is supported on a porous inorganic oxide support treated with aluminoxane.

The zirconium compound having a conjugated π-electron group as a ligand in the catalyst component [A] is, for example, the following formula (1) R ¹ _k R ² ₁ R ³ _m R ⁴ _n Zr (1) [where R ¹ Represents a cycloalkadienyl group, R ² , R ³
And R ⁴ cycloalkadienyl group, aryl group, alkyl group, aralkyl group, alkoxyl group, halogen atom or hydrogen, and k ≧ 1, k + 1 + m = 4].

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. The alkoxy group can be exemplified by a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2-ethylhexoxy group, etc., and the halogen atom can be exemplified by fluorine, chlorine, bromine and the like. . Of these zirconium compounds, bis (alkyl-substituted cyclopentadienyl) zirconium dihalide is preferable. 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 (methylcyclopentadienyl) ) Zirconium Monochloride Monohydride, Bisindenyl Zirconium Monochloride Monohydride, Bis (cyclo Pentadienyl) zirconium dichloride, Bis (cyclopentadienyl) zirconium dibromide, Bis (cyclopentadienyl) methylzirconium monochloride, Bis (cyclopentadienyl) ethylzirconium monochloride, Bis (cyclopentadienyl) cyclohexylzirconium monochloride Chloride, 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 diphenyl, bis (cyclo) Pentadienyl) 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) benzylzirconium ethoxide, bis (methylcyclopentadienyl) ethoxyzirconium chloride, bisendenyl Toxyzirconium chloride, bis (cyclopentadienyl) ethoxyzirconium, bis (cyclopentadienyl) butoxyzirconium, bis (cyclopentadienyl) 2-ethylhexoxyzirconium.

Prior to supporting the zirconium compound having the conjugated π-electron-containing group as a ligand in the catalyst component [A] on the inorganic oxide carrier, it is necessary to treat these carriers with aluminoxane in advance. General formula (II) and general formula (III) as aluminoxane used in this treatment [In the formula, R ⁵ represents a hydrocarbon group, and a is usually 0 to 10
And an organic aluminum compound represented by 0, preferably 4 to 50]. In the aluminoxane, R ⁵ is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, and particularly preferably a methyl group. 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 of reacting a trialkylaluminum while suspending cerium hydrate or the like in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(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.

The mixing ratio of the aluminoxane to the porous inorganic oxide carrier in the above treatment is 0.001 to 100 mmol, preferably 0.01 to 10 mmol, and more preferably 0.05 to 5 mmol of aluminoxane per gram of carrier compound. is there. Further, it is preferable to remove the liquid part containing the surplus aluminoxane and the like from the reaction mixture after the above treatment by a method such as excess or declination.

The treatment of the porous inorganic oxide support with aluminoxane in the catalyst component [A] is carried out at a temperature of -50 to 200 ° C, preferably 0 to 100 ° C, more preferably 20 to 70 ° C for 10 minutes to 10 hours, preferably It can be carried out for 20 minutes to 5 hours under normal pressure, reduced pressure or elevated pressure.

Further, the above treatment is preferably carried out in an inert solvent, and examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as pentane, hexane, isooctane, decane and dodecane. Alicyclic hydrocarbons such as cyclohexane and halogenated hydrocarbons such as chlorobenzene and ethylene dichloride. Of these, aromatic hydrocarbons are preferred.

Specific examples of the porous inorganic oxide carrier used in the catalyst component [A] include SiO ₂ , Al ₂ O ₃ , MgO and Zr.
O ₂ , TiO ₂ or a mixture thereof can be exemplified. Among these, a carrier containing as a main component at least one component selected from the group consisting of SiO ₂ , Al ₂ O ₃ and MgO is preferable. The compounds used as these carriers preferably have a specific surface area of 50 m ² / g or more, and particularly preferably 100 m ² / g or more.

In addition, it is preferable that physically adsorbed water does not exist in the inorganic oxide carrier, and accordingly, it is preferable to use by calcination at 200 to 800 ° C. for 1 to 24 hours.

The inorganic oxide carrier having an average particle size of usually 1 to 500 μm, preferably 5 to 100 μm, and particularly 10 to 50 μm is preferably used.

When a zirconium compound having a group having a conjugated π electron as a ligand (hereinafter sometimes referred to as “zirconium compound”) is supported on a porous inorganic oxide support treated with aminooxane in the catalyst component [A] ,
When the zirconium compound is a liquid substance, an inert solvent may or may not be used, but when the zirconium compound is a solid substance at room temperature, an inert solvent capable of dissolving the zirconium compound is generally used. It is preferable to use.

As the inert solvent that can be used in this case, the inert solvent that may be used when treating the porous inorganic oxide carrier with aluminoxane can be similarly exemplified. Aromatic hydrocarbons such as benzene and toluene or halogenated hydrocarbons such as chlorobenzene are particularly preferable.

The amount of the zirconium compound used in the above supporting reaction is 0.001 to 10 mmol, more preferably 0.005 to 5 mmol, and particularly 0.01 to 1 per 1 g of the porous inorganic oxide support treated with aluminoxane.
The millimolar range is preferred.

The amount of the inert solvent used in the above supporting reaction is 0.5 to 1000 ml, preferably 1 to 10 m, per 1 g of the porous inorganic oxide support treated with aluminoxane.
A range of 1, especially 2 to 50 ml is preferred. In the supporting reaction, the porous inorganic oxide support treated with aluminoxane and the zirconium compound are used in an amount of 0 to 200.
1 minute to 10 hours, 5 minutes to 5 hours, 10 ° C., preferably 0 to 100 ° C., especially 20 to 80 ° C.
It can be carried out by contact mixing for 3 to 3 minutes.

After carrying out the supporting reaction by the above method, it is preferable to remove the liquid part in the reaction mixture solution by a method such as excessive or decanting, and further wash several times with an inert solvent.

Solid catalyst component [A] prepared by such a method
There is 1 g of the component [A], and the zirconium compound is usually 0.005 mmol to 5 mmol, preferably 0.01
It is contained in an amount of 1 to 1 mmol, particularly preferably 0.03 to 0.3 mmol.

The specific surface area of the component A is usually 50 m ² / g or more, preferably 100 m ² / g to 2000 m ² / g.

The catalyst component [B] is an aluminoxane or a halogenated aluminoxane.

As the aluminoxane used as the catalyst component [B], the general formula (III) and the general formula (IV) [In the formula, R ⁶ represents a hydrocarbon group, b is usually 2 to 50,
And preferably 4 to 30]. In the aluminoxane, R ⁶ is a methyl group, an ethyl group, a propyl group,
It is a hydrocarbon group such as a butyl group, and particularly preferably a methyl group. The halogenated aluminoxane used as the catalyst component [B] is represented by the general formula (V) and the general formula (VI). The organoaluminum compound represented by can be exemplified. In the formula, R ⁷ is a methyl group, an ethyl group, a propyl group,
It is a hydrocarbon group such as a butyl group, preferably a methyl group or an ethyl group, and particularly preferably a methyl group. X is a halogen atom such as chlorine or bromine, and R ⁸ is R ⁷
And the above-mentioned halogen. Also,
d is usually 0 to 40, preferably 3 to 30, and e
Is usually 1 to 40, preferably 3 to 30 and d +
e is usually 4 to 50, preferably 8 to 30. Further, in the general formulas (V) and (VI), They may be block-bonded or may be regularly or irregularly randomly bonded.

When d is 0, it is preferable to use an organoaluminum compound represented by the general formula (VII) AlR ⁹ _f X _3-f (VII) in addition to the halogenated aluminoxane. In the formula, R ⁹ represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, X represents a halogen atom such as chlorine and bromine, and f represents 1 to 3. Examples thereof include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, diethylaluminum chloride and ethylaluminum sesquichloride. The use ratio of the halogenated aluminoxane represented by the general formula (V) or (VI) and the organoaluminum compound represented by the general formula (VII) is generally the aluminum halide represented by the general formula (V) or (VI). The amount of the organoaluminum compound represented by the general formula (VII) is 0.3 to 3.0 mol, preferably 0.5 to 2.0 mol, and particularly 0.7 to 1.5 mol, per 1 mol of Al atom in nooxane.

Even when the halogenated aluminoxane represented by the general formula (III) or (IV) is used, the organoaluminum compound represented by the general formula (VII) may be used in combination.

The catalyst used in the present invention can be formed by contacting the catalyst component [A] with the catalyst component [B]. The catalyst used in the present invention may be formed before the introduction of α-olefin in the polymerization reaction vessel or after the introduction of α-olefin.

Examples of α-olefins which 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.

INDUSTRIAL APPLICABILITY The present invention is effective for producing an ethylene polymer, particularly a copolymer of ethylene and other α-olefin. When producing a copolymer of ethylene, the content of ethylene in the polymerization raw material α-olefin is usually 50 to 99 mol%, preferably 80 to 98 mol%, the content of the α-olefin is usually 1 to 50 mol%, preferably 2 to
It is in the range of 20 mol%.

In the method of the present invention, so-called liquid phase polymerization or gas phase polymerization such as suspension polymerization or solution polymerization can be adopted when carrying out the polymerization of α-olefin, but when suspension polymerization or gas phase polymerization is adopted. The effect of the present invention is exerted well, and the effect is exerted particularly in gas phase polymerization.

In any of the above polymerization methods, a hydrocarbon medium can be used if necessary, but as the hydrocarbon medium, specifically, butane, isobutane, pentane, hexane,
Octane, decane, dodecane, hexadecane, octadecane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane and other alicyclic hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons, In addition to petroleum fractions such as gasoline, kerosene, and light oil, the raw material olefin is also a hydrocarbon medium.

In the method of the present invention, the temperature during the polymerization reaction is usually −
The range is 50 to 200 ° C, preferably 0 to 150 ° C, particularly preferably 20 to 120 ° C.

The proportion of the zirconium compound in the practice of the method of the present invention, the concentration as usually 10 ^-9 to 10 ^-3 gram atom / l of zirconium metal atom in the polymerization reaction system, and preferably contains 10 ^-7 10 ^- It is in the range of ⁴ grams atom / l. The proportion of aluminoxane or halogenated aluminoxane used is usually 10 ^-5 to 10 ^-1 gram atom / l, preferably 10 as the concentration of aluminum atoms in the polymerization reaction system.
^-4 to 5 × 10 ^-2 gram atom / l, and the ratio of aluminum metal atom to zirconium metal atom in the polymerization reaction system is usually 10 to 10 ⁷ , preferably 50.
To 10 ⁴ range. The molecular weight of the polymer can be adjusted by hydrogen and / or the polymerization temperature.

In the method of the present invention, the pressure during the polymerization reaction is usually atmospheric pressure to 100 kg / cm ² G, preferably 1 to 70 kg / cm ² G.
Particularly, 5 to 40 kg / cm ² G is preferable.

The composition of the ethylene polymer of the present invention has an ethylene component of 70
To 100% by weight, preferably 80 to 100% by weight,
The olefin component is in the range 0 to 30% by weight, preferably 0 to 20% by weight.

Further, the MFR value of the ethylene polymer of the present invention measured at 190 ° C. and a weight of 2.16 kg is usually 0.001 to 200 g.
/ 10 min, preferably with a value in the range 0.005 to 100 g / min.

In addition, the molecular weight distribution (w / n) of the α-olefin polymer, for example, ethylene copolymer, usually measured by gel permeation chromatography (GPC).
Is 4 or less, preferably 3 or less.

In the method of the present invention, the amount of n-decane-soluble component at 25 ° C was measured as a measure for examining the composition distribution of the produced copolymer. 25 ° C n-decane soluble component amount is measured with a stirring blade 1
In a flask of 5 g of copolymer sample, 0.3 g of 2,6-ditert
-Butyl-4-methylphenol, 500 ml of n-decane are added and dissolved in an oil bath at 140 ° C. After the solution is dissolved, it is naturally cooled at room temperature for about 3 hours and then cooled on a water bath at 25 ° C for 12 hours. The n-decane solution containing the precipitated copolymer and dissolved polymer was over-separated with a G-4 glass filter, the solution was dried at 10 mmHg at 150 ° C. until a constant weight was obtained, and the weight thereof was measured. The soluble component content of the copolymer therein is determined as a percentage of the weight of the sample copolymer.

〔Example〕

[Synthesis of aluminoxane] Aluminoxane-I 37 g of Al ₂ (SO ₄ ) ₃ .14H ₂ O and 125 ml of toluene were placed in a 400 ml glass flask equipped with a stirrer, which had been sufficiently replaced with nitrogen, and
After cooling to ℃, toluene containing 50 ml of trimethylaluminum
125 ml was added dropwise over 1 hour. Then 2 hours 4
The temperature was raised to 0 ° C., and the reaction was continued at that temperature for 10 hours. After the reaction, solid-liquid separation was performed due to excess, low-boiling substances were removed from the separated liquid using an evaporator, and toluene was added to the remaining viscous liquid to collect a toluene solution. The molecular weight determined from the freezing point depression in benzene was 885, and thus the degree of polymerization of this aluminoxane was 15.

Aluminoxane-II Aluminoxane-II except that the reaction time at 40 ° C. was changed from 10 hours to 2 hours in the synthesis of aluminoxane-I.
It was synthesized in the same manner as I. The degree of polymerization of aluminoxane was 6.

Aluminoxane-III Aminooxane-I was synthesized in the same manner as aluminoxane-I except that the amount of trimethylaluminum added was changed from 50 ml to 24.7 ml and dimethylaluminum chloride 25.3 ml was simultaneously added at the time of synthesis of aluminoxane-I. The degree of polymerization of aluminoxane was 12.

Example 1 [Preparation of solid catalyst component [A]] Silica (Davison Corporation ^# 9) calcined at 800 ° C. for 12 hours in a 400 ml glass flask equipped with a stirrer that had been sufficiently replaced with nitrogen.
52) After adding 50 ml of a toluene solution containing 2 mmol of aluminoxane to a suspension consisting of 5 g and 100 ml of toluene at room temperature, the temperature of this mixture was raised to 50 ° C. and the reaction was carried out at 50 ° C. for 2 hours. It was After the reaction was completed, the liquid portion was removed from this reaction liquid using a filter, and the remaining solid portion was resuspended in 100 ml of toluene. 9.4m containing 0.38mmol bis (cyclopentadienyl) zirconium dichloride in this suspension
l Toluene was added at 25 ° C., and the reaction was carried out at 25 ° C. for 2 hours with stirring. After the reaction was completed, the liquid portion was removed from this suspension using a filter, and the remaining solid portion was washed twice with toluene to obtain a solid catalyst component [A]. The amount of zirconium supported in the catalyst component [A] was 0.6 wt /%.

〔polymerization〕

250 g of sodium chloride was added as a dispersant to an autoclave having an internal volume of 2 liters that had been sufficiently replaced with nitrogen, and the autoclave was heated under a vacuum pump at 90 ° C. for 2 hours to reduce the internal pressure to 50 mlHg or less. Then, the temperature of the autoclave was lowered to 75 ° C., and after the inside of the autoclave was replaced with ethylene, 0.13 mmol of aluminoxane (aluminoxane-I) was added, and the mixture was stirred at a rotation speed of 50 rpm for 2 minutes, and then 0.87 mmol of aluminum was added. Nooxane (aluminoxane-I) and the solid catalyst component [A]
After adding 0.015 mmol in terms of zirconium atom,
The autoclave was used as a closed system, 20 Nml of hydrogen was added, and ethylene was pressurized so that the internal pressure of the autoclave was 8 kg / cm ² G. The stirring speed was increased to 300 rpm and polymerization was carried out at 80 ° C. for 1 hour.

After completion of the polymerization, the entire amount of the polymer and sodium chloride in the autoclave was taken out and put into about 1 water. After stirring for about 5 minutes, almost all of the sodium chloride was dissolved in water, and only the polymer was floating on the water surface. After collecting this floating polymer and thoroughly washing with methanol,
It was dried under reduced pressure at 80 ° C. overnight. The yield of the obtained polymer was 82.1 g, MFR was 7.9, and apparent bulk density was 0.43 g / m.
It was l. The fine powdery polymer having a particle size of 105 μm or less was 0.1 wt% of the whole, while no coarse polymer having a particle size of 1120 μm or more was found. The w / n was 2.7.

Example 2 Solid catalyst component [A] was prepared in the same manner as in Example 1 except that the aluminoxane used for treating silica in the preparation of the solid catalyst component [A] of Example 1 was changed from 2 mmol to 10 mmol. Was prepared and ethylene was polymerized.

Examples 3 and 4 A method similar to that of Example 1 except that the reaction temperature for supporting cyclopentadienylzirconium dichloride was changed from 25 ° C to 50 ° C and 80 ° C in the preparation of the solid catalyst component [A] of Example 1. Then, a solid catalyst component [A] was prepared and ethylene was polymerized.

Example 5 A solid catalyst was prepared in the same manner as in Example-1 except that the aluminoxane used in Example 1 was changed from aluminoxane-I to aluminoxane-II in the preparation of the solid catalyst component [A]. The component [A] was prepared and ethylene was polymerized.

Example 6 In Example 1, the aluminoxane used in the polymerization was changed from aluminoxane-I to aluminoxane-II.
Ethylene was polymerized in the same manner as in Example 1 except that

Example 7 Example-except that the monomer supplied in Example 1 was changed from ethylene alone to a butene-1 / ethylene mixed gas containing 9.5 mol% butene-1, and the polymerization temperature was changed from 80 ° C to 70 ° C. Polymerization was carried out in the same manner as in 1.

[Brief description of drawings]

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

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Claims (1)

[Claims] 1. A solid catalyst component comprising a [A] aluminoxane-treated porous inorganic oxide carrier and a zirconium compound having a group having a conjugated π electron as a ligand, and [B] alumino A process for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst formed from xane or a halogenated aluminoxane.