JPH0819183B2 - Method for producing solid catalyst for olefin polymerization - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a solid catalyst component for olefin polymerization.

More specifically, in the present invention, the [A] organomagnesium compound, the solution of the transition metal compound and the solid catalyst component supported on the magnesium compound carrier obtained by contacting the silicon halide compound with the [B] aluminoxane component are added. The present invention relates to a method for producing a supported solid catalyst for olefin polymerization.

[Prior art] Conventionally, as a method for producing an α-olefin polymer, particularly an ethylene homopolymer or an ethylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and an organoaluminum compound or a vanadium compound and an organoaluminum compound There is known a method of polymerizing ethylene or copolymerizing ethylene and α-olefin in the presence of a vanadium-based catalyst consisting of Generally, an ethylene / α-olefin copolymer obtained by a titanium-based catalyst 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, they are still insufficient for the applications in which these performances are required, and further, α-olefin polymers, particularly ethylene / α-olefin copolymers, in which these performances are improved are required.

On the other hand, a catalyst comprising a zirconium compound and an 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 ₆ -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 4 to 4].
Is a number of 20] or a linear aluminoxane represented by the following formula [Wherein R and n are the same as above] in the presence of a catalyst consisting of a cyclic aluminoxane represented by the following formula: ethylene and one or more of C _{3 to} C ₁₂ α-olefins; A method of polymerizing at a temperature of -50 ° C to 20 ° C is described. The publication states that in order to control the density of the resulting polyethylene, the polymerization of ethylene should be carried out in the presence of small amounts of up to 10% by weight of somewhat longer-chain α-olefins or mixtures. .

JP-A-59-95292 discloses the following formula [Where n is 2 to 40 and R is C _{1 to} C ₆ ], and a linear aluminoxane represented by the following formula: [Wherein the definitions of n and R are the same as described above], the invention relating to a method for producing a cyclic aluminoxane is described. The publication discloses that, for example, a mixture of methylaluminoxane and a bis (cyclopentadienyl) compound of titanium or zirconium produced by the same production method and polymerization of olefin gives 1 g of transition metal and It is stated that over 25 million g of polyethylene are obtained per hour.

JP-A-60-35005 discloses the following formula [Wherein R ¹ is C ₁ -C ₁₀ alkyl and R ⁰ is R ¹ or is bonded to represent —O—] and the aluminoxane compound represented by A method for producing a polymerization catalyst for olefin by chlorinating a reaction product and further treating it with a compound of Ti, V, Zr or Cr is disclosed. The publication states 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 alumino. A combination of xane (b) is disclosed. In Example 1 of the publication, ethylene and propylene are polymerized using bis (pentamethylcyclopentadienyl) zirconium dimethyl and aluminoxane as catalysts to give a number average molecular weight of 15,300 and a weight average molecular weight of 3
It is disclosed that a polyethylene containing 6,400 and 3.4% propylene component was obtained. Moreover, in Example 2, ethylene and propylene were polymerized using bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride and aluminoxane as catalysts to give a number average molecular weight of 2,200 and a weight. Toluene-soluble portion containing propylene component of average molecular weight 11,900 and 30 mol% and number average molecular weight 3,
000, a weight average molecular weight of 7,400 and a number average molecular weight consisting of a toluene insoluble portion containing a propylene component of 4.8 mol% 2,
000, a weight average molecular weight of 8,300 and a blend of polyethylene and an ethylene-propylene copolymer containing a propylene component of 7.1 mol% are obtained. Similarly, in Example 3, the molecular weight distribution ( _w / _n ) of 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 molecular weight distribution 3.04 and 2.9 mol% insoluble part of propylene component.

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 aluminoxane represented by the following formula: [Here, the definitions of R and n are the same as above.] A method of polymerizing in the presence of a catalyst system containing a linear aluminoxane represented by the following formula: According to the description of the publication, the polymer obtained by the same method is about 500 to about 1
It has a weight average molecular weight of 400,000 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 aluminoxane, polyethylene having a broad molecular weight distribution or ethylene and ethylene and C ₃ -C ₁₀ α-olefins are disclosed. It is described that a copolymer of The publication describes that the above copolymer has a molecular weight distribution ( _w / _n ) of 2 to 50.

The catalysts formed from the transition metal compounds and aluminoxane proposed in these prior arts have remarkably excellent polymerization activity as compared with the catalyst systems formed from conventionally known transition metal compounds and organoaluminum compounds. However, most of the catalyst systems proposed for these are soluble in the reaction system, and solution polymerization systems are often adopted, and the solution viscosity of the polymerization system is significantly increased. The bulk specific gravity of the resulting polymer obtained by the post-treatment 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, or alumina, a suspension polymerization system or gas Attempts have also been made to polymerize olefins in phase polymerization systems.

For example, in the above-cited JP-A-60-35006, JP-A-60-35007 and JP-A-60-35008, transition metal compounds and aluminoxane are added to silica, silica-alumina, alumina, etc. It is described that a catalyst supported on the above can be used.

Further, JP-A-60-106808 and JP-A-60-1068.
No. 09 discloses a product obtained by subjecting a highly active catalyst component containing titanium and / or zirconium, which is soluble in a hydrocarbon solvent, and a filler in advance to a contact treatment, an organoaluminum compound, and a filler having affinity for polyolefin. There has been proposed a method for producing a composition comprising a polyethylene-based polymer and a filler by copolymerizing ethylene or ethylene and α-olefin in the presence of the material.

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

Further, JP-A-61-276805 discloses that a reaction mixture obtained by reacting a zirconium compound with an aluminoxane and a trialkylaluminum is further reacted with an inorganic oxide having a surface hydroxyl group such as silica. It has been proposed to polymerize olefins in the presence of a catalyst consisting of a mixture.

Furthermore, JP-A-61-108610 and JP-A-61-2960.
In JP-A-08, a method is proposed in which olefin is polymerized in the presence of a catalyst in which a transition metal compound such as metallocene and aluminoxane are supported on a support such as an inorganic oxide.

However, even if olefin is polymerized or copolymerized in a suspension polymerization system or a gas phase polymerization system using the carrier-supported solid catalyst components proposed in these prior arts, the polymerization activity is remarkably higher than that in the solution polymerization system described above. None of the catalysts, which have been reduced, fully exhibit the original characteristics of the catalyst composed of the transition metal compound catalyst component and the aluminoxane catalyst component, and the powder properties such as the bulk specific gravity of the produced polymer are also reduced. It was insufficient.

[Problems to be Solved by the Invention] An object of the present invention is to provide a catalyst for olefin polymerization capable of giving an olefin polymer having a large bulk specific gravity and excellent powder properties and having a large polymerization activity. .

[Means for Solving the Problems] The object is according to the present invention: [A] (i) General formula [In the formula, M is aluminum, R ¹ is a hydrocarbon group,
For example, it is an alkyl group, an aryl group, etc., X is a group such as halogen, OR ² , OSiR ³ R ⁴ R ⁵ , NR ⁶ R ⁷ and SR ⁸ , and a ≧
When 0, b> 0, c> 0, d ≧ 0 and the valence of M is n, na + 2b = c + d is satisfied, and c R ¹ and d X are the same or different. Can be different,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent hydrogen or a hydrocarbon group,
R ⁸ represents a hydrocarbon group] or a solution of these organomagnesium compounds in a liquid state, (ii) General formula (I) R ¹ _k R ² _l R ³ _m R ⁴ _n Zr (I) [Wherein R ¹ represents a cycloalkadienyl group or a substituted product thereof, R ² , R ³ and R ⁴ represent a cycloalkadienyl group,
Aryl group, alkyl group, cycloalkyl group, aralkyl group, halogen atom, hydrogen, OR ^a , SR ^b , NR ₂ ^c , or PR
₂ ^d , R ^a , R ^b , R ^c and R ^d are a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, a silyl group, and two R ^c and R ^d are It is also possible to connect to form a ring. k ≧ 1 and k + l + m + n = 4. Further, when R ² is a cycloalkadienyl group, R ¹
And R ² may be bonded with a lower alkylene group. ] A solution of a zirconium compound represented by, and (iii) the general formula [In the formula, R ³ represents a hydrocarbon group, X represents a halogen atom, and a + b + c = 4, 4> a ≧ 0, 4> b ≧ 0 and 4 ≧ c ≧ 0]. A solid component formed from a compound, which is a solid catalyst component supported on a magnesium compound carrier formed by catalytically reacting the component (i) and the component (iii) in the presence of the component (ii), [B] This is achieved by a method for producing a solid catalyst for olefin polymerization, which comprises supporting an aluminoxane component.

Moreover, the said object is according to this invention [A] (i) General formula [In the formula, M is aluminum, R ¹ is a hydrocarbon group,
For example, it is an alkyl group, an aryl group, etc., X is a group such as halogen, OR ² , OSiR ³ R ⁴ R ⁵ , NR ⁶ R ⁷ and SR ⁸ , and a ≧
When 0, b> 0, c> 0, d ≧ 0 and the valence of M is n, na + 2b = c + d is satisfied, and c R ¹ and d X are the same or different. Can be different,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent hydrogen or a hydrocarbon group,
R ⁸ represents a hydrocarbon group] or a solution of these organomagnesium compounds in a liquid state, (ii) General formula (I) R ¹ _k R ² _l R ³ _m R ⁴ _n Zr (I) [Wherein R ¹ represents a cycloalkadienyl group or a substituted product thereof, R ² , R ³ and R ⁴ represent a cycloalkadienyl group,
Aryl group, alkyl group, cycloalkyl group, aralkyl group, halogen atom, hydrogen, OR ^a , SR ^b , NR ₂ ^c , or PR
₂ ^d , R ^a , R ^b , R ^c and R ^d are a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, a silyl group, and two R ^c and R ^d are It is also possible to connect to form a ring. k ≧ 1 and k + l + m + n = 4. Further, when R ² is a cycloalkadienyl group, R ¹
And R ² may be bonded with a lower alkylene group. ] A solution of a zirconium compound represented by, and (iii) the general formula [In the formula, R ³ represents a hydrocarbon group, X represents a halogen atom, and a + b + c = 4, 4> a ≧ 0, 4> b ≧ 0 and 4 ≧ c ≧ 0]. A carrier-supported catalyst formed by contacting component (ii) with a particulate magnesium compound obtained by catalytically reacting component (i) and component (iii) This is achieved by a method for producing a solid catalyst for olefin polymerization, characterized in that a component [B] aluminoxane component is carried.

 The present invention will be described in detail below.

In the method for producing a solid catalyst for olefin polymerization of the present invention, [A] an aluminoxane component is supported on a [A] magnesium compound carrier-supporting solid catalyst component.

The above-mentioned [A] magnesium compound carrier-supported solid catalyst component is [A] (i) general formula [In the formula, M is aluminum, R ¹ is a hydrocarbon group,
For example, it is an alkyl group, an aryl group, etc., X is a group such as halogen, OR ² , OSiR ³ R ⁴ R ⁵ , NR ⁶ R ⁷ and SR ⁸ , and a ≧
When 0, b> 0, c> 0, d ≧ 0 and the valence of M is n, na + 2b = c + d is satisfied, and c R ¹ and d X are the same or different. Can be different,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent hydrogen or a hydrocarbon group,
R ⁸ represents a hydrocarbon group] or a solution of an organomagnesium compound in a liquid state [catalyst component (i)], (ii) general formula (I) R ¹ _k R ² _l R ³ _m R ⁴ _n Zr (I) [wherein R ¹ represents a cycloalkadienyl group or a substituted product thereof, R ² , R ³ and R ⁴ represent a cycloalkadienyl group,
Aryl group, alkyl group, cycloalkyl group, aralkyl group, halogen atom, hydrogen, OR ^a , SR ^b , NR ₂ ^c , or PR
₂ ^d , R ^a , R ^b , R ^c and R ^d are a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, a silyl group, and two R ^c and R ^d are It is also possible to connect to form a ring. k ≧ 1 and k + l + m + n = 4. Further, when R ² is a cycloalkadienyl group, R ¹
And R ² may be bonded with a lower alkylene group. ] A solution of a zirconium compound represented by [catalyst component (i
i)], and (iii) general formula [In the formula, R ³ represents a hydrocarbon group, X represents a halogen atom, and a + b + c = 4, 4> a ≧ 0, 4> b ≧ 0 and 4 ≧ c ≧ 0]. Compound [Catalyst component (ii
i)], can be obtained by catalytic reaction.

The organomagnesium compound in a liquid state [catalyst component (i)] used in the preparation of the solid catalyst for olefin polymerization of the present invention is represented by the following general formula M _a Mg _b R ¹ _c X _d [where M is aluminum, R ¹ is a hydrocarbon group,
For example, it is an alkyl group, an aryl group, etc., X is a group such as halogen, OR ² , OSiR ³ R ⁴ R ⁵ , NR ⁶ R ⁷ and SR ⁸ , and a
≧ 0, b> 0, c> 0, d ≧ 0, and the valence of M is n
And na + 2b = c + d are satisfied, c R ¹ and d X may be the same or different, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , R ⁷ represents hydrogen or a hydrocarbon group, and R ⁸ represents a hydrocarbon group].

Examples of such compounds include R ¹ in the above formula,
The hydrocarbon group for R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. , N-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, cyclohexyl, phenyl, p-tolyl and the like. The a is preferably 0 or more and a / b is 50 or less, particularly preferably 10 or less. Further, d is preferably 0 or more and smaller than a + b. Examples of the magnesium compound include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride. , Butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride and the like. These magnesium compounds can also be used in the form of complex compounds such as organic aluminum.

The zirconium compound used for preparing the solid catalyst for olefin polymerization of the present invention is a zirconium compound having a group having a conjugated π electron as a ligand.

The zirconium compound having a group having a conjugated π-electron as the ligand is represented by, 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 or The substituted form is shown, R ² , R ³ and R ⁴ are cycloalkadienyl groups,
Aryl group, alkyl group, cycloalkyl group, aralkyl group, halogen atom, hydrogen, OR ^a , SR ^b , NR ₂ ^c , or PR
₂ ^d , R ^a , R ^b , R ^c and R ^d are a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, a silyl group, and two R ^c and R ^d are It is also possible to connect to form a ring. k ≧ 1 and k + l + m + n = 4. Further, when R ² is a cycloalkadienyl group, R ¹
And R ² may be bonded with a lower alkylene group. ] It is a compound shown by these. Examples of the cycloalkadienyl group include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, dimethylcyclopentadienyl group, indenyl group, tetrahydroindene group. Examples include a nyl group and the like. As an alkyl group,
Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, and an oleyl group. Examples of the aryl group include phenyl. Base,
Examples thereof include a tolyl group and the like, examples of the aralkyl group include a benzyl group and a neophyl group, and examples of the cycloalkyl group include a cyclopentyl group,
Examples thereof include a cyclohexyl group, a cyclooctyl group, a norbornyl group, a bicyclononyl group, and alkyl substituents of these groups. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a phenyldimethylsilyl group, and a triphenylsilyl group. And the like. Other examples include unsaturated aliphatic groups such as vinyl group, allyl group, propenyl group, isopropenyl group and 1-butenyl group, and unsaturated alicyclic groups such as cyclohexenyl group. Examples of the halogen atom include fluorine, chlorine and bromine, and examples of the lower alkylene group include lower alkylene groups such as methylene group, ethylene group, propylene group and butylene group.

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 (methylcyclopentadiene) (Enyl) zirconium monochloride monohydride, bis (indenyl) zirconium monochloride monohydride, bis ( Cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) Cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis ( Indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, (Cyclopentadienyl) methoxyzirconium chloride, bis (cyclopentadienyl) methoxyzirconium chloride, bis (cyclopentadienyl) ethoxyzirconium chloride, bis (cyclopentadienyl) butoxyzirconium chloride, bis (cyclopentadienyl) 2-ethylhexoxy zirconium chloride, bis (cyclopentadienyl) methyl zirconium ethoxide, bis (cyclopentadienyl) methyl zirconium butoxide, bis (cyclopentadienyl) ethyl zirconium ethoxide, bis (cyclopentadienyl) Phenyl zirconium ethoxide, bis (cyclopentadienyl) benzyl zirconium ethoxide, bis (methylcyclopentadienyl) ethoxy zirconium chloride, bi Sindenyl ethoxy zirconium chloride, bis (cyclopentadienyl) ethoxy zirconium chloride, bis (cyclopentadienyl) butoxy zirconium chloride, bis (cyclopentadienyl) 2-ethylhexoxy zirconium chloride, bis (cyclopentadienyl) ) Phenyloxyzirconium chloride, bis (cyclopentadienyl) cyclohexoxyzirconium chloride, bis (cyclopentadienyl) phenylmethoxyzirconium chloride, bis (cyclopentadienyl) methylzirconium phenylmethoxide, bis (cyclopentapentyl) Dienyl) trimethylsiloxyzirconium chloride, bis (cyclopentadienyl) triphenylsiloxyzirconium chloride, bis (cyclopentadienyl) thiophene Nylzirconium chloride, bis (cyclopentadienyl) thioethylzirconium chloride, bis (cyclopentadienyl) bis (dimethylamido) zirconium, bis (cyclopentadienyl) diethylamide zirconium chloride, ethylenebis (indenyl) ethoxyzirconium chloride, Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ethoxyzirconium chloride, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) ) Dibenzylzirconium, ethylenebis (indenyl) methylzirconium monobromide, ethylenebis (indenyl) ethylzirconium monochloride Ethylenebis (indenyl) benzylzirconium monochloride, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (4,5,6,7-tetrahydro) -1-Indenyl) dimethylzirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, Tylene 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, ethylenebis (indenyl) zirconium dimethoxide, ethylenebis (indenyl) zirconium diethoxide, ethylenebis (indenyl) methoxyzirconium chloride, ethylenebis (indenyl) ethoxyzirconium chloride, ethylenebis (indenyl) methylzirconium ethoxide, Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethoxide, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium diethoxide, ethylenebis (4,5, 6,7-Tetrahydro-1-indenyl) methoxyzirconium chloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ethoxyzirconium chloride, ethylenebis (4,5,6,7-tetrahydro-1- Indenyl Methyl zirconium ethoxide.

In the catalyst component (ii), the zirconium compound having a group having a conjugated π electron as a ligand may be previously treated with an organoaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, or methylaluminum dichloride. Good.

Examples of the solvent for the zirconium compound (ii) include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, propylbenzene, butylbenzene and xylene, and halogen-containing hydrocarbons such as chlorobenzene and dichloroethane.

The halogenated silicon compound [catalyst component (iii)] used for the preparation of the solid catalyst for olefin polymerization of the present invention has the following general formula: ▲ R ³ _a ▼ H _b SiX _c [wherein R ³ represents a hydrocarbon group. X represents a halogen atom, and a + b + c = 4, 4> a0, 4> b0 and 4>C> 0], and is a halogenated silicon compound.

An example of such a halogenated silicon compound is HSiC.
l ₃ , HSiCl ₂ CH ₃ , HSiCl ₂ C ₂ H ₅ , HSiCl ₂ nC ₃ H ₇ , HSiCl ₂ iso
-C ₃ H ₇ , HSiCl ₂ nC ₄ H ₉ , HSiSiCl ₂ nC ₆ H ₁₃ , HSiCl ₂ CH = CH
₂ , HSiCl ₂ C ₆ H ₅ , HSiCl (CH ₃ ) ₂ , HSiClCH ₃ (C ₂ H ₅ ), H ₂ SiCl
C ₂ H ₅ , HSiCl ₂ CH ₂ CH = CH ₂ , SiCl ₄ , CH ₃ SiCl ₃ , C ₂ H ₅ SiC
l ₃ , CH ₂ = CH-SiCl ₃ , C ₆ H ₅ SiCl ₃ , CH ₃ SiCl ₂ MeOSiCl ₃
And the like can be exemplified C ₂ H ₅ OSiCl _3.

In the present invention, the magnesium compound carrier-supported solid catalyst component obtained from the above catalyst components (i), (ii) and (iii) is used. The magnesium compound carrier-supported solid catalyst component [A] can be produced, for example, by the following method.

(1) A method of catalytically reacting the catalyst components (i) and (iii) in the presence of the catalyst component (ii).

(2) A method in which the catalyst components (i) and (iii) are catalytically reacted to produce a fine particle magnesium compound, and the fine particle magnesium compound thus produced is catalytically reacted with the catalyst component (ii).

In the above method, the ratio of the catalyst component (ii) to the catalyst component (i) is 0.001 to 1, preferably 0.005 to 0.5, and more preferably 0.01 to 0.2 in terms of the atomic ratio of zirconium to magnesium (Zr / Mg).

In the above method, the ratio of the catalyst component (iii) to the catalyst component (i) is 0.1 to 100, preferably 0.5 to 10, in terms of atomic ratio of silicon to magnesium (Si / Mg).
It is more preferably 1 to 5.

The temperature of the above-mentioned catalytic reaction is -50 to 200 ° C, preferably 0 to 120 ° C, more preferably 30 to 80 ° C.

The contact reaction can be carried out under reduced pressure, normal pressure or increased pressure.

The contact reaction is preferably performed in an inert atmosphere, for example, a nitrogen atmosphere.

As the inert medium that can be used in the above reaction,
For example, hexane, heptane, octane, decane, kerosene, and other aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclopentane, and other aliphatic hydrocarbons; benzene, toluene, xylene, ethylbenzene, and other aromatic hydrocarbons; chloroethane, chloro Examples thereof include halogenated hydrocarbons such as benzene; ethers such as diethyl ether and tetrahydrofuran; or a mixture thereof.

 The catalyst component [B] is aluminoxane.

General formula (II) and general formula (III) as aluminoxane used as the catalyst component [B] The organoaluminum compound represented by can be exemplified. In the aluminoxane, R is a methyl group,
Hydrocarbon groups such as ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, etc., preferably methyl group, ethyl group, isobutyl group, particularly preferably methyl group, m is 2 or more, It is preferably an integer of 5 or more. Also, a part of R may be a halogenated aluminoxane having a halogen content of 40% by weight or less, which is substituted with a halogen atom such as chlorine or bromine. The following method can be exemplified as a method for producing the aluminoxane.

(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. For example, an organometallic compound component such as a halogen-containing organoaluminum compound or an organomagnesium compound may be present in addition to the above trialkylaluminum.

As a solvent for aluminoxane, for example, benzene,
Aromatic hydrocarbons such as toluene, ethylbenzene, propylbenzene, butylbenzene, xylene and chlorobenzene can be mentioned.

The solid catalyst for olefin polymerization of the present invention can be produced by supporting the aluminoxane component [B] on the above-mentioned magnesium compound carrier-supporting solid catalyst component [A].

In the present invention, the following methods (a), (b) and (c) may be used to support the aluminoxane component [B] on the magnesium compound carrier-supported solid catalyst component [A].
Can be illustrated.

(A) A method of forming a solid component by bringing a suspension of a solid catalyst component [A] dispersed in an insoluble or sparingly soluble solvent of aluminoxane into contact with a solution of aluminoxane component [B].

Specifically, by adding a solution of aluminoxane to a suspension of a solid catalyst component [A] dispersed in an insoluble or sparingly soluble solvent of aluminoxane, or insoluble or insoluble of aluminoxane in a solution of aluminoxane. Precipitating aluminoxane by adding a suspension composed of a poorly soluble solvent and a solid catalyst component [A], and optionally distilling off the solvent used to dissolve the aluminoxane from the mixed suspension. To accelerate the precipitation of aluminoxane to prepare a solid catalyst for olefin polymerization supported by the aluminoxane component [B].

In the suspension formed from the insoluble or sparingly soluble solvent of the aluminoxane and the solid catalyst component [A], the amount of the solid catalyst component [A] is usually 1 to 500 g, preferably 10 g per 1 solvent. To 200 g, more preferably 20 to 100 g. Further, the contact between the suspension and the solution of aluminoxane is usually -100 to 3
00 ° C, preferably -50 to 100 ° C, more preferably -3
It is carried out in the range of 0 to 50 ° C. The contact is usually carried out with stirring. The amount of the aluminoxane solution at the time of contact is usually 1 to 100 with respect to 100 parts by weight of the suspension.
It is in the range of 0 parts by weight, preferably 10 to 100 parts by weight.
It is also possible to add an electron donor component to any step of this method to form a solid catalyst for olefin polymerization containing the electron donor component.

The solution of aluminoxane used for the catalyst is formed by at least aluminoxane and the solvent used for dissolving the aluminoxane described above. Examples of a method for obtaining the solution include a method of simply mixing both compounds, and a method of mixing by heating. The amount of solvent in the solution is in the range of 0.1 to 50 liters, preferably 0.2 to 10 liters, more preferably 0.3 to 2 liters per gram atom of aluminum in the aluminoxane.

(B) A method of forming a solid component by bringing a suspension of a solid catalyst component [A] dispersed in a solution of aluminoxane into contact with an insoluble or sparingly soluble solvent of aluminoxane.

Specifically, an insoluble or sparingly soluble solvent of aluminoxane is added to a suspension composed of a solution of aluminoxane and a solid catalyst component [A], or a solution of aluminoxane and the solid catalyst component are added to the insoluble or sparingly soluble solvent. Precipitation of aluminoxane by adding a suspension consisting of [A] to precipitate aluminoxane and optionally evaporating away the catalyst used to dissolve the aluminoxane from the mixed suspension. Is promoted to prepare a solid catalyst for olefin polymerization in which aluminoxane is supported on the solid catalyst component [A].

In the step of contacting a suspension of the aluminoxane solution and the solid catalyst component [A] with an insoluble or sparingly soluble solvent of aluminoxane, the aluminoxane solution is added to 100 parts by weight of the aluminoxane solution. The proportion of the insoluble or sparingly soluble solvent is usually 10 to 10000 parts by weight, preferably 100 to 1000 parts by weight, the temperature at the time of contact is usually -100 to 300 ℃, preferably -50 to
100 ° C, more preferably in the range of -30 to 50 ° C,
Contacting is usually carried out with stirring. It is also possible to add an electron donor component to any step of this method to form a solid catalyst for olefin polymerization containing the electron donor component.

The aluminoxane solution is formed of at least aluminoxane and the solvent used for dissolving the aluminoxane described above. Examples of a method for obtaining an aluminoxane solution include a method of simply mixing both compounds or a method of mixing by heating. The amount of solvent in the aluminoxane solution may be from 0.1 to 50 per gram atom of aluminum in the aluminoxane.
l, preferably 0.2 to 10 l, more preferably 0.3 to
The range is 21.

The amount of the catalyst component in the suspension of the solid catalyst component [A] dispersed in the aluminoxane solution is 1 to 500 g, preferably 10 to 200 g, per 1 solution of aluminoxane. It is preferably in the range of 20 to 100 g.

(C) A method of removing the solvent used for dissolving the aluminoxane from a suspension composed of a solution of the solid catalyst component [A] and the aluminoxane by a method such as evaporation.

Among these methods, (a) and (b) can be exemplified as more preferable methods.

As an insoluble or poorly soluble solvent for aluminoxane,
Examples thereof include linear or branched aliphatic hydrocarbons such as pentane, hexane, decane, dotecan, kerosene and cyclohexane, and alicyclic hydrocarbons such as cyclohexane, norbornene and ethylcyclohexane. As the insoluble or hardly soluble solvent for aluminoxane, it is preferable to use a solvent having a higher boiling point than the solvent used for obtaining the solution of aluminoxane.

In the solid catalyst for olefin polymerization obtained by the production method of the present invention, the atomic ratio (Zr / Mg) of the zirconium compound (Zr) to magnesium is 0.0001 to 1, preferably 0.0005 to 0.5, and more preferably 0.001 to 0.1. When the atomic ratio (Zr / Mg) is larger than 1, the polymerization activity per Zr is lowered, while when the atomic ratio (Zr / Mg) is smaller than 0.0001, the polymerization activity per catalyst or aluminoxane is large. descend.

In the solid catalyst for olefin polymerization obtained by the process of the present invention, the atomic ratio of halogen to magnesium (X / Mg) is 0.1 to 10, preferably 0.5 to 5, and more preferably 1 to 3.

In the solid catalyst for olefin polymerization obtained by the production method of the present invention, the atomic ratio of silicon to magnesium (Si / M
g) is usually 2 or less, preferably 0.0001 to 1, and more preferably 0.001 to 0.5.

In the solid catalyst for olefin polymerization obtained by the production method of the present invention, the atomic ratio (Al / Zr) of aluminum atoms in the aluminoxane component to the zirconium compound is 5
To 2000, preferably 10 to 1000, more preferably
20 to 500. If the atomic ratio (Al / Zr) is less than 5, the polymerization activity will decrease, while the atomic ratio (Al / Zr)
When the value is larger than 2000, the amount of aluminoxane used increases more than necessary.

In the solid catalyst for olefin polymerization obtained by the production method of the present invention, the average particle size of the catalyst is 1 to 200 μm,
Preferably 10 to 150 μm, more preferably 20 to 1
It is 00 μm. When the average particle size is larger than 200 μm, the polymer particles produced are significantly large, while when the average particle size is smaller than 1 μm, the weight of the polymer obtained by using the solid catalyst for olefin polymerization obtained by the process of the present invention is large. The particle size of the coalesced particles is significantly reduced, and at the same time, the bulk specific gravity is not large enough to obtain a polymer having excellent powder properties.

The solid catalyst component obtained by the method of the present invention may contain a component such as an electron donor as an optional component, or may be supplied to the polymerization reaction system. Examples of electron donors include metal atoms such as carboxylic acids, esters, ethers, ketones, aldehydes, alcohols, phenols, acid amides, aluminum, and silicon-OC.
Examples thereof include oxygen-containing compounds such as bond-containing compounds, nitriles, amines and phosphines. For example,
The content of the electron donor is usually 0 to 1 mol, preferably 0.1 to 0.6 per 1 gram atom of the zirconium.
It is in the molar range.

The solid catalyst for olefin polymerization obtained by the method of the present invention is effective for producing an olefin polymer, particularly an ethylene polymer and a copolymer of ethylene and α-olefin.
As an example of the olefin that can be polymerized with the solid catalyst for olefin polymerization obtained by the method of the present invention, the number of carbon atoms is 2
To 20 alpha-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. Of these, polymerization of ethylene or ethylene and 3 to 3 carbon atoms
Copolymerization of 10 α-olefins is preferred.

Olefin polymerization using the catalyst for olefin polymerization obtained by the method of the present invention is usually carried out by a gas phase polymerization method or a liquid phase polymerization method such as a slurry polymerization method or a solution polymerization method.
In the slurry polymerization, an inert hydrocarbon may be used as a solvent, or olefin itself may be used as a solvent.

Specific examples of the hydrocarbon medium include butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane, and other alicyclic groups. Examples include petroleum fractions such as system hydrocarbons, kerosene, and light oil.

In the above method, the use ratio of the zirconium compound when used in a liquid phase polymerization method such as a slurry polymerization method or a solution polymerization method or a gas phase polymerization method is usually 10 ⁻⁸ as the concentration of the zirconium atom in the polymerization reaction system. ^Or 10 ^-2 g atom / l,
It is preferably in the range of 10 ⁻⁷ to 10 ⁻³ gram atom / l.

Further, when the above invention is carried out by a liquid phase polymerization method or a gas phase polymerization method, the amount of aluminoxane used is 10 mg atom / l in terms of aluminum atom in the reaction system.
Or less, preferably 5 mg / l or less, more preferably 0.01 to 2 mg / l, particularly preferably
It is in the range of 0.02 to 1 milligram atom / l. In the method of the present invention, the ratio of aluminum atoms of the aluminoxane component to zirconium atoms in the reaction system is usually in the range of 5 to 2000, preferably 10 to 1000, particularly preferably 20 to 500.

When the above method is carried out by a liquid phase polymerization method such as a slurry polymerization method or a solution polymerization method, the polymerization temperature is usually -50 to 200.
C., preferably in the range 0 to 170.degree.

When the above method is carried out by a gas phase polymerization method, the polymerization temperature is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C.

The polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably 2
To 50 kg / cm ² under pressurized condition, polymerization is batch type,
It can be carried out by any of a semi-continuous method and a continuous method.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

In the above method, when a slurry polymerization method or a gas phase polymerization method is adopted, it is preferable to carry out olefin prepolymerization in the presence of the solid catalyst prior to olefin polymerization. The prepolymerization is 1 to 1000 g, preferably 5 to 500, per milligram atom of zirconium in the solid catalyst.
g, more preferably from 10 to 200 g of olefin, is polymerized. As the olefin used in the prepolymerization, ethylene and α-olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-
Although decene, 1-dodecene, 1-tetradecene, etc. can be illustrated, ethylene is preferable.

Prepolymerization temperature is -20 ° C to 70 ° C, preferably -10 ° C
To 60 ° C, more preferably 0 ° C to 50 ° C.

The treatment can be performed either in a batch system or a continuous system, and can be performed under normal pressure or under pressure. In the prepolymerization, a molecular weight modifier such as hydrogen may coexist, but the intrinsic viscosity [η] measured in decalin at at least 135 ° C. is 0.1 dl / g or more, preferably
It is preferable to control the amount so that a prepolymer of 0.5 to 20 dl / g can be produced.

The prepolymerization is carried out without solvent or in an inert hydrocarbon medium. Preliminary polymerization in an inert hydrocarbon medium is preferred from the viewpoint of operability. Examples of the inert hydrocarbon medium used for the prepolymerization include the above-mentioned solvents as insoluble or hardly soluble solvents for aluminoxane.

As the concentration of the solid catalyst in the prepolymerization reaction system in the prepolymerization, usually as the concentration of the transition metal atom in the solid catalyst
10 ^-6 to 1 gram atom / l, preferably 10 ^-4 to 10 ^-2
It is in the range of gram atom / l.

[Effect of the Invention] According to the present invention, a solid catalyst for olefin polymerization having extremely high polymerization activity for homopolymerization and copolymerization of olefin, which has a large bulk specific gravity, a uniform particle size, a small amount of fine powder, a narrow molecular weight distribution, and further copolymerization It is possible to provide a catalyst that gives polymers and copolymers having a narrow composition distribution.

[Examples] Hereinafter, the present invention will be specifically described with reference to Examples.

[Preparation of methylaminooxane] Al ₂ (SO ₄ ) ₃ · 14H ₂ O 37g and toluene 125 ml were put into a 400-ml glass flask equipped with a stirrer, which had been sufficiently replaced with nitrogen.
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 42 hours. After the reaction, solid-liquid separation was performed by filtration, 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 calculated from the freezing point depression in benzene is 88.
Therefore, the degree of polymerization of this methylaluminoxane was 15.

Example 1 [Preparation of solid catalyst component] n-BuM was added to a 400 ml glass reactor sufficiently replaced with nitrogen.
After adding 100 ml of dibutyl ether solution containing 195 mM gCl
The temperature was raised to 50 ° C., and a mixture of 140 ml of a toluene solution containing 5.7 mM of biscyclopentadienylzirconium dichloride and 22.2 ml of silicon tetrachloride was added dropwise over 2 hours. Then, after raising the temperature to 60 ° C and reacting for about 1 hour,
Separate the solid part by filtration and add 1 with about 200 ml of purified hexane.
Washed twice. The solid catalyst component obtained contained 0.12% by weight.
It contained Zr, 23 wt% magnesium and 60 wt% chlorine. The catalyst particles were spherical particles having a diameter of about 50 μm.

[Immobilization of aluminoxane] The above solid catalyst component was collected into a glass reactor of 0.13 mM in terms of Zr atom and 400 ml and suspended in 200 m of purified n-decane, and then methylaluminum equivalent to 40 mM in terms of aluminum atom. 20 ml of a toluene solution of nooxane was added.

Then, the pressure in the reactor was reduced to 5 torr at 20 ° C. under stirring to remove toluene, and then the reaction solution was kept at −20 for 1 hour.
The mixture was cooled to ℃ and transferred to a filter to collect a solid part. The aluminum content in the solid part was 6.2% by weight.

[Preliminary Polymerization] Purification of 100 ml under a nitrogen atmosphere in a 400 ml reactor equipped with a stirrer
After adding decane and the solid catalyst in an amount corresponding to 0.1 mmol of Zr, ethylene was fed at a rate of 4 Nl / hour for 1 hour. During this period, the temperature was kept at 20 ° C. After the supply of ethylene was completed, the system was replaced with nitrogen, washed once with purified hexane, resuspended in hexane and stored in a catalyst bottle.

[Polymerization] Add 250 g of sodium chloride as a dispersant to an autoclave with an internal volume of 2 liters that has been sufficiently replaced with nitrogen, and heat it to 90 ° C to reduce the internal pressure of the autoclave to 50 mmHg or less with a vacuum pump for 2 hours. It was Then, the temperature of the autoclave was lowered to 75 ° C., and after the inside of the autoclave was replaced with ethylene, 0.01 mmol of the solid catalyst component which had been subjected to the prepolymerization was added in terms of silconium atom, and then 50 Nml of hydrogen was added to the autoclave as a closed system, and ethylene was added. 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 sodium chloride was dissolved in water, and only the polymer floated 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 89 g, the MFR was 2.3 dg / min, and the apparent bulk density was 0.4.
It was 5 g / ml.

Example 2 [Preparation of solid catalyst component] 22.2 m in a 400 ml glass reactor sufficiently replaced with nitrogen.
n-BuMgCl 195 mM was added to this mixture after adding 140 ml of a toluene solution containing 1 ml of silicon tetrachloride and 5.7 mM biscyclopentadienyl zirconium chloride and heating to 50 ° C.
100 ml of a dibutyl ether solution containing the above was added dropwise over 2 hours, and then the mixture was stirred and mixed at 60 ° C. for 1 hour. Then, the solid portion was separated by filtration and washed once with about 200 ml of purified hexane. The obtained solid catalyst component contained 0.10% by weight of Zr, 20% by weight of magnesium and 55% by weight of chlorine. The catalyst particle size was about 25 μm.

In the same manner as in Example 1 below, aluminoxane was fixed, prepolymerized, and ethylene was polymerized.

 The results are shown in Table-1.

Example 3 [Preparation of solid catalyst component] n-BuM was added to a 400 ml glass reactor sufficiently replaced with nitrogen.
After adding 138 ml of dibutyl ether solution containing 195 mM gCl 5
The temperature was raised to 0 ° C., and a mixture of 140 ml of a toluene solution containing 5.7 mM of biscyclopentadienylzirconium dichloride and 44.4 ml of silicon tetrachloride was added dropwise over 2 hours.

Then, the temperature was raised to 60 ° C. and the reaction was carried out for about 1 hour. Then, the solid portion was separated by filtration and washed once with about 200 ml of purified hexane. The solid catalyst component obtained contained 1.0% by weight of Zr, 2
It contained 0% by weight magnesium and 59% by weight chlorine. The catalyst particles were spherical particles having a diameter of about 30 μm.

In the same manner as in Example 1 below, immobilization of aluminoxane, prepolymerization and polymerization of ethylene were carried out.

Example 4 [Preparation of solid catalyst component] n-BuM was added to a 400 ml glass reactor sufficiently replaced with nitrogen.
After adding 100 ml of dibutyl ether solution containing 195 mM gCl 5
The temperature was raised to 0 ° C., and a mixture of 140 ml of a toluene solution containing 5.7 mM of biscyclopentadienylzirconium dichloride and 19.8 ml of silicon tetrachloride was added dropwise over 2 hours.

Then, the temperature was raised to 60 ° C. and the reaction was carried out for about 1 hour, then the solid part was separated by filtration and washed once with about 200 ml of purified hexane. 0.51% by weight of Zr in the obtained solid catalyst component,
It contained 19% by weight of magnesium and 61% by weight of chlorine. The catalyst particles were spherical particles having a diameter of about 13 μm.

In the same manner as in Example 1 below, aluminoxane was fixed, prepolymerized, and ethylene was polymerized.

Example 5 [Preparation of solid catalyst component] n-BuM was added to a 400 ml glass reactor sufficiently replaced with nitrogen.
After adding 100 ml of dibutyl ether solution containing 195 mM gCl 5
The temperature was raised to 0 ° C., and 70 ml of a toluene solution containing 22.2 ml of silicon tetrachloride was added dropwise thereto over 2 hours.

Then, the temperature was raised to 60 ° C., the reaction was carried out for about 1 hour, the solid portion was separated by filtration, resuspended in about 200 ml of purified n-decane, and then returned to the reactor.

Next, 10 ml of a 1.2-dichloroethane solution containing 5.7 mM of biscyclopentadienyl zirconium dichloride was added to this reactor, and the reaction was carried out at 60 ° C for 1 hour. Then, the solid portion was separated by filtration and about 200 ml of purified hexane was added. It was washed once with. The obtained solid catalyst component contained 0.11% by weight of Zr, 22% by weight of magnesium and 60% by weight of chlorine. The catalyst particles were about 40 μm.

In the same manner as in Example 1 below, aluminoxane was fixed, prepolymerized, and ethylene polymerized. The results are shown in Table-1.

Example 6 7.5 instead of n-BuMgCl in [Preparation of Solid Catalyst Component Example _{1 (nC 4 H 9) 2} Mg ·
(C ₂ H ₅ ) ₃ Al (Magala 7.5E) converted to Mg atom 195 mmol, performed in the same manner except that 40 ml of silicon tetrachloride was used.
Of 0.10 wt%, Mg of 21 wt%, Al of 2.9 wt% and chlorine of 64 wt% were obtained.
The average particle size of the catalyst was 23 μm.

[Immobilization of aluminoxane] The same procedure as in Example 1 was carried out to obtain a solid component having an aluminum content of 8.9% by weight.

[Preliminary Polymerization] The same procedure as in Example 1 was carried out.

[Polymerization] The same procedure as in Example 1 was carried out to obtain 71 g of a polymer having an MFR of 1.9 dg / min and an apparent bulk density of 0.40 g / ml.

[Brief description of drawings]

FIG. 1 is a flow chart illustrating the steps for producing the catalyst according to the present invention.

Claims (2)

[Claims] 1. A general formula of [A] (i) [Wherein, M is aluminum, R ¹ is a hydrocarbon group, X is a halogen, OR ² , OSiR ³ R ⁴ R ⁵ , NR ⁶ R ⁷ or SR ⁸ group, and a ≧ 0, b > 0, c> 0, d ≧ 0,
When the valence of M is n, na + 2b = c + d is satisfied, and c
R ¹ and d X may be the same or different, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent hydrogen or a hydrocarbon group, and ⁸ represents a hydrocarbon group], or a solution of these organomagnesium compounds in a liquid state, (ii) the general formula (I) R ¹ _k R ² _l R ³ _m R ⁴ _n Zr (I) [ Here, R ¹ represents a cycloalkadienyl group or a substituted product thereof, R ² , R ³ and R ⁴ are cycloalkadienyl group, aryl group, alkyl group, cycloalkyl group, aralkyl group, halogen atom, hydrogen, OR ^a , SR ^b , NR ₂ ^c , or PR ₂ ^d
And R ^a , R ^b , R ^c and R ^d are a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, a silyl group, and two R ^c and R ^d are linked to each other. Can also form a ring. k ≧ 1 and k + l + m + n = 4. Further, when R ² is a cycloalkadienyl group, R ¹
And R ² may be bonded with a lower alkylene group. ] A solution of a zirconium compound represented by, and (iii) the general formula [Wherein, R ³ represents a hydrocarbon group, X represents a halogen atom, a + b + c = 4, 4> a ≧ 0, 4> b ≧ 0 and 4
≧ c ≧ 0], which is a solid component formed of a halogenated silicon compound represented by the formula: and is formed by catalytically reacting the component (i) and the component (iii) in the presence of the component (ii). A method for producing a solid catalyst for olefin polymerization, comprising: [B] an aluminoxane component supported on a magnesium compound carrier-supporting solid catalyst component. 2. A general formula of [A] (i) [Wherein, M is aluminum, R ¹ is a hydrocarbon group, X is a halogen, OR ² , OSiR ³ R ⁴ R ⁵ , NR ⁶ R ⁷ or SR ⁸ group, and a ≧ 0, b > 0, c> 0, d ≧ 0,
When the valence of M is n, na + 2b = c + d is satisfied, and c
R ¹ and d X may be the same or different, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent hydrogen or a hydrocarbon group, and ⁸ represents a hydrocarbon group], or a solution of these organomagnesium compounds in a liquid state, represented by the general formula (I) R ¹ _k R ² _l R ³ _m R ⁴ _n Zr (I) [where R ¹ represents a cycloalkadienyl group or a substituted product thereof, R ² , R ³ and R ⁴ are cycloalkadienyl group, aryl group, alkyl group, cycloalkyl group, aralkyl group, halogen atom, hydrogen, OR ^a , SR ^b , NR ₂ ^c , or PR ₂ ^d
And R ^a , R ^b , R ^c and R ^d are a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, a silyl group, and two R ^c and R ^d are linked to each other. Can also form a ring. k ≧ 1 and k + l + m + n = 4. Further, when R ² is a cycloalkadienyl group, R ¹
And R ² may be bonded with a lower alkylene group. ] A solution of a zirconium compound represented by, and (iii) the general formula [Wherein, R ³ represents a hydrocarbon group, X represents a halogen atom, a + b + c = 4, 4> a ≧ 0, 4> b ≧ 0 and 4
≧ c ≧ 0], which is a solid component formed of a halogenated silicon compound represented by the formula: wherein a fine particle magnesium compound obtained by catalytically reacting the component (i) and the component (iii) A method for producing a solid catalyst for olefin polymerization, comprising: [B] an aluminoxane component supported on a carrier-supported catalyst component formed by contacting ii).