JPH07110885B2 - Olefin Polymerization Method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for polymerizing olefins.

More particularly, it relates to a method for polymerizing olefins in the presence of a catalyst formed from a high activity zirconium solid catalyst component containing magnesium, zirconium and halogen as essential components and an aluminoxane catalyst component.

[Prior Art] Conventional methods for producing an α-olefin polymer, particularly an ethylene homopolymer or an ethylene / α-olefin copolymer, include a titanium-based catalyst composed of a titanium compound and an organoaluminum compound, or a vanadium compound and an organoaluminum compound. It is known to polymerize ethylene or copolymerize ethylene and α-olefin in the presence of a vanadium-based catalyst comprising 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, as a new Ziegler type olefin polymerization catalyst,
A catalyst composed of a zirconium compound and aluminoxane has recently been proposed.

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 20].
The linear aluminoxane represented by [Wherein R and n are the same as defined 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 200 ° C is described. The publication describes 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 [Wherein n is 2 to 40 and R is C _{1 to} C ₆ ] 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 is polymerized. It is stated that more than 25 million g of polyethylene can be 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 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 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. In Example 2, ethylene and propylene were polymerized using bis (pentamethylcyclopentadienyl) zirconium chloride, 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) is 4.57 and the propylene component is 20.6.
LLDPE and ethylene consisting of mol% soluble part and molecular weight distribution 3.04 and 2.9% propylene component insoluble part
Blends of propylene copolymers 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 aluminoxane represented by the following formula: [Wherein R and n have the same definitions as above], and a method of polymerizing in the presence of a catalyst system comprising a linear aluminoxane represented by the formula is described. According to the description of the publication, the polymer obtained by the method has 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 C ₃ -C ₁₀ α- It is described that olefin copolymers are produced. 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, JP-A-60-35006 and JP-A-60-35006 cited above
In JP-A-60-35007 and JP-A-60-35008, transition metal compounds and aluminoxane are added to silica, silica.
It is described that a catalyst supported on alumina, alumina or the like can be used.

Further, JP-A-60-106806 and JP-A-60-106809.
Japanese Patent Laid-Open Publication No. 2003-242242 discloses a product obtained by pre-contacting a highly active catalyst component containing titanium and / or zirconium, which is soluble in a hydrocarbon solvent, and a filler, and 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-61-296008
The publication discloses a method of polymerizing olefin 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 method for polymerizing olefins capable of giving an olefin polymer having a large bulk specific gravity and excellent powder properties.

[Means for Solving the Problems] According to the present invention, the above-mentioned object is: [A] a magnesium compound (a) formed from a zirconium compound (b) having a group having a conjugated π electron as a ligand; A method for polymerizing olefin, which comprises polymerizing olefin in the presence of a solid catalyst formed from a highly active zirconium solid catalyst component containing zirconium and halogen as essential components, and [B] aluminoxane catalyst component. Achieved by

The present invention will be described in detail below.

The olefin polymerization method of the present invention is carried out in the presence of a specific catalyst.

The catalyst used in the olefin polymerization method of the present invention is formed from [A] a highly active zirconium solid catalyst component and [B] an aluminoxane catalyst component, and the highly active zirconium solid catalyst component is It is formed from (a) a magnesium compound and (b) a zirconium compound having a group having a conjugated π electron as a ligand, and contains magnesium, zirconium and halogen as essential components. The magnesium compound (a) forming the highly active zirconium solid catalyst component [A] is preferably an organomagnesium compound in a liquid state. The organic magnesium compound in the liquid state, the general formula ^{_{M a Mg b R 1 c X}} d [ where, M is aluminum, zinc, boron, beryllium, sodium, potassium, etc., R ¹ is a hydrocarbon group, such as 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 , SR ^{8 and the} like, 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 and R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ represent hydrogen or a hydrocarbon group, and R ⁸ represents a hydrocarbon group] or an organic solvent solution of these organomagnesium compounds.

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-
Examples thereof include ethylhexyl, n-decyl, cyclohexyl, phenyl and p-tolyl. Alternatively, a is 0 or more and a / b is 50 or less, particularly 10
The following are preferred. Further, d is 0 or more, and a + b
It is preferably smaller.

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 (b) forming the high activity zirconium solid catalyst component is a zirconium compound having a group having a conjugated π electron as a ligand.

The zirconium compound (b) having a group having a conjugated π electron as a 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 cycloalkadi An enyl group or a substituted form 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 , 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 can also be joined to form a ring. k ≧ 1, 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 olein 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, 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 ( Cyclopentadienyl) zirconium chloride, 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, bis 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 Phenyl zirconium ethoxide, bis (cyclopentadienyl) benzyl zirconium ethoxide, bis (methylcyclopentadienyl) ethoxy zirconium chloride, bis Indenyl ethoxy zirconium chloride, bis (cyclopentadienyl) ethoxy zirconium chloride, bis (cyclopentadienyl) butoxy zirconium chloride, bis (cyclopentadienyl) 2-ethylhexoxy zirconium chloride, bis (cyclopentadienyl) Phenoxyzirconium chloride, bis (cyclopentadienyl) cyclohexoxyzirconium chloride, bis (cyclopentadienyl) phenylmethoxyzirconium chloride, bis (cyclopentadienyl) methylzirconium phenylmethoxide, bis (cyclopentadienyl) (Enyl) trimethylsiloxy zirconium chloride, bis (cyclopentadienyl) triphenylsiloxy zirconium chloride, bis (cyclopentadienyl) thiophene Ruzirconium chloride, bis (cyclopentadienyl) thioethyl zirconium chloride, bis (cyclopentadienyl) bis (dimethylamide)
Zirconium, bis (cyclopentadienyl) diethylamide zirconium chloride, ethylenebis (indenyl) ethoxyzirconium chloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ethoxyzirconium chloride, ethylenebis (indenyl) dimethylzirconium Ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) dibenzyl zirconium, ethylene bis (indenyl) methyl zirconium monobromide, ethylene bis (indenyl) ethyl zirconium monochloride, ethylene bis ( Indenyl) benzyl zirconium monochloride, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis ( Indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ) Methyl zirconium 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, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) Zirconium dichloride, ethi Bis (5-methoxy-1-indenyl) zirconium dichloride, ethylenebis (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-yne Denyl) zirconium diethoxide, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methoxyzirconium chloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ethoxyzirconium chloride, ethylene Bis (4,5,6,7-tetrahydro-1-indenyl) methyl zirconium ethoxide.

In the catalyst component [A], the zirconium compound (b) having the above-described group having a conjugated π electron as a ligand is treated with an organoaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride and methylaluminum dichloride in advance. May be done.

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

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. Further, it may be a halogenated aluminoxane in which a part of R is substituted with a halogen atom such as chlorine or bromine and the halogen content is 40% by weight or less, preferably 30% or less. 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, in addition to the following trialkylaluminum, an organometallic compound component such as a halogen-containing organoaluminum compound or an organomagnesium compound may be present.

Examples of the solvent for aluminoxane include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, xylene and chlorobenzene.

As an insoluble or sparingly soluble solvent for aluminoxane, for example, pentane, hexane, decane, dodecane, kerosene,
Mention may be made of straight-chain or branched aliphatic hydrocarbons such as cyclohexane and alicyclic hydrocarbons such as cyclohexane, norbornane, ethylcyclohexane. As the insoluble or sparingly soluble solvent for aluminoxane, it is preferable to use a solvent having a boiling point higher than that of the solvent used for obtaining the solution of aluminoxane.

The olefin polymerization method of the present invention comprises [A] a magnesium compound (a) and a zirconium compound (b) having a group having a conjugated π electron as a ligand, and contains magnesium, zirconium and halogen as essential components. It is characterized in that olefin is polymerized in the presence of a catalyst formed from a highly active zirconium solid catalyst component and [B] aluminoxane catalyst component.

In the above catalyst, the atomic ratio of zirconium to magnesium (Zr / Mg) is 0.0001 to 1, preferably 0.000.
It is 5 to 0.5, and more preferably 0.001 to 0.1. When the atomic ratio (Zr / Mg) is greater than 1, the polymerization activity per Zr atom is greatly reduced, while when the atomic ratio (Zr / Mg) is less than 0.0001, the polymerization activity per catalyst or per Zr is reduced. To do.

In the above catalyst, the atomic ratio of halogen to magnesium (X / Mg) is 0.1 to 10, preferably 0.5 to 5,
More preferably, it is 1 to 3. The atomic ratio (X / Mg) is
If it is larger than 10, the atomic ratio (X / Mg is smaller than 0.1 also lowers the polymerization activity.

In the above catalyst, the atomic ratio of aluminum to zirconium (Al / Zr) is 5 to 2000, preferably 10 to 1000, more preferably 20 to 500. When the atomic ratio (Al / Zr) is larger than 2000, the polymerization activity per aluminoxane is lowered, and when the atomic ratio (Al / Zr) is smaller than 5, the polymerization activity is lowered.

The average particle size of the above catalyst is 2 to 200 μm, preferably 1
It is 0 to 150 μm, more preferably 20 to 100 μm. When the average particle size is less than 2 μm, the amount of finely divided polymer in the polymer obtained by the method for polymerizing olefin of the present invention is significantly increased, and the bulk specific gravity is not large enough to satisfy the powder property. I can't get a coalescence. On the other hand, 200μ
If it is larger than m, the production of coarse particles increases, and a polymer having excellent powder properties cannot be obtained.

The catalyst component for olefin polymerization of the present invention can be produced, for example, by the following method.

For example the magnesium compound (a), specific to the general formula ^{_{M a Mg b ▲ R 'c}} ▼ halogenated silicon compound which will be described later as needed magnesium compound in a liquid state and represented by X _d described above, the zirconium described above method of manufacturing a solid catalyst component by contacting the reaction in the presence of a compound or a magnesium compound (a), a liquid state and specifically represented by the general formula ^{_{M a Mg b ▲ R 'c}} ▼ X d described above, The method for producing the solid catalyst component can be exemplified by bringing the above-mentioned zirconium compound into contact with the fine-particle magnesium compound obtained by the catalytic reaction of the magnesium compound of 1) and the later-described silicon halide compound.

As the above-mentioned halogenated silicon compound, a compound represented by the general formula: ▲ R ³ _a ▼ H _b SiX _c [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]] can be exemplified.

An example of such a halogenated silicon compound is HSiC.
l ₃ , HSiCl ₃ , HSiCl ₂ C ₂ H ₅ , HSiCl ₂ n-C ₃ H ₇ , HSiCl ₂
iso-C ₃ H ₇ , HSiCl ₂ n-C ₄ H ₉ , HSiSiCl ₂ n-C ₆ H ₁₃ , H
SiCl ₂ CH = CH ₂ , HSiCl ₂ C ₆ H ₅ , HSiCl (CH ₃ ) ₂ , HSiClC
H ₃ (C ₂ H ₅ ), H ₂ SiClC ₂ H ₅ , HSiCl ₂ CH ₂ CH = CH ₂ , Si
Cl ₄ , CH ₃ SiCl ₃ , C ₂ H ₅ SiCl ₃ , CH ₂ = CH-SiCl ₃ , C ₆ H
₅ SiCl _3, and the like can be exemplified _{(CH 3) 2 SiCl 2,} MeOSiCl 3, C 2 H 5 OSiCl 3.

The solid catalyst component may contain a component such as an electron donor as an optional component or may be supplied to the polymerization reaction system. As the electron donor, oxygen-containing compounds such as carboxylic acids, esters, ethers, ketones, aldehydes, alcohols, phenols, acid amides, compounds containing metal atom-O-C bond such as aluminum and silicon , Nitriles, amines, phosphines, and the like. For example, the content ratio of the electron donor is usually in the range of 0 to 1 mol, preferably 0.1 to 0.6 mol per 1 gram atom of the zirconium.

INDUSTRIAL APPLICABILITY The polymerization method of the present invention is effective for producing olefin polymers, particularly ethylene polymers and ethylene / α-olefin copolymers. Examples of olefins that can be polymerized by the polymerization method of the present invention include those having 2 to 20 carbon atoms.
Α-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 copolymerization of ethylene with α-olefin having 3 to 10 carbon atoms is preferable.

In the polymerization method of the present invention, the polymerization of olefin is usually
It is 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,
Aliphatic hydrocarbons such as pentane, hexane, octane, decane, dodecane, hexadecane and ontadecane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane, petroleum fractions such as kerosene and light oil Is mentioned.

In the polymerization method of the present invention, the ratio of the transition metal compound 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 defined as the concentration of the transition metal atom in the polymerization reaction system. It is usually in the range of 10 ^-8 to 10 ^-2 gram atom / l, preferably 10 ^-7 to 10 ^-3 gram atom / l.

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

When the polymerization method of the present invention 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
It is in the range of 200 ° C, preferably 0 to 170 ° C.

When the polymerization method of the present invention 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 atmospheric pressure to 100 kg / cm ² , preferably 2 to 50 kg / cm ² , and the polymerization can be carried out by any of batch, semi-continuous and continuous methods. .

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

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

The prepolymerization temperature is in the range of -20 ° C to 70 ° C, preferably -10 ° C to 60 ° C, more preferably 0 ° C to 50 ° C.

The treatment may be carried out in a batch system or a continuous system, and may be carried out 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 0.5
It is preferable to control the amount so that a prepolymer of 20 dl / g can be produced.

The prepolymerization is carried out without solvent or in an inert hydrocarbon medium. From the viewpoint of operability, prepolymerization in an inert hydrocarbon medium is preferred. Examples of the inert hydrocarbon medium used in the prepolymerization include the above-mentioned solvents as the insoluble or sparingly soluble solvent of aluminoxane.

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

[Effect of the Invention] According to the olefin polymerization method of the present invention, the bulk specific gravity is large, the particle size is uniform, the fine powder is small, and the molecular weight distribution is narrow.
Further, in the case of copolymerization, an olefin polymer or copolymer having a narrow composition distribution can be obtained.

[Preparation of Methylaminooxane] Al ₂ (SO ₄ ) ₃ · 14H ₂ O 37 g and toluene 125 ml were placed in a 400 ml glass flask equipped with a stirrer, which had been sufficiently replaced with nitrogen.
After cooling to 0 ° C, 125 ml of toluene containing 50 ml of trimethylaluminum was added dropwise over 1 hour. Then, the temperature was raised to 40 ° C. over 2 hours, 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 887.
Therefore, the degree of polymerization of this methylaluminoxane is
It 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 liquid containing gC195 mM
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 component was spherical particles having a diameter of about 50 μm.

[Preliminary Polymerization] 100 ml of purified n- in a 400 ml reactor equipped with a stirrer under a nitrogen atmosphere.
Decane, methylaluminoxane equivalent to 20 milliatoms in terms of aluminum atoms, and 0.1 mM of Zr equivalent to the above solid catalyst were added, and ethylene was added at a rate of 4 Nl / hr.
Supplied for hours. 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 Next, the temperature of the autoclave was lowered to 75 ° C., and after replacing the inside of the autoclave with ethylene, methylaluminoxane corresponding to 10 mmol in terms of aluminum atom and 0.02 mmol in terms of zirconium atom of the solid catalyst component subjected to the preliminary polymerization were added. The autoclave as a closed system and hydrogen
Nml was added and the internal pressure of the autoclave was 8 kg / c with ethylene.
Pressurized to m ² G. Increase the stirring speed to 300 rpm,
Polymerization was carried out at 80 ° C for 1 hour.

After the completion of the assembly, the entire amount of the polymer and sodium chloride in the autoclave was taken out and put into about 1 water. About 5
By stirring for 1 minute, almost all the 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 obtained polymer yield was 83 g, MFR was 2.4 dg / min, and apparent bulk density was 0.4.
It was 1 g / ml.

Example 2 [Preparation of solid catalyst component] 22.2 ml in a 400 ml glass reactor sufficiently replaced with nitrogen.
N-BuMgC1 was added to this mixture after adding 140 ml of a toluene solution containing silicon tetrachloride of No. 1 and 5.7 mM biscyclopentadienyl zirconium chloride.
100 ml of a dibutyl ether solution containing 95 mM 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.

Preliminary polymerization and ethylene polymerization were carried out in the same manner as in Example 1 below.

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 gEt 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, 20
It contained magnesium by weight and 59% by weight chlorine. The catalyst particles were spherical particles having a diameter of about 30 μm.

Then, prepolymerization and ethylene polymerization were carried out in the same manner as in Example 1.

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 gEt 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 portion was separated by filtration and washed once with about 200 ml of purified hexane. The resulting solid catalyst component contained 0.51% by weight of Zr, 19
It contained wt.% Magnesium and 61 wt.% Chlorine. The catalyst particles were spherical particles having a diameter of about 13 μm.

Then, prepolymerization and ethylene polymerization were carried out in the same manner as in Example 1.

Example-5 [Preparation of solid catalyst component] n-BnM was added to a 400 ml glass reactor sufficiently replaced with nitrogen.
After adding 100 ml of dibutyl ether solution containing 195 mM gC
The temperature was raised to 50 ° C., and 70 ml of a toluene solution containing 22.2 ml of silicon tetrachloride was added dropwise 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 excess, resuspended in about 200 ml of purified n-decane, and then returned to the reactor.

A solution of 1.2-dichloroethane containing 5.7 mM biscyclopentadienyl zirconium dichloride was then added to the reactor.
After adding 10 ml and carrying out a reaction at 60 ° C. for 1 hour, the solid portion was separated by filtration and washed once with about 200 ml of purified hexane. 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.

Then, prepolymerization and ethylene polymerization were carried out in the same manner as in Example 1.

The results are shown in Table-1.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing steps for producing a catalyst according to the present invention.

Claims (1)

[Claims] 1. An [A] organomagnesium compound (a),
General formula ▲ R ³ _a ▼ H _b SiX _c [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]] and a halogenated silicon compound represented by the following 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 or a substituted product thereof, an aryl group, an alkyl group, a cycloalkyl group, an aralkyl group, a halogen atom, hydrogen, OR
^a , SR ^b , NR ^c ₂ or PR ^d ₂ , wherein R ^a , R ^b , R ^c and R ^d are each a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or a silyl group. Yes,
Two R ^c and R ^d can also be joined to form a ring. k ≧ 1 and k + l + m + n = 4. When R ² is a cycloalkadienyl group or a substituted product thereof, R ^2
1 and R ² may be bonded by a lower alkylene group. ] A high activity zirconium solid catalyst component formed from the zirconium compound (b) represented by the formula (b), containing magnesium, zirconium and halogen as essential components, and [B] an aluminoxane catalyst component, The atomic ratio of zirconium to magnesium (Zr / Mg) is 0.0001 to 1, the atomic ratio of halogen to magnesium (X / Mg) is 0.1 to 10 and the atomic ratio of aluminum to zirconium (Al / Zr) is in the range of 5 to 2000. A method for polymerizing olefin, which comprises polymerizing olefin in the presence of a catalyst having an average particle size of 2 to 200 μm.