JPH04100808A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To produce a polyolefin having a narrow molecular weight distribution, low stickiness and high bulk density by polymerizing an olefin in the presence of a catalyst comprising a specified solid catalyst component and a modified organoaluminum compound. CONSTITUTION:A polyolefin is obtained by (co)polymerizing an olefin in the presence of a catalyst comprising a solid catalyst prepared by bringing a porous inorganic oxide (having a surface area of most suitably 150-350m<2>/g and a pore volume of desirably 1.0-2.5cm<3>/g, e.g. alumina or silica), an alkoxysilane compound of formula I (wherein R is a 1-24 C hydrocarbon group; X is halogen and 0<n<=3) and an organometallic compound of formula II (wherein M is a group TV transition metal; R<1> is cyclopentadienyl, indenyl, 7-24 C aralkyl or the like; X is halogen, H or a 1-24 C hydrocarbon group; 2<=p<=4; 0<=r<=2; and p+r=4) into contact with each other and an Al-O-Al bond-containing modified organoaluminum compound prepared by reacting an organoaluminum compound with water.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polyolefin using a specific catalyst. More specifically, the present invention is a method for producing polyolefins with narrow molecular weight distribution or composition distribution, low stickiness, and high bulk density by polymerizing or copolymerizing olefins in the presence of a specific highly active catalyst. Regarding.

[Prior art] In recent years, a catalyst system consisting of a metallocene component and methyl ammoxane has been used for the homopolymerization of ethylene and for the polymerization of ethylene and α-
It is attracting attention in the copolymerization of olefins. This catalyst system has relatively high activity per transition metal, and the resulting polymer has a narrow molecular weight distribution, a relatively narrow composition distribution for ethylene/α-olefin copolymers, and low stickiness. There is.

For example, JP-A-58-19309 describes the above catalyst system. Is this catalyst system a homogeneous polymerization catalyst?
When this is used for gas phase polymerization, a block polymer is generated in the polymerization reactor and this adheres to the walls of the polymerization reactor or the stirrer, making continuous operation almost impossible. There was a point.

In order to solve this problem, a method has been proposed in which the catalyst component is supported on an inorganic oxide carrier (Japanese Unexamined Patent Publication No. 6
No. 1-296008, JP-A-61-108610).

However, even with the proposed method, the catalytic activity is still insufficient, and in order to improve this, a method of additionally supplying an activator compound as a co-catalyst has been proposed (Japanese Patent Laid-Open No. 63-51
No. 407, JP-A No. 1-101315).

[Problem to be solved by the invention H] However, although these conventional techniques can improve the catalytic activity per transition metal, the bulk density of the obtained polymer is still insufficient, and the particle shape is not satisfactory. It wasn't something.

In particular, in polymerization under gas phase conditions in the absence of a substantial solvent, good polymer particle shape and high bulk density are important factors during continuous operation, and it is desirable to develop a method that can meet these requirements. It was rare.

[Means for Solving the Problem] As a result of intensive studies to solve the above-mentioned drawbacks and demands, the present inventors finally found a new method for producing polyolefin that meets the intended purpose, and arrived at the present invention. . That is, the method of the present invention comprises [I] (i) porous inorganic oxide, (if) general formula Al(OR) indicates a halogen atom, n is Ow
(n≦3), and (lii) a compound represented by the general formula R' MX (wherein M represents a transition metal element of Group I of the periodic table, R1 is a cyclopentadienyl group, a substituted cyclo It represents a pentagenyl group, an indenyl group, a substituted indenyl group, or an aralkyl group having 7 to 24 carbon atoms, R1 may be bonded to each other via an alkylene group having 2 to 8 carbon atoms, and X is a halogen atom or a hydrogen atom. or a hydrocarbon residue having 1 to 24 carbon atoms, and p and r are 2≦p
≦4.0≦r≦2 and p + r-4) A solid catalyst component obtained by contacting each other with [11] an organoaluminum compound and water It is characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst comprising a modified organoaluminum compound containing a ^l-0-Al bond obtained by .

The novel polymerization catalyst used in the method of the present invention has an extremely high activity per transition metal and can be continuously polymerized.Moreover, the resulting polyolefin has good particle shape and high bulk density. Polymerization products produced under gas phase polymerization conditions in the absence of a solvent also have the above-mentioned features. In addition, the polyolefin obtained by the method of the present invention, particularly the copolymer of ethylene and α-olefin, not only has excellent features such as a narrow composition distribution and extremely low surface tackiness. ,
It has features such as a large die swell ratio.

The present invention will be explained in more detail below.

In the polyolefin production method of the present invention, a specific catalyst consisting of the above-mentioned "solid catalyst component" and "modified organoaluminum compound" is used, and first, these catalyst components will be explained in detail.

[1] Solid catalyst component As described above, the solid catalyst component used in the present invention is (D
It is obtained by bringing a porous inorganic oxide, (ii) a compound represented by Al(OR)nXa-n, and a compound represented by (111) R' MX into contact with each other.

The porous inorganic oxide used in the present invention is usually
Surface area 50-1000 i/g 1 preferably io.

~500 go/g, more preferably 150-350 go/g
g, and the pore volume is usually 0.5 to 3. OcI′/g
An inorganic oxide having a porosity of 1.0 to 25 α''/g is desirable. Examples of such porous inorganic oxides include silica, alumina, silica/alumina, titania, zirconia, and thoria. Alternatively, mixtures thereof may be mentioned, and silica and alumina are particularly preferred. Commercially available commercial products of these porous inorganic oxides may be used as they are in the preparation of the catalyst of the present invention, but they may be heat-treated in an inert gas in advance. The heating or drying conditions at this time are not particularly limited, but are usually 150 to 800°C, preferably 200 to 60°C.
A temperature range of 0° C. is desirable, and the heating or drying time is usually 0.5 to IO hours, preferably 2 to 5 hours.

General formula Al(OR)
- 3-n 24, preferably an alkyl group of 1 to 12, X represents a l\logen atom, and n is 0<y1≦3) Examples of the compound include trimethoxyaluminum, dimethoxymonochloroaluminum, , methoxydichloroaluminum, triethoxyaluminum, jetoxymonochloraluminum, ethoxydichloroaluminum,
Triisopropoxyaluminum, diisopropoxymonochloraluminum, isopropoxydichloroaluminum, tri-n-butoxyaluminum, dibutoxymonochloraluminum, n-butoxydichloroaluminum, tri5ec-butoxyaluminum, di5e
e-Butoxymonochloroaluminum, 5eC-butoxydichloroaluminum, tripentoxyaluminum, jetoxymonochloraluminum, pentoxydichloroaluminum, triphenoxyaluminum, diphenoxymonochloroaluminum, monophenoxydichloroaluminum, tritolyloxyaluminum, ditolyloxy Examples include monochloroaluminum, tolyloxydichloroaluminum, tribenzyloxyaluminum, etc., and preferably triethoxyaluminum,
Examples include triisopropoxyaluminum and tri-n-butoxyaluminum.

In the compound represented by the general formula R' MX, r M in the formula is a transition element of group Ⅰ of the periodic table, and R1 is a cyclopentagenyl group, a substituted cyclopentagenyl group, an indenyl group, a substituted indenyl group. or an aralkyl group having 7 to 24 carbon atoms, preferably 7 to 13 carbon atoms, R1 may be bonded to each other through an alkylene group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, and X is chlorine, bromine or A halogen atom such as fluorine, a hydrogen atom, or a carbon number of 1 to 24, preferably 1
~12 hydrocarbon residues, p, q and r are 2≦p
≦4゜0≦r≦2. This is a number that satisfies p+r-4.

More specifically, when R1 in the formula is a substituted cyclopentadienyl group or a substituted indenyl group, the substituent includes an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, etc. or a hydrogen atom, and R
As the aralkyl group of 1, benzyl group, phenethyl group, benzhydryl group, trityl group, phenylbutyl group,
Examples include phenylpropyl group.

When there is an alkylene group that connects R1 to each other, the alkylene group usually connects such a ring when R1 is a cyclopentagenyl group, a substituted cyclopentagenyl group, an indenyl group, or a substituted indenyl group. Also, X
Hydrocarbon residues include alkyl groups such as methyl, ethyl and propyl groups, aryl groups such as phenyl and tolyl groups, benzyl groups, phenethyl groups, benzhydryl groups,
Examples include aralkyl groups such as trityl, phenylbutyl and phenylpropyl groups, alkoxy groups such as ethoxy, propoxy and phenoxy groups, and aryloxy groups. Moreover, in the case of r-2, X may be the same or different.

Specific examples of compounds represented by the general formula R' MX and r include bis(cyclopentagenyl)dichlorotitanium, bis(cyclopentagenyl)methylchlorotitanium, bis(cyclopentagenyl)dimethyltitanium, Bis(cyclopentadienyl)ethoxychlorotitanium, bis(cyclopentadienyl)propoquine chlorotitanium, bis(cyclopentadienyl)phenoxychlorotitanium, bis(cyclopentadienyl)
Propylchlorotitanium, bis(cyclopentagenyl)diphenyltitanium, bis(cyclopentagenyl)ditolyltitanium, bis(cyclopentagenyl)titaniumbenzyl, bis(cyclopentagenyl)
Titanium monochloromonohalide, bis(methylcyclopentadienyl)dimethyltitanium, tetracyclopentadienyltitanium, bis(indenyl)dichlorotitanium, bis(indenyl)dimethyltitanium, ethylenebis(indenyl)titanium dichloride,
Ethylene bis(tetrahydroindenyl) titanium dichloride, tetraneopentyl titanium, tetraneophyl titanium, tetrabenzyl titanium, bis(
cyclopentagenyl) dichlorozirconium, bis(
cyclopentagenyl) methylchlorozirconium, bis(cyclopentagenyl) dimethylzirconium, bis(indenyl) dimethylzirconium, bis(indenyl) dichlorozirconium, ethylenebis(indenyl)dichlorozirconium, ethylenebis(tetrahydroindenyl)dichlorozirconium , bis(methylcyclopentadienyl) dimethylzirconium, bis(cyclopentajenyl)zirconium monochloromonohydride, bis(cyclopentajenyl)zirconium dibenzyl, tetracyclopentajenylzirconium, tetrabenzylzirconium, bis(cyclopentajenyl)zirconium genyl)ethoxychlorozirconium, bis(cyclopentagenyl)propoxychlorozirconium, bis(
cyclopentagenyl) phenoxychlorozirconium, bis(cyclopentagenyl)propylchlorozirconium, bis(cyclopentagenyl)diphenylzirconium, bis(cyclopentagenyl)ditolylzirconium, bis(cyclopentagenyl)monomethylmono Zirconium halide, bis(cyclopentagenyl) monoethyl monochloride zirconium, bis(cyclopentagenyl) monoethyl monochloride zirconium, tetraneopentyl zirconium, tetraneophyl zirconium, bis(cyclopentagenyl) dimethyl hafnium, bis (cyclopentagenyl)dichlorohafnium, bis(cyclopentagenyl)methylchlorohafnium, bis(cyclopentagenyl)ethylchlorohafnium, bis(cyclopentagenyl)propylchlorohafnium, bis(cyclopentagenyl)phenyl Chlorhafnium, bis(cyclopentagenyl)
Diphenylhafnium, bis(cyclopentagenyl)
Ditolyl hafnium, bis(cyclopentagenyl) monochloromonohalide hafnium, bis(cyclopentagenyl) monomethyl monohalide hafnium, bis(
Examples thereof include bis(cyclopentagenyl) dibenzyl hafnium, ethylene bis(indenyl) dichlorohafnium, ethylene bis(tetrahydroindenyl) dichlorohafnium, tetraneopentyl hafnium, and tetraneophyl hafnium. ) dichlorotitanium, bis(cyclopentagenyl) dimethyltitanium, bis(cyclopentagenyl) dichlorozirconium, bis(cyclopentagenyl) dimethylzirconium, bis(cyclopentagenyl) dichlorohafnium, bis(cyclopentagenyl) ) dimethyl hafnium.

Of course, two or more of these compounds can also be used in combination.

The solid catalyst component used in the present invention consists of the three components mentioned above, namely (i) porous inorganic oxide, (ii) general formula Al(O
R). A compound represented by X3-0 and (Ili) -
It can be obtained by bringing compounds represented by the general formula R' MX into contact with each other.

The order of contact can be arbitrarily selected, but generally components (i) to (iii) are contacted simultaneously, component (i) is contacted with component (i), and component (i) is contacted with component (i).
Either a procedure of bringing f) into contact and then contacting component (jii) or a procedure of bringing component (i) and component (jii) into contact and then contacting component (ji) is adopted.

Among them, after bringing component (i) and component (i i) into contact,
A procedure of contacting component (iii) is preferred. In addition, the contact method can be arbitrarily selected. For example, inert hydrocarbons such as heptane, hexane, pentane, nonane, benzene, toluene, etc., various alcohols, phenols, ethers, ketones, An organic compound selected from esters, amines, nitriles, halogen-containing compounds such as 1.2 dichloroethane, tetrachloroethane, ethylidene chloride, carbon tetrachloride, chloroform, chlorobenzene, dichlorobenzene, etc., or mixtures thereof. In a solvent, usually 0 to 200°C,
Preferably, a method can be employed in which the organic solvent is removed after contacting at a temperature of 50 to 100°C for usually 5 minutes to 30 hours, preferably 30 minutes to 10 hours.

In producing the solid catalyst component in the present invention, component (i) and component (if) are brought into contact as described above, and then component (
It is particularly preferable to contact iii), which will be explained in more detail. Components (i) and (if) may be brought into contact by dissolving component (ii) in advance in the solvent and impregnating component (j) with the solution, or by dissolving component (i) and component (if) in the solvent. ii) can be added at the same time. In any case, component (i) and component (j
i) is usually 0 to 200" C1, preferably 20 to 1
At a temperature of 00℃, usually 5 minutes to 30 hours, preferably 30 hours.
It is desirable that the contact be carried out for 20 minutes to 20 hours. Ingredients (if
) in a solvent is not particularly limited, but it is usually 0.1 to 5 mol, preferably 0.5 to 1.5 mol per liter of solvent. In addition, the usage ratio of component (i) and component (ji) is usually component (+)
It is preferable to select the component (N) so that it is contained in an amount of 0.01 to 5 mmol, preferably 0.1 to 1.5 mmol, per 1 g. In addition, upon contact with component (+), at least a portion of component (ii) is converted to component (i).
It is presumed that this will be the reaction.

After adding the desired amount of component (ji) to component (+),
This is preferably washed with a similar solvent and then brought into contact with component (iiD). In this case, component (iii) is
> may be brought into contact with the component (fil) after drying, or may be brought into contact with the component (jjj) as a dispersion without any drying.

The conditions for contacting the component (jij) are also not particularly limited, but - the inside of the shell is heated in the organic solvent at a temperature of usually 20 to 200°C, preferably 50 to 100°C, usually for 5 minutes to 30 hours. Examples of suitable methods include a method in which the organic solvent is removed after contacting the organic solvent with stirring, preferably for 30 minutes to 10 hours.

The abundance ratio of each component in the solid catalyst component of the present invention is as follows: per Ig of component (1) containing component (11), component (j
l) is usually 0. 1-5 mmol of O, preferably 0.1-
It is desirable that the content is 1.5 mmol, and
Component (iii) is usually 0.1 to 10% by weight as a transition metal element in the solid catalyst component obtained by contacting each component.
, preferably in a range of 0.5 to 8.0% by weight.

[11] Modified organoaluminum compound The modified organoaluminum compound used in the present invention is a reaction product of an organoaluminum compound and water, and contains at least ^1-0-^1 bonds in the molecule, The number of bonds is 1 to 10o, preferably 1 to 50
It is individual. The reaction between organoaluminium and water is usually carried out in an inert hydrocarbon.

Inert hydrocarbons include pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene,
Examples include aliphatic, alicyclic, and aromatic hydrocarbons such as toluene and xylene, and aliphatic and aromatic hydrocarbons are preferred.

The organoaluminum compound has the general formula RnAlX
(R represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12-n, X represents a hydrogen atom or a halogen atom, and n represents 1≦n≦ 3), and trialkylaluminum is preferably used.

The alkyl group of trialkylaluminum includes methyl group, ethyl group, propyl group, isopropyl group, butyl group,
Isobutyl group, pentyl group, hexyl group, octyl group,
Examples include decyl group and dodecyl group, but methyl group is particularly preferred.

Ratio of water and organoaluminum compound (water/A1 molar ratio)
is 0.25/1 to 1.2/1, especially 0.5/1 to 1/
1 is preferred, and the reaction temperature is usually -70 to 100°C,
Preferably it is -20 to 20°C. Reaction time is usually 5~
48 hours, preferably 10 to 24 hours. The reaction can also be carried out using crystal water of copper sulfate hydrate, aluminum sulfate hydrate, etc. as the water required for the reaction.

Olefin Polymerization or Copolymerization The present invention is for producing an olefin polymer or copolymer in the presence of a catalyst consisting of the solid catalyst component described above and a modified organoaluminum compound. The solid catalyst component and the modified organoaluminum can be supplied separately into the polymerization system, or they may be brought into contact with each other beforehand and then supplied into the polymerization system.

The usage ratio of the solid catalyst component and the modified organoaluminum compound is 1 to 1 in terms of the atomic ratio of aluminum in the modified organoaluminum compound to the transition metal in the solid catalyst component.
00,000, preferably in the range of 5 to 1,000.

The method of the present invention is applicable to the polymerization of all off-ynes that can be polymerized with Ziegler catalysts, and α-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, butene-1, hexene-1,4- Homopolymerization of α-olefins such as methylpentene-1, ethylene and propylene, ethylene and butene-11, ethylene and hexene-1, ethylene and 4-methylpentene-1, etc., and ethylene with 3 to 12 carbon atoms, preferably 3 Copolymerization of α-olefins 1 to 6, copolymerization of propylene and butene-1, copolymerization of ethylene and two or more other α-olefins, etc. are preferably used.

Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 1,4-hexadiene, ethylidenenorbornene, dicyclopentadiene, and the like.

The comonomer content during copolymerization can be selected arbitrarily, but for example, ethylene and carbon atoms of 3 to 12
In the case of copolymerization with α-olefin, the α-olefin content of the ethylene/α-olefin copolymer is 40 mol%.
or less, preferably 30 mol% or less, more preferably 20
It is desirable that it be less than mol%.

Polymerization of olefins using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization.

In particular, the catalyst of the present invention can be suitably used for gas phase polymerization. All polymerization reactions are carried out substantially in the absence of oxygen, water, etc., and in the presence or absence of inert hydrocarbons. In its absence, a fluidized bed gas phase reaction method in which polymerization is carried out while keeping the produced polymer in a fluidized state and a stirring gas phase reaction method can be applied, and both continuous and batch methods can be applied. Can be applied. The polymerization conditions at this time are that the temperature is usually 20 to 200°C, preferably 50 to 100°C, and the pressure is normal pressure to 70kg/c7G.

Preferably, the pressure is normal pressure to 20 kg/cjG, and the time is not particularly limited, but the residence time is usually 5 minutes to 10 hours,
Preferably it is carried out for 10 minutes to 5 hours. Although the molecular weight of the produced polymer or copolymer can be controlled to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any hindrance.

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to the following Examples.

The physical properties of the polymers obtained in Examples and Comparative Examples were measured by the following method.

Melt Index (M I ) Measured based on ASTM D 1238757T. At that time, the conditions were 190'c, 2.16kg load M l
2'6, Iokg load is expressed as 1vl) IQ.

Dice swell ratio (DSR) It is defined by the following equation using an Ml measuring device.

Orifice diameter (2.1mm) density Compliant with ASTM D 1505-68.

Melting point measurement by DSC: Seiko Electronics DSC-20 type melting point measuring device was used (sample amount 5i+g).

The measurement method is as follows. The temperature was maintained at 180'C for 3 minutes, then cooled to 0°C at a rate of 10°C/min, held at 0°C for 10 minutes, and then raised at a rate of 10°C/min.

Preparation of methylalumoxane (MAO) 13 g of copper sulfate pentahydrate was added to 300 m1 with an electromagnetic induction stirrer.
The mixture was placed in a third flask, and 50 ml of toluene was added thereto for suspension. Then, 1 m of tolumethylaluminum was added at 0°C.
■Drop 150ml of solution of/m+ over 2 hours,
After the dropwise addition was completed, the temperature was raised to 25°C, and the reaction was continued at that temperature for 24 hours.

The reaction product was then filtered to remove toluene from the liquid containing the reaction product to obtain 4 g of white crystalline methylalumoxane.

Preparation of Tetrabenzylzirconium 500 ml of a diethyl ether solution containing 70 g of benzylmagnesium chloride is placed in a three-bottle flask equipped with an electromagnetic induction stirrer at 0° C. under a nitrogen atmosphere.

Next, 30 g of zirconium tetrachloride was added over 30 minutes under a nitrogen atmosphere. The mixture was stirred for 2 hours, during which time the temperature was allowed to rise to room temperature.

Then, 300 ml of decalin was added and stirred at room temperature for 1 hour. The produced magnesium chloride was separated, and the resulting decalin solution was heated to 50° C. and ether was removed while blowing nitrogen gas. 32 g of tetrabenzylzirconium was obtained from the obtained decalin solution.

Solid catalyst component A: 20 g of silica (Fuji Davison grade #952) calcined at 460°C was placed in a
0 ml in a three-bottle flask, and add 100 g of aluminum isopropylate Al (O4Prh 2.Og).
A solution of m1 in n-hexane was added at room temperature. Then, the temperature was raised to 50°C under a nitrogen atmosphere, and the mixture was stirred for 2 hours. After stirring, the supernatant was removed, washed with 100 ml of n-hexane, and dried with nitrogen blow.

Next, bis(cyclopentadienyl)dichloroethane (hereinafter Cp2TiC) was added to 70ml of 1,2-dichloroethane.
A solution in which 1.2 g (abbreviated as 12) was dissolved was added to the above dried product at room temperature over nitrogen, and then after stirring at room temperature for 2 hours,
Solid catalyst component A was obtained by removing 1.2 dichlorotitanium using nitrogen blowing at 50°C. This solid catalyst component A is 1.03
It contained vt% of Ti.

Solid catalyst component B Same as solid catalyst component A except that the amount of aluminum isopropylene (OiPr)3 dissolved in 100 ml of n-hexane was increased from 2.0 g to 4.0 g. Solid catalyst component B was prepared. This solid catalyst component B
contained 0.95 wt% Ti.

Solid catalyst component C In the preparation of solid catalyst component A, instead of a solution of 1.2 g of CI)2 TlCI2 dissolved in 70 ml of 1,2-dichloroethane, bis(cyclopentadienyl) dichlorozirconium ( Below CI
)2 ZrCl2) Solid catalyst component C was prepared in the same manner as solid catalyst component A, except that a solution in which 0.73 g of ZrCl2 was dissolved was used. This solid catalyst component C is 0.99v
It contained t% of Zr.

Solid Catalyst Component In the preparation of solid catalyst component B, 0.8 g of Cp2 TiCl2 was dissolved in 100 ml of toluene instead of a solution of 1.2 g Cp2TiCl2 dissolved in 70 ml 1,2-dichloroethane.
A solid catalyst component was prepared in the same manner as solid catalyst component B except that a solution in which p2 ZrCl2 was dissolved was used. This solid catalyst component is 1. It contained Ovt% of Z''.

Solid catalyst component E In the preparation of solid catalyst component A, aluminum secondary butoxide Al (Osec
Bu) 32.5 g was used, and cI) 2TiC1z
Except for increasing the usage amount from 1.2g to 2.6g,
Solid catalyst component E was prepared in the same manner as solid catalyst component A. This solid catalyst component E contained 2.0 wt% of Tj.

Solid catalyst component F In the preparation of solid catalyst component A, 460°C calcined silica (
#952) was replaced with 600°C combustion silica (#952), and 70ml of 1,2-dichloroethane was added with 1.
A solid catalyst component was used in the same manner as solid catalyst component A, except that a solution of 1 g of bis(cyclopentagenyl)dimethyltitanium dissolved in 100 ml of toluene was used instead of a solution of 2 g of Cp2TiCl2 dissolved therein. F was prepared. This solid catalyst component F contained 1.03 νt% of Ti.

Solid catalyst component G In the preparation of solid catalyst component F, 0.65 g of bis(cyclopentadienyl)dimethylzirconium was added to 100 ml of toluene instead of a solution of 1 g of bis(cyclopentadienyl)dimethyltitanium dissolved in 100 ml of toluene.
Solid catalyst component G was prepared in the same manner as solid catalyst component F, except that a solution in which . This solid catalyst component G contained 1 Ovt% of Zr.

Solid catalyst component H In the preparation of solid catalyst component A, Al (OiPr)3
instead of diisopropoquine aluminum chloride A
Solid catalyst component H was prepared in the same manner as solid catalyst component A, except that 1.8 g of l(OiPr)2Cl was used.

This solid catalyst component H contained 1.05 wt% of Ti.

Solid catalyst component I In the preparation of solid catalyst component A, 50 ml of toluene and 9250 ml of Deca instead of a solution of 1.2 g of Cp2TiCl2 dissolved in 70 ml of 1,2-dichloroethane
1 mixed solvent with tetrabenzylzirconium (hereinafter (Bz
) a A solution in which 1.2 g of (abbreviated as Zr) was dissolved was used. Solid catalyst component I was obtained by removing the toluene-proline mixed solvent. This solid catalyst component I contains Zr (1,98
It contained vt%.

Solid catalyst component J In the preparation of solid catalyst component A, bis(cyclopentadienyl) dichlorohafnium (hereinafter abbreviated as Cp2 Hfeb) was added to 70 ml of toluene instead of a solution of Cp2 TiCl2 dissolved in 70 ml of 1,2-dichloroethane. A solution containing 0.5g was used. Solid catalyst component J was obtained by removing toluene. This solid catalyst component J contained 0.99 wt% and 9 wt% of Hf.

In preparing the solid catalyst component, bis(indenyl) dichlorotitanium (hereinafter abbreviated as (Ind) 2 TiCl2) was added to 70 ml of toluene instead of a solution of Cp2 TiCl2 dissolved in 70 ml of 1,2-dichloroethane. A solution in which 1.75g of was dissolved was used. Solid catalyst component K was obtained by removing toluene. This solid catalyst component contained 1 wt% of Ti.

25 1/2 inch diameter stainless steel poles with solid catalyst component
Al (OiPrh lOg and Cp2 Ti
55 g of C120 was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours. 1 g of the obtained solid powder contained 1.0 νt% titanium.

Solid catalyst component M: 20 g of silica (Fuji Davison grade #952) calcined at 460°C was placed in a 300-meter tube equipped with an electromagnetic induction stirrer
A solution of 1.1 g of Cp2TiCl2 in 70 ml of 1,2-dichloroethane was added at room temperature over nitrogen. After stirring at room temperature for 2 hours, 12-dichloroethane was removed by nitrogen blowing at 50° C. to obtain solid catalyst component M. This solid catalyst component M is 1
．． It contained 0 wt% Ti.

Example 1 A stainless steel autoclave with a capacity of 3 mm equipped with a stirrer was purged with nitrogen, 20 g of polyethylene pellets were added, and 100 mm of solid catalyst component A and 3.9 ml of methyl ammoxane 2,7 aa+ol/m+ solution were added. The mixture was heated to 60° C. with stirring. Then ethylene and butene
1 mixed gas (butene-1/ethylene molar ratio 0.25
) was charged into the autoclave at 94 cgf/dG to start polymerization, and while continuously supplying a mixed gas of ethylene and butene-1 (mole ratio of butene-1 ethylene: 0.05), the total pressure was increased. maintained at 9kgr/cdG, 2
Polymerization was carried out for hours.

After the polymerization was completed, the excess mixed gas was discharged and cooled, and eight of the reactants were taken out and the pellets were removed to obtain 43 g of a white polymer.

Examples 2 to 11 Instead of the solid catalyst component A used in Example 1,
Polymerization was carried out in the same manner as in Example 1 except that solid catalyst components B-K were used.

Comparative Example 1 Instead of solid catalyst component A used in Example 1,
Methyl ammoxane 2 using Cp2TiCh 10
．． Polymerization was carried out in the same manner as in Example 1, except that the amount of the 7+aa+ol/ml solution used was increased from 3.9 ml to 7.4 ml.

Comparative Example 2 Instead of the solid catalyst component A used in Example 1,
Polymerization was carried out in the same manner as in Example 1 except that a solid catalyst component was used.

Comparative Example 3 Instead of the solid catalyst component A used in Example 1,
Polymerization was carried out in the same manner as in Example 1 except that solid catalyst component M was used.

Comparative Example 4 Instead of solid catalyst component A used in Example 1,
Polymerization was carried out in the same manner as in Example 1, except that 10 ml of CI)2 ZrCh was used and the amount of the 2.7 maol/ml solution of methylamoxane was increased from 3.9 ml to [i, 3 ml.

Table 1 shows the composition of the polymerization catalyst used in each of the above Examples and Comparative Examples and the physical property measurement results of the obtained polymers.
and shown in Table 2.

[Effects of the Invention] The catalyst used in the method of the present invention has extremely high activity per transition metal and enables continuous polymerization, and the resulting polyolefin has good particle shape and high bulk density, and is substantially Polymerization products produced under gas phase polymerization conditions in the absence of a solvent also have the above-mentioned features. Polyolefin obtained by the production method of the present invention,
In particular, a copolymer of ethylene and α-olefin has excellent features such as a high die swell ratio, a narrow composition distribution, and extremely low surface tackiness. In the production method of the present invention, even when zirconium is used as the transition metal of the solid catalyst component, high molecular weight ethylene and α-
Olefin copolymers can be produced.

Claims (1)

[Claims] 1 [I] (i) Porous inorganic oxide, (ii) General formula Al(OR)_nX_3_-_n (wherein, R is a hydrocarbon group having 1 to 24 carbon atoms, and X is a halogen and (iii) a catalytic reactant represented by the general formula R^1_pMX_r (where M represents a transition metal element of Group IV of the periodic table, and R ^1 represents a cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, or aralkyl group having 7 to 24 carbon atoms, and R^1 are bonded to each other through an alkylene group having 2 to 8 carbon atoms. X represents a halogen atom, a hydrogen atom, or a hydrocarbon residue having 1 to 24 carbon atoms, and p and r satisfy 2≦p≦4, 0≦r≦2, and p+r=4. [II] A modified organoaluminum compound containing an Al-O-Al bond obtained by the reaction of an organoaluminum compound and water. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst.