JPH0641231A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To provide a catalyst which allows control of a wide mol.wt. distribution in an olefin polymn., enables the production of a polymer at a high activity, and gives a copolymer having a narrow compsn. distribution when used in copolymn. CONSTITUTION:At least one alpha-olefin is polymerized in the presence of a catalyst system comprising a solid catalyst component and an organoaluminum compd. and/or an organoaluminumoxy compd. The solid catalyst component is prepd. by deposting a compd. having a ligand consisting of a cyclopentadienyl of zirconium and/or hafnium on a solid component essentially contg. zirconium, magnesium, and hafnium.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyolefin. More specifically, the present invention is a method for producing a polyolefin having excellent polymerization activity, capable of arbitrarily controlling the molecular weight distribution, and also excellent in heat resistance. Further, in the copolymerization of olefins, the transparency is good and the melt tension, etc. The present invention relates to a method for producing a polyolefin capable of obtaining a copolymer having excellent melt property.

[0002]

It is already known to use a catalyst system comprising a combination of a transition metal compound and an organometallic compound as a method for producing a polyolefin by polymerizing an olefin. Further, in recent years, a method for producing a polyolefin in the presence of a catalyst component composed of an organometallic compound and a solid catalyst component containing magnesium, titanium, or halogen as a main component using a highly active catalyst such as magnesium chloride and titanium tetrachloride has been proposed. Many have been proposed. However, in the catalyst system based on this titanium compound,
There is a limit to the control of the molecular weight distribution of the produced polymer, and there is a demand for a catalyst capable of arbitrarily controlling the molecular weight distribution according to the diversification of the quality of polyolefin.

Therefore, Japanese Patent Publication No. 52-39714
High activity by using a catalyst system consisting of metal magnesium, an organic compound of hydroxide, an organic oxygen compound of a transition metal, a halogen-containing compound of a transition metal and a reaction product of an aluminum halide with an organometallic compound. Polymerization processes have been proposed which can maintain and produce polyolefins with any molecular weight distribution. In this proposal, since metal magnesium, which is relatively easy to handle compared to magnesium chloride and titanium tetrachloride, a hydroxylated organic compound such as alcohol and an organic oxygen compound of a transition metal such as zirconium tetrabutoxide and titanium tetrabutoxide are used, Disclosed is a method for preparing a catalyst, which is industrially advantageous in that the preparation of the catalyst component does not have the problems of controlling water content and corrosion of the preparation equipment. However, the polymerization activity of the catalyst system according to this proposal is not yet sufficient, and there is room for improvement. In addition, when an ethylene / α-olefin copolymer is produced by the catalyst system according to this proposal, the composition distribution is wide, and the α-olefin unit incorporated in the polymer is present in a large amount on the low molecular weight side. There is a problem with poor transparency.

[0004]

The object of the present invention is to control the molecular weight distribution over a wide range, to produce a polymer with high activity, and to have excellent heat resistance. The purpose of the present invention is to provide a catalyst capable of obtaining a coalescence.

[0005]

Therefore, the present inventors have
A catalyst using metal oxides such as magnesium metal, alcohols and organic metal compounds of transition metals such as zirconium tetrabutoxide, which is industrially advantageous in the preparation of catalyst components without problems of water control and corrosion of preparation equipment. As a result of further intensive studies on the production method, it is possible to control the molecular weight distribution with extremely high activity, and also to control the composition distribution at the time of copolymerization. Furthermore, the transition metal in the catalyst contains titanium. Therefore, the inventors have found a surprising catalyst system capable of producing a polymer having excellent weather resistance and being free from coloring, and have completed the present invention.

That is, according to the present invention, in the production of a polyolefin in the presence of a catalyst composed of a transition metal compound and an organometallic compound, as a component (A), a solid component containing zirconium, magnesium and halogen as essential components is added, In the presence of a solid catalyst component supporting a compound having a cyclopentadienyl of zirconium and / or hafnium as a ligand, and a catalyst system comprising an organoaluminum compound and / or an organoaluminumoxy compound as the component (B) And at least one or more α-
A method for producing a polyolefin, which comprises polymerizing an olefin.

[0007]

In preparing the solid catalyst component (A) in the present invention, the solid component preparation method is, for example, as follows:
There is a method by co-pulverization of magnesium chloride and a zirconium compound, a method of reacting a magnesium compound and a zirconium compound, and then a reaction with an organoaluminum halide compound. preferable. In more detail, in preparing the solid component, (i) at least one member selected from metal magnesium, a hydroxylated organic compound, and an oxygen-containing organic compound of magnesium;
i) A homogeneous solution containing at least one zirconium compound selected from oxygen-containing organic compounds of zirconium and halogen-containing compounds and a silicon compound used for improving the shape of the polymer, and (iii) at least 1 The solid component can be obtained by reacting one or more organoaluminum halide compounds.

The solid component thus obtained is added with (i
v) The solid catalyst component (A) can be prepared by supporting a compound having at least one or more transition metal cyclopentadienyls as a ligand.

Hereinafter, these solid components and the method for preparing the solid catalyst component (A) using them will be described in detail.

Examples of the above-mentioned (i) metallic magnesium, a hydroxylated organic compound, and an oxygen-containing organic compound of magnesium, which are reactants, include the following. First, in the case of using metallic magnesium and an organic hydroxide compound, various forms of metallic magnesium can be used, that is, any shape such as powder, particles, foil or ribbon can be used. , Alcohols and phenols are suitable.

As alcohols, straight-chain or branched-chain aliphatic alcohols having 1 to 18 carbon atoms, alicyclic alcohols or aromatic alcohols can be used. Examples include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, n-hexanol, 2-ethylhexanol, n-.
Octanol, i-octanol, n-stearyl alcohol, cyclopentanol, cyclohexanol, ethylene glycol and the like can be mentioned.

Further, phenols include phenol, cresol, xylenol, hydroquinone and the like.

These hydroxylated organic compounds are used alone or as a mixture of two or more kinds. Of course, it may be used alone, but when it is used as a mixture of two or more kinds, it may bring about a peculiar effect on the powder characteristics of the polymer.

In addition, when metal magnesium is used to obtain the solid catalyst component described in the present invention, a substance which reacts with metal magnesium or produces an addition compound, for example, for the purpose of promoting the reaction, for example, Iodine, second chloride
It is preferable to add one or more polar substances such as mercury, alkyl halides, organic acid esters and organic acids.

Next, as compounds belonging to the oxygen-containing organic compounds of magnesium, magnesium alkoxides such as methylate, ethylate, isopropylate, decanolate, methoxyethylate and cyclohexanolate, magnesium alkylalkoxides,
For example ethyl ethylate, magnesium hydroalkoxides such as hydroxymethylate, magnesium phenoxides such as phenate, naphthenate, phenanthrenate and cresolate, magnesium carboxylates such as acetate, stearate, benzoate, phenylacetate, adipate, sebacate. , Phthalates, acrylates and oleates, oximates such as butyl oximate, dimethylglyoxymate and cyclohexyl oximate, hydroxamates, hydroxylamine salts such as N.
-Etroso-N-phenyl-hydroxylamine derivatives, enolates such as acetylacetonate, magnesium silanolates such as triphenylsilanolate, complex alkoxides of magnesium with other metals,
Such as Mg [Al _{(OC 2} H _{5) 4] 2.}
These oxygen-containing organomagnesium compounds can be used alone or as a mixture of two or more kinds.

Examples of the oxygen-containing organic compound and halogen-containing compound of zirconium which are the above-mentioned (ii) reactants include the following.

As the oxygen-containing organic compound of zirconium, a compound represented by the general formula [ZrO _a (OR ¹ ) _b X ¹ _c ] _n is used. However, in the general formula, R ¹ has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
Represents a hydrocarbon such as a straight chain or branched chain alkyl group, a cycloalkyl group, an arylalkyl group, an aryl group, and an alkylaryl group, wherein X ¹ represents a halogen atom, F,
Cl, Br, or I. a, b and c are a ≧
0, b> 0, 4> c ≧ 0 are numbers compatible with the valence of zirconium, and n is an integer. Above all, a
It is desirable to use an oxygen-containing organic compound in which 0 ≦ a ≦ 1 and n is 1 ≦ n ≦ 6.

Specific examples include tetraethoxyzirconium, tetrapropoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium, Zr ₂ O (Oi-C ₃ H ₇ ) ₆ and Zr (OC
H ₃ ) [OC (CH ₃ ) ₃ ] ₃ , Zr [OZr (OC ₂
H _{5) 3] 4,} and the like. The use of oxygen-containing organic compounds containing several different hydrocarbon groups is also within the scope of the invention.

These oxygen-containing organic compounds of zirconium are used alone or as a mixture of two or more kinds.

The halogen-containing compound of zirconium includes halides such as ZrF ₄ and ZrCl.
₄ etc., oxyhalides such as ZrOF ₂ and ZrOC
L _{2 and the} like, halogeno alkoxides such as Zr (O-n)
_{-C 4 H 9) Cl 3,} Zr (O-n-C 4 H 9) 2 Cl
_{2, Zr (OC 2 H 5} ) 3 Cl, Zr (O-i-C 3 H
_{7) Cl 3, Zr (O} -n-C 3 H 7) such as Cl ₃ and the like. Also within the scope of the invention are halogen-containing compounds of zirconium containing several different organic groups.

In the present invention, a silicon compound may be used for the purpose of improving the shape of the polymer. Specifically, the following polysiloxanes and silanes are used. Chain polysiloxanes such as dimethylpolysiloxane and methylhydropolysiloxane, and alkoxysilanes such as methyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane.

The above organosilicon compounds may be used alone, or may be used by mixing or reacting two or more kinds.

As the halogenated organoaluminum compound as the above-mentioned (iii), a compound represented by the general formula R ² _n AlX ² _3-n is used. However, in the general formula, R ² represents a hydrocarbon group having 1 to 20, preferably 1 to 8 carbon atoms, X ² represents a halogen atom, and n is a number of 0 <n <3, preferably Represents a number of 0 <n ≦ 2. Further, R ² is preferably selected from a linear or branched alkyl group, a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group.

Specific examples of the halogenated organoaluminum compound include dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, dipropyl aluminum chloride, ethyl aluminum dichloride, i-butyl aluminum dichloride, methyl aluminum sesquichloride and ethyl aluminum. Examples thereof include sesquichloride, i-butylaluminum sesquichloride, and a mixture of triethylaluminum and aluminum trichloride.

The above organoaluminum halide compounds can be used alone or as a mixture of two or more kinds.

These reactions are preferably carried out in a liquid medium. Therefore, it should be carried out in the presence of an inert organic solvent, especially if these reactants themselves are not liquid under the operating conditions or if the amount of liquid reactant is insufficient.
As the inert organic solvent, all those commonly used in the art can be used, and examples thereof include aliphatic, alicyclic or aromatic hydrocarbons or halogen derivatives thereof or a mixture thereof, for example, isobutane, Hexane, heptane, cyclohexane, benzene, toluene, xylene, monochlorobenzene and the like are preferably used.

The transition metal compound having cyclopentadienyls, which is the above-mentioned (iv), as a ligand, has a general formula (cyclopentadienyls) _p MeL _q-p (wherein Me is zirconium). Or represents hafnium,
L is a ligand other than cyclopentadienyls that coordinates with a transition metal, and represents, for example, a hydrocarbon group, an alkoxy group, halogen or hydrogen. Moreover, p is an integer showing the coordination number of cyclopentadienyls, and q shows the valence of a transition metal.
p and q are in the range of 1 ≦ p ≦ q, and when p is p ≧ 2, the two ligands of cyclopentadienyls are silylene group, substituted silylene group, alkylene group, and substituted alkylene. Two or more may be bonded via a group and sulfur. ).

The cyclopentadienyl ligands include, for example, cyclopentadienyl group, indenyl group, fluorenyl group and the like.

Examples of ligands other than cyclopentadienyls include hydrocarbon groups such as methyl, ethyl and propyl groups, and alkoxy groups such as methoxy and ethoxy groups. Examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

Specific examples of transition metal compounds having cyclopentadienyls as ligands will be given below. For example, bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (methyl, n-butylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadiene Nil) zirconium methoxy chloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, thiobis (cyclopentadienyl) zirconium dichloride, And so on. Further, in these zirconium compounds, transition metal compounds in which the transition metal is replaced with hafnium can also be used.

These reactants are preferably used in an inert organic solvent. Examples of the inert organic solvent include those similar to the solvent used in the reaction step (iii) above.

In the present invention, an organoaluminum oxy compound can be further used for the purpose of increasing the particle size of the polymer. Specific examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, and the like.

The amount of the reactant used in the present invention is not particularly limited, but Mg in the magnesium compound (i) is used.
And the atomic ratio of the gram atom of zirconium (Zr) in the zirconium compound of (ii) above is 0.
05 ≦ Mg / Zr ≦ 100, preferably 0.2 ≦ Mg /
Zr ≦ 20. If Mg / Zr is out of this range and is too large, it becomes difficult to obtain a uniform solution during catalyst preparation, or the activity of the catalyst becomes low during polymerization. On the other hand, if it is too small, the activity of the catalyst becomes low, which causes problems such as coloring of the product.

In the present invention, the kind and amount of the organoaluminum halide of (iii) above should be appropriately selected. That is, the catalytic properties of active species generated from the oxygen-containing organic compound of zirconium (ii) are controlled by the type and amount of organoaluminum halide. More specifically, the atomic ratio of the gram atom of Mg in the magnesium compound of (i) to the gram atom of aluminum in the organoaluminum halide of (iii) is 0.01 ≦ Mg / Al ≦ 10. , Preferably 0.05 ≦ Mg / Al ≦ 1.

The reaction conditions in each step are not particularly limited, but are inert for 0.5 to 50 hours, preferably 1 to 6 hours at a temperature in the range of -50 to 300 ° C, preferably 0 to 200 ° C. It is carried out under normal pressure or under pressure in a gas atmosphere.

On the solid component thus obtained, the above (i
The atomic ratio of the gram atom of a transition metal (Me) having a cyclopentadienyl ligand of v) to the gram atom of zirconium (Zr) in the zirconium compound of (ii) above is 0.01 ≦ Me. / Zr ≦ 10, especially 0.05 ≦ Me
It is desirable that the carrier be loaded in an amount such that / Zr ≦ 5.

The solid catalyst component (A) thus obtained can be used as it is for the polymerization in a suspended state, but it may be separated from the solvent in some cases, and further heated under normal pressure or reduced pressure to remove the solvent. It can also be used in a dried state after removing the.

In the present invention, the catalyst component (B) may be an organoaluminum compound and / or an organoaluminum oxy compound composed of aluminum metal and an organic group.

As the above organic group, an alkyl group can be mentioned as a representative. As this alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms is used. Specifically, for example, trimethyl aluminum, triethyl aluminum, tri-i-butyl aluminum, tri-n-butyl aluminum or tri-n-
Examples include decyl aluminum. Above all, it is preferable to use a trialkylaluminum having a linear or branched alkyl group having 1 to 10 carbon atoms.

As the organoaluminum compound, an alkyl metal hydride having an alkyl group having 1 to 20 carbon atoms may be used. Specific examples of such a compound include diisobutylaluminum hydride. Further, an alkyl metal halide having an alkyl group having 1 to 20 carbon atoms such as ethyl aluminum sesquichloride, diethyl aluminum chloride, diisobutyl aluminum chloride or an alkyl metal alkoxide such as diethyl aluminum ethoxide can be used.

An organoaluminum compound obtained by reacting a trialkylaluminum or dialkylaluminum hydride having an alkyl group having 1 to 20 carbon atoms with a diolefin having 4 to 20 carbon atoms, for example, a compound such as isoprenylaluminum. Can also be used.

Further, as the organoaluminum oxy compound, aluminoxane which is a reaction product of the above organoaluminum compound and water can be used. In particular, aluminoxanes such as methylaluminoxane, ethylaluminoxane and propylaluminoxane produced from trialkylaluminum are preferable.

The above organoaluminum compounds may be used alone, or two or more kinds may be mixed or reacted and used.

The olefin polymerization according to the present invention can be carried out either in the liquid phase or in the gas phase, and can be carried out under the general reaction conditions of the so-called Ziegler method. That is, the polymerization is carried out at a temperature of 20 to 250 ° C. in a continuous system or a batch system. The polymerization pressure is not particularly limited, but under pressure,
Particularly, the use of 1.5 to 2500 kg / cm ² G is suitable.

When the polymerization is carried out in the liquid phase, it is carried out in the presence of an inert solvent. As the inert solvent, any commonly used one may be used. Particularly suitable are alkanes or cycloalkanes having 4 to 20 carbon atoms, such as isobutane, pentane, hexane, cyclohexane and the like.

When the polymerization is carried out in the gas phase, it is desirable to carry out a preliminary polymerization with 0.01 to 50 g of ethylene or an α-olefin having 3 or more carbon atoms per 1 g of the solid catalyst component (A). The contact conditions with the monomer are not particularly limited,
It should be performed in the absence of oxygen and water. Generally, this contact treatment is -50 to 100 ° C, preferably 0.
It can be carried out in a temperature range of up to 50 ° C under normal pressure or under increased pressure. When it is processed in a gas phase, it is in a fluidized state, and when it is processed in a liquid phase, it is sufficiently contacted under stirring. Preferably. The monomers used in the prepolymerization may be used alone or in combination of two or more kinds, and when prepolymerizing two or more kinds, the prepolymerization may be carried out sequentially or simultaneously. In the preliminary polymerization, it is desirable to use the organoaluminum compound in a proportion of 0.1 to 1000 mol with respect to 1 mol of the transition metal atom in the solid catalyst component (A).

In the case of carrying out the gas phase polymerization, the reactor used in the polymerization step can be appropriately used as long as it is one which is usually used in the technical field concerned, such as a fluidized bed type polymerization device and a stirred tank type polymerization device. When a fluidized bed type polymerizer is used, it is carried out by blowing a gaseous olefin and / or an inert gas into the system while keeping the reaction system in a fluidized state. When using a stirring tank type polymerizer, various types of stirrers such as an Ikari type stirrer, a screw type stirrer, and a ribbon type stirrer can be used as the stirrer.

The polymerization of the present invention includes not only homopolymerization of α-olefins but also copolymerization of two or more α-olefins. As the α-olefin used for the polymerization, ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene and the like can be mentioned. Further, in order to introduce a double bond into the polymer, α
It is also possible to carry out the copolymerization using a mixture of olefins and dienes such as butadiene and isoprene. The amount of α-olefin used for copolymerization needs to be selected according to the density of the target polymer. The density of the polymer according to the present invention can be produced in the range of 0.890 to 0.970 g / cm ³ .

The polymerization operation of the present invention can be carried out not only in ordinary one-step polymerization carried out under one polymerization condition, but also in multi-step polymerization carried out under a plurality of polymerization conditions.

In carrying out the present invention, the amount of the solid catalyst component (A) used is 1 liter of the solvent or 1 liter of the reactor.
Therefore, it is preferable to use an amount corresponding to 0.001 to 2.5 mmol of the transition metal atom, and it is also possible to use a higher concentration depending on the conditions.

The amount of the organoaluminum compound as the catalyst component (B) is 0.0 per 1 l of the solvent or 1 l of the reactor.
2 to 1000 mmol, preferably 0.2 to 100 mm
Used at a concentration of ol.

In the present invention, the molecular weight of the produced polymer can be adjusted by a known means, that is, a method of allowing an appropriate amount of hydrogen to exist in the reaction system.

[0053]

EFFECTS OF THE INVENTION According to the present invention, firstly, a polymer having an extremely high polymerization activity and not requiring a deashing step for the purpose of removing a catalyst can be obtained. In addition, since the transition metal in the catalyst does not contain titanium, a polymer having excellent weather resistance and free from coloring can be produced.

Secondly, when copolymerization is carried out, a copolymer having an extremely good copolymerizability and a narrow composition distribution can be easily produced.

Thirdly, the molecular weight distribution can be easily controlled by the amount of the reactant used for producing the catalyst. Therefore, polymers having various physical properties can be easily produced.

[0056]

EXAMPLES The present invention will be shown below with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, HLMI / M
I is the high load melt index (HLMI, ASTMD
-1238 Condition F) and melt index (M
I, according to ASTM D-1238 condition E) and is a measure of the molecular weight distribution. It is considered that when the HLMI / MI value is small, the molecular weight distribution is narrow.

The activity represents a polymer production amount (g) per 1 g of the solid catalyst component.

The number of ethyl branches was quantified by a Fourier transform infrared spectrophotometer (FT-IR) from a peak derived from a methyl group appearing near 1378 cm ^-1 .

The weather resistance is based on the polymer having an antioxidant (Seeno).
x326M) 250ppm, light stabilizer (Tinuvin
770) 250 ppm was added to the test piece, and the accelerated exposure test (JIS A 1415) was performed. In the accelerated exposure test, a sunshine carbon arc lamp was used as a light source. The weather resistance evaluation method is JIS A 1411 4.
Tensile test (JIS K 691
1). The elongation rate (%) in the tensile test was calculated by the following formula.

Elongation rate (%) = ((standard mark interval at break)-
(Initial gauge interval) / (Initial gauge interval) The accelerated exposure test time until the elongation (%) of the test piece reached 50 (%) was taken as the weather resistance time required for deterioration.

Example 1 (a) [Preparation of solid catalyst component (A)] In a 3 liter glass flask equipped with a stirrer, 25.0 g (1.03 mol) of magnesium metal powder and 197.4 g (0 of zirconium tetrabutoxide) were added. .41mo
1) was added, and 167.7 g (2.26 mol) of n-butanol in which 1.25 g of iodine was dissolved was added at 90 ° C. to 2
The mixture was added over a period of time, and the mixture was stirred at 140 ° C. for 2 hours under a nitrogen blanket while eliminating hydrogen gas generated. This one
After being brought to 10 ° C., 42.9 g of tetraethoxysilane
(0.21 mol) and tetramethoxysilane 31.3 g
(0.21 mol) was added, and the mixture was further stirred at 140 ° C. for 2 hours. Then, 1750 ml of hexane was added, and Mg was added.
A homogeneous solution containing and Zr was obtained.

95.0 g of this homogeneous solution (0.
(Equivalent to 058 mol) was placed in a separately prepared 500 ml glass flask, the temperature was raised to 45 ° C., and 129 ml of a hexane solution containing 0.35 mol of i-butylaluminum dichloride was added over 2 hours. Then, raise the temperature,
The mixture was stirred at 70 ° C for 1 hour. Furthermore, after removing the supernatant liquid and drying in a nitrogen atmosphere, a part thereof was sampled and subjected to elemental analysis, whereupon Zr was 14.1% by weight. Next, 5.0 g of this solid component was placed in a 300 ml glass flask, and then 20 ml of toluene and 0.23 g of bis (cyclopentadienyl) zirconium dichloride.
(0.77 mmol) was added, and the mixture was stirred at 30 ° C. for 1 hour. Then, toluene was removed under reduced pressure using an evaporator. Hexane was added to the product, and the product was washed 7 times by the gradient method. Thus, a slurry of the solid catalyst component (A) suspended in hexane was obtained. A part of the sample was taken, the supernatant was removed, the sample was dried under a nitrogen atmosphere, and elemental analysis revealed that Zr was 16.9% by weight.

(B) [Polymerization] The interior of the stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 1.2 l of hexane was charged, and the internal temperature was adjusted to 80 ° C. Then, the catalyst component (B)
As the above, a slurry containing 5.8 mg of methylaluminoxane in terms of aluminum atom and 10.7 mg of the solid catalyst component (A) obtained above was sequentially added. After adjusting the internal pressure of the autoclave to 1 kg / cm ² G, polymerization was carried out for 1.5 hours while ethylene was continuously added so that the internal pressure of the autoclave became 7.0 kg / cm ² G. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, polyethylene was taken out, separated from the solvent by filtration and dried.

As a result, the melt index was 0.01.
Polyethylene 2 with g / 10 min and HLMI / MI of 150
76 g were obtained. The activity corresponds to 25800 g / g. The weather resistance time was 1800 hours.

Example 2 (a) [Preliminary Polymerization] The inside of a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen to obtain the solid catalyst component (A) 2. 12 g was suspended in 400 ml of hexane and added. Subsequently, 0.22 g (2.0 mmol) of triethylaluminum was sequentially added as the catalyst component (B). Then, the internal temperature of the autoclave is set to 30.
Propylene was supplied while maintaining the temperature at 1 ° C. and the pressure at 1 to ² kg / cm ² G, 21.2 g of propylene was reacted, and the solid catalyst component (A) was prepolymerized with propylene. By this operation, 10 g of propylene was absorbed per 1 g of the solid catalyst component (A). Hexane was added to the product, and the product was washed 7 times by the gradient method. Thus, a prepolymerized catalyst suspended in hexane was obtained.

(B) [Polymerization] Copolymerization of ethylene and 1-butene was carried out by a gas phase method using the prepolymerized catalyst obtained above. That is, the inside of a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, and 200 g of salt dried at 200 ° C for 30 hours was added as a catalyst dispersion medium to adjust the internal temperature to 80 ° C. Thereafter, as the component (B), methylaluminoxane of 5.2 mg in terms of aluminum atom, and 102.3 mg of the prepolymerized catalyst obtained above were obtained.
(Including 9.3 mg of the solid catalyst component (A)) were added in sequence. After adjusting the inside of the polymerization vessel to 1 kg / cm ² G with nitrogen, the internal pressure of the autoclave was adjusted to 17.0 kg / cm ² while adjusting 1-butene / ethylene (mol ratio) in the gas phase to 0.20. Polymerization was carried out for 1.5 hours while ethylene and 1-butene were continuously added so as to give G. After the completion of the polymerization, the mixture was cooled, unreacted gas was expelled, and a mixture of the produced polymer and sodium chloride was taken out. The mixture was washed with pure water, dissolved in sodium chloride and then dried to obtain a polymer.

As a result, the melt index was 0.50.
g / 10 min, HLMI / MI is 86, and the number of ethyl branches is 19 (polyethylene / carbon number 1000) polyethylene 21
5 g was obtained. The activity per gram of the solid catalyst component (A) was 23100 g / g. The weather resistance time is 20
It was 00 hours.

Example 3 (a) [Preparation of solid catalyst component (A)] 5.0 g of the solid component obtained in Example 1 was placed in a 300 ml glass flask, and then 100 ml of toluene and bis (cyclopentadienyl) were added. Zirconium dichloride (1.15 g, 3.9 mmol) was added, and the mixture was stirred at 30 ° C. for 1 hour. Then, toluene was removed under reduced pressure using an evaporator. Hexane was added to the product, and the product was washed 7 times by the gradient method. Thus, a slurry of the solid catalyst component (A) suspended in hexane was obtained. A part of the sample was collected, the supernatant was removed, the sample was dried under a nitrogen atmosphere, and the elemental analysis showed that Zr was 20.2% by weight.

(B) [Polymerization] The interior of the stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 1.2 l of hexane was charged, and the internal temperature was adjusted to 80 ° C. Then, the catalyst component (B)
As the slurry, methylaluminoxane was added successively, containing 1.3 mg atom of aluminum atom and 2.9 mg of the solid catalyst component (A) obtained above.
After adjusting the internal pressure of the autoclave to 1 kg / cm ² G,
Polymerization was carried out for 1.5 hours while continuously adding ethylene so that the internal pressure of the autoclave was 7.0 kg / cm ² G. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, polyethylene was taken out, separated from the solvent by filtration and dried.

As a result, the melt index was 0.04.
g / 10min, HLMI / MI is 141 polyethylene 1
30 g was obtained. The activity corresponds to 44700 g / g. The weather resistance time was 1800 hours.

Example 4 (a) [Preliminary Polymerization] The solid catalyst component (A) obtained in Example 3 was preliminarily polymerized in the same manner as in Example 2.

(B) [Polymerization] Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 2 using the prepolymerized catalyst obtained above.

As a result, the melt index was 1.3 g.
/ 10 minutes, HLMI / MI is 72, and the number of ethyl branches is 23 (polyethylene / 1000 carbons) polyethylene 116.
g was obtained. The activity per gram of the solid catalyst component (A) was 33000 g / g. The weather resistance time is 190
It was 0 hours.

Comparative Example 1 (a) [Catalyst preparation] 0.06 in terms of Mg of the homogeneous solution obtained in Example 1 (a)
Add 6 mol to a 500 ml flask, bring to 45 ° C.,
152 ml (0.41 mol) of a 50% hexane solution of i-butylaluminum dichloride was added over 2 hours. After adding everything, raise the temperature and raise to 70 ° C. 1
The mixture was stirred for a time to obtain a solid catalyst component. Hexane was added to this solid catalyst component and the mixture was washed 5 times, then 26.5 g (0.14 mol) of titanium tetrachloride was added and the temperature was raised.
The temperature was raised to 70 ° C. and the reaction was performed for 1 hour. Hexane was added to the product and washed 7 times to obtain a solid catalyst. Collect a part of it, remove the supernatant and dry it under a nitrogen atmosphere.
Elemental analysis revealed that Ti was 7.9% by weight and Zr was 6.
It was 8% by weight.

(B) [Polymerization] The interior of the stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 1.2 l of hexane was charged, and the internal temperature was adjusted to 80 ° C. Then, the catalyst component (B)
As the slurry, 0.285 g of triisobutylaluminum and 31 mg of the solid catalyst obtained above were sequentially added. After adjusting the internal pressure of the autoclave to 1 kg / cm ² G, add hydrogen at 13.3 kg / cm ² , and then continuously add ethylene so that the internal pressure of the autoclave becomes 20.0 kg / cm ² G for 1.5 hours. Polymerization was carried out. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, polyethylene was taken out, separated from the solvent by filtration and dried.

As a result, the melt index was 0.16.
Polyethylene 3 with g / 10 minutes and HLMI / MI of 102
71 g were obtained. The activity corresponds to 11800 g / g. The weather resistance time was 1500 hours.

Comparative Example 2 (a) [Catalyst preparation] 7.0 g (0.288 mol) of magnesium metal powder and 49.0 g (0.144 mol) of titanium tetrabutoxide were placed in a 1 liter glass flask equipped with a stirrer. N-Butanol in which 0.35 g of iodine was dissolved 44.
8 g (0.60 mol) was added at 90 ° C. over 2 hours,
The mixture was stirred at 140 ° C. for 2 hours under a nitrogen blanket while eliminating further generated hydrogen gas. After making this 110 degreeC, 18 g (0.086 mol) of tetraethoxysilane
And tetramethoxysilane 13.2g (0.086mo
1) was added, and the mixture was further stirred at 140 ° C. for 2 hours. Then, 490 ml of hexane was added to obtain a Mg-Ti solution.

96.8 g of this Mg-Ti solution (corresponding to 0.058 mol as Mg) was placed in a separately prepared 500 ml glass flask, and then 63 m of a hexane solution containing 0.17 mol of i-butylaluminum dichloride.
1 was added, and the mixture was stirred at 70 ° C. for 1 hour. Hexane was added to the product, and the product was washed 7 times by the gradient method. Thus, a slurry of the solid complex suspended in hexane was obtained. Collect a part of it, remove the supernatant and dry it under a nitrogen atmosphere.
Elemental analysis revealed that Ti was 11.1% by weight.

(B) [Polymerization] The inside of a stainless steel electromagnetic stirring autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, 1.2 l of hexane was charged, and the internal temperature was adjusted to 80 ° C. Then, the catalyst component (B)
As tri-i-butylaluminum 0.23 g (1.
2 mmol) and a slurry containing 7.1 mg of the catalyst component obtained above were sequentially added. After adjusting the internal pressure of the autoclave to 1 kg / cm ² G, hydrogen was added to 4 kg / cm ²
Then, the internal pressure of the autoclave is 11.0 kg / cm
While continuously adding ethylene so as to obtain ² G, 1.
Polymerization was carried out for 5 hours. After completion of the polymerization, the mixture was cooled, unreacted gas was expelled, polyethylene was taken out, separated from the solvent by filtration and dried.

As a result, the melt index was 0.8 g.
/ 10 minutes, HLMI / MI is 34 polyethylene 273
g was obtained. The activity corresponds to 38400 g / g. The weather resistance time was 1500 hours.

[Brief description of drawings]

FIG. 1 is a flow chart of catalyst preparation in the present invention.

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[Procedure amendment]

[Submission date] July 22, 1992

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Correction target item name] All drawings

[Correction method] Change

[Correction content]

[Figure 1]

Claims (1)

[Claims] 1. When producing a polyolefin in the presence of a catalyst composed of a transition metal compound and an organometallic compound, zirconium and / or zirconium and / or a solid component containing zirconium, magnesium and halogen as essential components are used as the component (A). In the presence of a solid catalyst component supporting a compound having a hafnium cyclopentadienyl ligand as a ligand, and (B) a catalyst system comprising an organoaluminum compound and / or an organoaluminumoxy compound, at least 1 A method for producing a polyolefin, which comprises polymerizing at least one α-olefin.