Process for the preparation of an ethylene copolymer and an olefin polymer, and catalysts for olefin polymerization

IS 2 165 347 T3

DESCRIPTION

Process for the preparation of a copolymer of ethylene and an olefinic polymer and catalysts for the polymerization of olefins.

Field of the invention

The present invention relates to a new ethylene copolymer and, more particularly, to a new ethylene copolymer having a narrow compositional distribution and excellent melt tension compared to known ethylene copolymers.

Furthermore, the present invention relates to a process for the preparation of the ethylene copolymer which has an excellent melt tension and which exhibits a narrow compositional distribution.

Background of the invention

Ethylene copolymers have hitherto been molded by various molding methods and have been used in many fields. The requirements regarding the characteristics of ethylene copolymers differ depending on the molding methods and fields of application. For example, when a high speed bubble film is molded, it is necessary to select an ethylene copolymer having a high melt tension compared to its molecular weight, in order to stably perform high speed molding without fluctuation or bursting of the bubbles. An ethylene copolymer exhibiting similar characteristics is required in order to avoid bending or tearing in blow molding or in order to suppress width loss to a minimum value in T die molding.

A high-pressure, low-density polyethylene has a high melt tension compared to an ethylene copolymer prepared with a Ziegler-type catalyst, and is used as a material for films and hollow containers. The low-density, high-pressure polyethylene described above has low mechanical strength, such as tensile strength, tear resistance and impact resistance, and also has low heat resistance, low resistance to stress cracking, etc.

On the other hand, Japanese Patents LOP Nos. 90810/1981 and 106806/1985 propose a method to improve the tension in the melt state and the blowing ratio (nozzle / swelling ratio) of the ethylene polyomers obtained through the use of catalysts of the Ziegler type, especially a titanium type catalyst.

However, ethylene polymers made using a titanium catalyst, especially low density ethylene polymers, generally present problems such as their wide compositional distribution and tackiness of articles molded therefrom, such as films.

Therefore, it would be of great value initially to have ethylene polyomers having excellent melt tension and narrow compositional distribution.

Recently, a new Ziegler-type catalyst for olefin polymerization has been developed, comprising a zirconium compound and an aluminoxane, said catalyst being capable of producing ethylene / α-olefin copolymers with high polymerization activities. Likewise, a process has been proposed for the preparation of ethylene / α-olefin copolymers using this new type of catalyst.

For example, Japanese Patent LOP No. 19309/1983 describes a process for polymerizing ethylene with one or at least two α-olefins C₃-Ci₂ at a temperature of -50 to 200^ORC, in the presence of a catalyst consisting of a transition metal compound represented by the formula:

(cyclopentadienyl) ₂MeRHal where R is cyclopentadienyl, Ci-C alkyl₆ or halogen, Me is a transition metal and Hal is halogen, and a linear aluminoxane represented by the formula

IS 2 165 347 T3

To the₂OR4 [Al (R) -O] „where R is methyl or ethyl and n is a number from 4 to 20, or a cyclic aluminoxane represented by the formula

<img file="ES2165347T3_D0001.tif" />

<img file="ES2165347T3_D0002.tif" />

where R and n are defined as above.

Japanese Patent LOP No. 19309/1983 describes procedures for the preparation of a linear aluminoxane represented by the formula

R \

Al - O ^/

R

I

Al - O

<img file="ES2165347T3_D0003.tif" />

n

R ^/

To the ^\

R where n is a number from 2 to 40 and R is Ci-C alkyl₈, and a cyclic aluminoxane represented by the formula ^{—— Al (R) -O—}—P where n and R are defined as above. The same Patent Publication also describes a process for the polymerization of olefins using a catalyst prepared by mixing, for example, methylaluminoxane prepared by the above-mentioned process and a titanium or zirconium bis (cyclopentadienyl) compound.

Japanese Patent LOP No. 35005/1985 describes a process for preparing a catalyst for the polymerization of olefins, wherein the process comprises reacting an aluminoxane represented by the formula _Ri ^\

Al - O ^/

R⁰_Ri

--Al - O -

<img file="ES2165347T3_D0004.tif" />

n _Ri ^/

To the ^\_R0 where R¹ is C alkyl₁-C₁₀ and R⁰ is R¹, or R⁰ represents -O-, with a magnesium compound and subsequent chlorination of the reaction product and treatment with a Ti, V, Zr or Cr compound.

Japanese Patent LOP No. 35006/1985 describes a catalyst consisting of mono-, di- or tricyclopentadienyl-transition metals (the transition metals being at least two different metals) or their derivatives, and an alumoxane (aluminoxane) in combination. Example 1 of this Patent Publication describes that ethylene and propylene are polymerized to form a polyethylene in the presence of a catalyst consisting of bis (pentamethylcyclopentadienyl) -zirconiodimethyl and an aluminoxane. In Example 2 of this Patent Publication ethylene and propylene are polymerized to form a polymeric mixture of a polyethylene and an ethylene / propylene copolymer in the presence of a catalyst consisting of bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl dichloride ) zirconium and an alumoxane.

Japanese Patent LOP No. 35007/1985 describes a process in which ethylene is polymerized only, or ethylene and an α-olefin of not less than 3 carbon atoms are copolymerized in the presence of metallocene, and of a cyclic aluminoxane represented by formula —-Al (R) -O —- where R is an alkyl group of 1 to 5 carbon atoms and n is an integer of approximately 1 to 20, or of a linear aluminoxane represented by the formula

IS 2 165 347 T3

<img file="ES2165347T3_D0005.tif" />

where R and n are defined as above.

Japanese Patent LOP No. 35008/1985 describes a process for the preparation of a polyethylene or a copolymer of ethylene and an α-olefin C₃-C₁₀, wherein a catalytic system is used comprising not less than two types of metallocene and an alumoxane.

Although the catalysts formed from a transition metal compound and an aluminoxane, proposed by the state of the art, are excellent in terms of their activity in polymerization, especially in the polymerization of ethylene, in comparison with those catalysts that have been disclosed the value of the appearance of these catalysts and that they are formed by a transition metal compound and an organoaluminum compound, Most catalysts are soluble in the reaction system, and, in most cases, polymerization processes are limited to a solution polymerization system. Furthermore, catalysts have the problem that the productivity of a polymer decreases as a consequence of a notable increase in the viscosity of the reaction solution containing polymer when the production of a polymer having a high molecular weight is attempted. also presenting the problems that the polymer obtained by means of a post-polymerization treatment has a low apparent specific density and that it is difficult to prepare a spheric polymer having excellent properties in the form of particles.

On the other hand, olefin polymerization has been attempted in a suspension polymerization system or in a gas phase polymerization system, using catalysts in which at least one of the components constituted by the transitional metal compound and the aluminoxane , described previously, is supported on a porous support of inorganic oxide such as solid, alumina and silica-alumina.

For example, Japanese LOP Patents Nos. 35006/1985, 35007/1985 and 35008/1985 described above, describe that catalysts can be used in which a transition metal compound and an aluminoxane are supported on silica, alumina, silica-alumina , etc.

Furthermore, Japanese Patent LOP No. 106808/1985 and 106809/1985 describe a process for the preparation of a composition consisting of an ethylene polymer and a filler, which process comprises polymerizing ethylene or copolymerizing ethylene and an α-olefin in the presence of a product prepared by contacting a highly active catalytic component comprising a hydrocarbon soluble titanium compound and / or a zirconium compound with a filler, an organoaluminum compound and a filler having an affinity for polyolefin.

Japanese Patent LOP No. 31404/1986 describes a process for the polymerization of ethylene or copolymerization of ethylene and an α-olefin in the presence of a catalytic mixture consisting of a transition metal and a product obtained by reaction of trialkylaluminum and water in the presence silicon dioxide or aluminum oxide.

On the other hand, Japanese Patent LOP No. 276805/1986 describes the polymerization of an olefin in the presence of a catalyst constituted by a zirconium compound and a reaction mixture obtained by reacting an aluminoxane with trialkylaluminum first, and further reacting the resulting reaction mixture with an inorganic oxide having a hydroxide group on the surface, such as solid.

In addition, Japanese LOP Patents Nos. 108610/1986 and 296008/1986 describe a process for polymerizing olefins in the presence of a catalyst wherein a transition metal compound, such as metallocene, and an aluminoxane are supported on a support such as an inorganic oxide.

EP-A-0 347 128 describes a process for the production of a high molecular weight ethylene / αolefin elastomer with a metallocene-alumoxane catalyst. However, the polyomers obtained by the process of said reference do not satisfy all the properties that are required in a copolymer according to the present invention.

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However, during the polymerization or copolymerization of olefins in suspension or in the gas phase, using said solid catalytic component supported on a support as described in the referred Patent publications, the catalytic component considerably decreases the polymerization activities compared to the referred one. solution polymerization, and the resulting polymers do not have a satisfactory bulk density.

The Journal of Polymer Science / Part A, 26 (1988) 3089-3102 describes metallocenomethylaluminoxane catalysts for olefin polymerization, using trimethylaluminum as a coactivator. The reference does not specify anything regarding the important properties of the copolymers produced by these catalysts and only describes the polymerization of ethylene.

Objects of the invention

The present invention is intended to solve those problems associated with the state of the art, previously described, and thus an object of the invention is to provide an ethylene copolymer which has excellent melt tension and which has a narrow distribution. compositional.

Another object of the present invention is to provide a process for the preparation of ethylene polymers which are excellent in melt tension and, in the case of a copolymer, have a narrow compositional distribution.

A further object of the invention is to provide solid catalysts for the polymerization of olefins, capable of producing, with high activity, spheric olephonic polyomers excellent in terms of particulate properties and melt tension, even when applied to the polymerization in suspension and in the gas phase using a small quantity of an oxy-organoaluminum compound. Another object is the polymerization of olefins using such catalysts that have such good properties.

Summary of the invention

The ethylene copolymer according to the present invention is an ethylene copolymer that comprises constituent units (a) derived from ethylene and constituent units (b) derived from an α-olefin that has 3 to 20 carbon atoms, and is characterized in that:

(A) has a density (d) of 0.87 to 0.94 g / cm³;

(B) has an MFR value of 0.001 at 50 g / 10 min, measured at a temperature of 190^ORC and under a load of 2.16 Kg;

(C) the melt stress (MT) and the MFR of the ethylene copolymer satisfy the relationship:

log MT&gt; -0.66 log MFR + 0.6; and (D) the temperature (T) at which the endothermic curve of the ethylene copolymer, measured by a differential scanning calorimeter (DSC), shows the highest peak, and the density (d) satisfies the relationship:

T &lt;400 d - 250.

Furthermore, a first process to prepare the olephonic polymer of the present invention comprises polymerizing the olefin in the presence of a solid catalyst formed from:

(A) a compound of a transition metal of Group IVB of the Periodic Table having at least two groups each of which has a cyclopendadienyl backbone, said two groups being at least cross-linked through a group containing carbon and / or silicon; and (B) an organoaluminum oxy-compound; and under the condition that the polymer produced exists in a solid state in the polymerization system, to form an olephonic polymer that satisfies the following conditions:

a) the olephonic polymer has an MFR of 0.001 to 100 g / 10 min at a temperature of 190^ORC and under a load of 2.16 kg; Y

IS 2 165 347 T3

b) the melt stress (MT) and the MFR of the olefinic polymer satisfy the relationship:

log MT&gt; -0.66 log MFR +0.6.

A first solid prepolymerized catalyst containing polyolefin (hereinafter referred to as prepolymerized solid catalyst) for the polymerization of olefins, used in the present invention, is characterized in that the solid catalyst is formed by prepolymerization of the olefin in suspension or in the gas phase, in the presence of a catalyst comprising:

[A] a support in the form of fine particles;

[B] a transition metal compound (hereinafter referred to as a non-bridged type transition metal compound) comprising ligands having a cyclopentadienyl backbone, said cyclopentadienyl backbones not being mutually linked;

[C] a transition metal compound (hereinafter referred to as a bridged-type methyl compound) comprising at least two ligands each of which has a cyclopentadienyl backbone, said two ligands being linked to each other except through an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group;

[D] an oxy-organoaluminum compound.

A second catalyst for the polymerization of olefins, used in the present invention, is characterized in that it is formed by the aforementioned components [A], [B], [C], [D] and [E] and by an organoaluminum compound.

Furthermore, a second process for the preparation of olefinic polymers according to the present invention comprises polymerizing or copolymerizing the olefins in the presence of the solid catalyst described above.

Brief description of the drawings

Figure 1 shows an endothermic curve obtained by measuring the heat absorption of an ethylene copolymer (prepared in Example 2) of the invention, using a DSC (Differential Scanning Calorimeter).

Figure 2 is an example of an IR spectrum of an organoaluminum oxy-compound of the invention.

Figure 3 is an example of an IR spectrum of a known benzene soluble organoaluminum oxy-compound.

Detailed description of the invention

First, the ethylene copolymer according to the present invention will be specifically described below.

The ethylene copolymer according to the invention is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. The ethylene copolymer has a density (d) of 0.87 to 0.94 g / cm³, preferably 0.88 to 0.93 g / cm³.

Density is determined by means of a density gradient tube using the filament obtained at the time of MFR measurement at 190^ORC under a load of 2.16 kg, and that it is treated by heating it to 120^ORC for 1 hour and slowly cooling it to room temperature over 1 hour.

The ethylene copolymer described above conveniently comprises constituent units (a) derived from ethylene in an amount of 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 70 to 96% by weight, and constituent units (b) derived from an α-olefin having 3 to 20 carbon atoms in an amount of 1 to 45% by weight, preferably 2 to 35% by weight, more preferably 4 to 30% by weight .

The composition of the copolymer is usually determined by spectrum analysis. ¹³C-NMR of a sample prepared by uniformly dissolving 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a sample tube having a diameter of 10 mm, under the following conditions: a

ES 2 165 347 T3 measuring temperature 120^orC, a measurement frequency of 25.05 MHz, a spectrum width of 1,500 Hz, a pulse repetition period of 4.2 seconds, and a pulse width of 6 psec.

Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene-1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1- tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

The ethylene copolymer according to the present invention suitably has an MFR of 0.001 to 50 g / 10 min, preferably 0.01 to 20 g / 10 min.

The determination of the MFR is carried out according to ASTM D1238-65T under the conditions of a temperature of 190^orC and a load of 2.16 kg.

On the other hand, the melt tension (MT) and the MFR of the ethylene copolymer of the invention satisfy the following relationship:

log MT&gt; -0.66 log MFR + 0.6, preferably log MT&gt; -0.66 log MFR + 0.7, more preferably log MT&gt; -0.66 log MFR + 0.8.

As described above, the ethylene copolymer of the invention is excellent in melt tension (MT) and exhibits good moldability.

In addition, melt tension (MT) is determined by measuring the tension of a molten copolymer while it is being drawn at a constant speed. The sample to be measured is a powdered copolymer or a polymer obtained by dissolving the powdered copolymer in decane at once and pouring the solution into a methanol / acetone solution (1/1) in an amount 5 times greater than the amount of dean to precipitate. The measurement is carried out by extruding the sample at a resin temperature of 190^orC, at an extrusion speed of 10 mm / minute and a collection speed of 10-20 m / minute using a MT measuring apparatus (manufactured by Toyo Seiki Seisakusho KK) having a nozzle diameter of 2.09 mm and a nozzle length of 8 mm. During the melt tension measurement, the ethylene copolymer is premixed with 0.1% by weight of 2,6-di-tert-butyl-p-cresol as a crosslinking stabilizer.

On the other hand, in the ethylene copolymer of the invention, the temperature (T) at which its endothermic curve, measured by a differential scanning calorimeter (DSC), shows the highest peak, and its density (d) satisfies the following relationship:

T &lt;400 d - 250, preferably

T &lt;450 d - 297, more preferably

T &lt;500 d - 344, very particularly

T &lt;550 d - 391.

In addition, the measurement by the DSC is carried out using an apparatus of the DSC-7 type manufactured by Perkin Elmer Co., Ltd. The temperature (T) at which the endothermic curve shows the maximum peak, is derived from an endothermic curve obtained introducing about 5 mg of a sample in an aluminum tray, heating to 200^or C at a speed of 10^orC / min, keeping the sample at 200^or C for 5 minutes, decreasing the temperature to room temperature at a rate of 20 ^orC / min. and then heating at a speed of 10^orC / min.

In the ethylene copolymer of the invention, it is convenient that the fraction of the amount (W) of a component soluble in m-decane and the density of the copolymer at 23^or C satisfy the following relation:

log W &lt;-50 d + 46.5, preferably log W &lt;-50 d + 46.4, more preferably log W &lt;-50 d + 46.3.

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From the relationship between temperature (T) and density (d) and the relationship between the fraction of the amount (W) of a component soluble in n-decane and the density (d), the conclusion can be reached that the ethylene copolymer of the present invention has a narrow compositional distribution.

Furthermore, the amount of the n-decane soluble component is obtained by the following procedure.

The measurement of the amount of the soluble component in n-decane (polymer having the smallest amount of soluble component with the narrowest compositional distribution) is carried out by adding 3 g of the copolymer to 450 ml of n-decane, dissolving the copolymer at 145^or C, cooling the solution to 23 ° C, filtering off a component insoluble in n-decane and recovering from the filtrate a component soluble in n-decane.

The ethylene copolymer according to the present invention, which has the characteristics described above, can be prepared, for example, by copolymerizing ethylene with an α-olefin having from 3 to 20 carbon atoms, in the presence of a catalyst consisting of:

(i) a catalytic component obtained by the reaction of a bidentate compound in which two groups selected from negatively ionized indenyl groups or substituents thereof are linked together through a group containing carbon and / or silicon, such as a lower alkylene group and a halide of a transition metal from Group IVB of the Periodic Table (the catalytic component is practically the same as the transition metal compound comprising at least two ligands each with a backbone of cyclopentadienyl, said two ligands being linked together at least through a group containing carbon and / or silicon such as a lower alkylene group);

(ii) an organoaluminum oxy-compound;

(iii) an organoaluminum compound; and (iv) a support;

so that the copolymer obtained has a density of 0.87 to 0.94 g / cm³.

In the catalytic component (i) of the invention, the bidentate compound (i-1) having two groups selected from negatively ionized indenyl groups or their substituents, which are linked to each other through a group containing carbon and / or silicon such as a lower alkylene group, it is represented by the formula:

MR¹-R²-R³M where R¹ and R³ are each an indenyl anion, a substituted indenyl anion, or a partially hydrogenated anion of any of these anions, R¹ and R³ they can be the same or different, R² is a lower alkylene group and M is an alkali metal cation. Concrete examples of the bidentate compound (i-1) include:

Ethylenebisindenyldilithium, ethylenebisidenedilithium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dilithium, ethylenebis (4-methyl-1-indenyl) dilithium, ethylenebis (5-methyl-5-methyl-1-indenyl) dilithium, ethylenebis ( 6-methyl-1-indenyl) dilithium and ethylenebis (7-methyl-1-indenyl) dilithium.

Concrete examples of the halide (i-2) of a transition metal from group IVB of the Periodic Table include zirconium tetrachloride, hafnium tetrachloride, titanium tetrachloride and titanium tetrabromide.

The catalytic component (i) used in the invention is prepared by mixing and contacting said bidentate compound as described above, with said transition metal compound and with said halide as described above, in an organic solvent, such such as ether, tetrahydrofuran, benzene, toluene, and methylene dichloride. During preparation, the mixing molar ratio (MR¹-R²-R³M / transition metal) of the bidentate compound (i-1) to the halide (i-2) of a transition metal by 0.5 to 2, preferably 0.75 to 1.25, and the concentration of the metal transition is usually 0.03 to 0.5 mol / l, preferably 0.05 to 0.3 mol / l.

Next, a discussion is made regarding the organoaluminum oxy-compound (ii).

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The organoaluminum oxy-compound (ii) may be a known aluminoxane or the benzene-insoluble organoaluminum oxy-compound discovered by the present inventors.

Said aluminoxane can be prepared, for example, by the following procedures:

(1) A process for recovering an aluminoxane as its hydrocarbon solution, which comprises adding an organoaluminum compound, such as trialkylaluminum, to a suspension in a hydrocarbon medium of a compound containing adsorbed water, or a salt containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, and hydrated waxy chloride, reacting the organoaluminum compound; and (2) a process for recovering an aluminoxane as its hydrocarbon solution, which comprises reacting water, ice, or steam directly with an organoaluminum compound such as trialkylaluminum, in a solvent such as benzene, toluene, etholic ether, and tetrahydrofuran.

In addition, the aluminoxane may contain a small amount of an organometallic compound. On the other hand, the solvent or unreacted organoaluminum compound can be separated from said recovered solution containing aluminoxane by distillation and the aluminoxane can be dissolved again in a solvent.

Concrete examples of the organoaluminum compound used in the preparation of the aluminoxane include:

trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butyylaluminum, tri-tert -butylaluminio, tripenteylaluminio, trihexilatilacilalinario, tripenteylaluminio, trihexilatilaciloaluminio;

dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride;

dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride;

dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Among these compounds, trialkylaluminum compounds are particularly preferred.

Furthermore, as an organoaluminum compound, isoprenylaluminum can also be used, represented by the general formula:

u-Cdlm Al. (C5H10K where x, y and z are each a positive number and z&gt; 2x.

The organoaluminum compounds mentioned above can be used either alone or in combination.

Solvents used for the aluminoxane solutions include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alichoclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and halogenated compounds derived from said aromatic hydrocarbons, alifaotic hydrocarbons and alicyclic hydrocarbons, especially chlorinated and brominated hydrocarbons.

In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among the solvents discussed above, aromaotic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy-compounds used in the invention contain an Al component soluble in benzene at 60^orC in an amount not more than 10%, preferably not more than 5%, especially not more than 2% in terms of Al atoms, and they are insoluble or poorly

ES 2 165 347 T3 soluble in benzene.

The solubility in benzene of said organoaluminum oxy-compounds is obtained by suspending, in 100 ml of benzene, the organoaluminum oxy-compound in an amount corresponding to 100 mg-atoms in terms of Al, mixing the resulting suspension at 60^orC for 6 hours with stirring, filtering the resulting mixture with a G-5 glass filter equipped with a jacket maintained at 60^or C, washing the separated solid portion on the filter four times with 50 ml of benzene at 60^or C and measuring the amount (x mmol) of Al atoms present in the entire filtrate.

When the benzene-insoluble organoaluminum oxy-compounds described above are analyzed by infrared (IR) spectrophotometry, the ratio (D₁₂₆₀/ D₁₂₂₀) of absorbance (D1260) at 1260 cm^-1approximately to absorbance (D₁₂₂₀) at 1220 cm^-1 about is preferably not more than 0.09, more particularly not more than 0.08 and especially of the order of 0.04 to 0.07.

The infrared spectrophotometric analysis of the organoaluminum oxy-compounds was carried out in the following manner.

First, the organoaluminum oxy-compound is ground, together with nujol, in an aógate mortar, in a nitrogen box, to form a paste.

Next, the pasta sample obtained is kept between KBr plates and the IR spectrum is measured in a nitrogen atmosphere by means of an IR-810 apparatus manufactured by Nippon Bunko KK.

The IR spectrum of the organoaluminum oxy-compound used in the present invention is shown in Figure 2.

From the IR spectrum thus obtained, the relationship D is obtained₁₂₆₀/ D₁₂₂₀ as follows.

(a) As reference line L1, we take a line that connects a maximum point at around 1280 cm^-1 and a maximum point at around 1240 cm^-1;

(b) The transmittance (T%) of a minimum absorption point at 1260 cm is read^-1 approximately and the transmittance (T_or %) of an intersection point formed by a vertical line from said absorbing point with an axis of number of waves (abscissa) and said reference line L₁, and the absorbance (D₁₂₆₀= log T_or/ T);

(c) Similarly, as the L2 reference line, we take a line that connects the maximum points at 1280 cm^-1 approximately and in 1180 cm^-1 approximately;

(d) Calculate the transmittance (T '%) of a multiple point of absorption at about 1220 cm^-1and the transmittance (T '_or %) of an intersection point formed by a vertical line from said absorption monymous point to an axis of number of waves (abscissa) and said reference line L₂, and the absorbance (D₁₂₂₀= log T '_or/ T ');

(e) From these values ​​thus obtained, the relation D is calculated₁₂₆₀/ D₁₂₂₀.

The IR spectrum of a known benzene-soluble organoaluminum oxy-compound is shown in Figure 3. As can be seen from Figure 3, the benzene-soluble organoaluminum oxy-compound has a D value.₁₂₆₀/ D₁₂₂₀ from about 0.10 to 0.13, and thus the benzene-insoluble organoaluminum oxy-compound used in the present invention obviously differs from, as regards the D-value₁₂₆₀/ D₁₂₂₀, of the already known benzene-soluble organoaluminum oxy-compound.

The benzene insoluble organoaluminum oxy-compounds described above are believed to have an alkyloxyaluminum unit represented by the formula _R1

I ^-TO&gt;-°^— where R¹ is a hydrocarbon group with 1 to 12 carbon atoms.

IS 2 165 347 T3

In said alkyloxyaluminum unit, R¹ includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl, and cyclooctyl. Among these hydrocarbon groups, the preferred ones are methyl and ethyl and in particular methyl.

In addition to the alkyloxyaluminum unit [I] of formula _R1

I ^{-Al - O -} where R¹ is a hydrocarbon group with 1 to 12 carbon atoms, benzene-insoluble organoaluminum oxy-compounds may contain an oxyaluminum unit [II] represented by the formula

R²

I ^{—Al - O -} where R² is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an aryloxy group of 6 to 20 carbon atoms, a hydroxyl, halogen or hydrogen group, provided that R¹ in the alkyloxyaluminum unit [I] and R² are different from each other. In this case, the organoaluminum oxy-compounds suitably contain the alkyloxyaluminum unit [I] in a proportion of not less than 30 mole%, preferably not less than 50 mole% and especially not less than 70 mole%.

The procedure for preparing the benzene-insoluble organoaluminum oxy-compounds described above is concretely illustrated below.

The benzene-insoluble organoaluminum oxy-compound is obtained by contacting a solution of an aluminoxane with water or with an active hydrogen-containing compound.

Examples of the active hydrogen-containing compound include: alcohols such as methanol, ethanol, n-propanol, and isopropanol; diols such as ethylene glycol and hydroquinone; and organic acids such as acetic acid and propionic acid.

Among these compounds, alcohols and diols are preferred, and alcohols in particular.

The water or active hydrogen-containing compound with which the aluminoxane solution is contacted can be used as a solution or a dispersion in a hydrocarbon solvent such as benzene, toluene and hexane, in an ether solvent such as tetrahydrofuran or in an amine solvent such as triethylamine, can either be used in vapor form or in saline form. The water with which the aluminoxane solution comes into contact can be water of crystallization of a salt such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate and waxy chloride, or it can be water adsorbed on an inorganic compound such as silica, alumina and aluminum hydroxide or on a polymer.

The reaction of the aluminoxane solution with water or with an active hydrogen-containing compound is normally carried out in a solvent, for example a hydrocarbon solvent. Examples of the solvent used in this case include: aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclohexane; petroleum fractions such as gasoline, kerosene, and diesel; or halogenated compounds of said aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, in particular chlorides and bromides; and ethers such as ethereal and tetrahydrofuran.

Among these solvents, aromatic hydrocarbons are particularly preferred.

In said reaction, the water or the active hydrogen-containing compound is used in an amount of 0.1-5 moles, preferably 0.2-3 moles, based on 1 g atom of Al present in the aluminoxane solution. The concentration in terms of aluminum atoms in the reaction system is conveniently 1 x 10^-3 - 5 g-atoms / l, preferably 1 x 10 ² - 3 g-atoms / l, and the water concentration in the reaction system is conveniently 2 x 10^-4 - 5 moles / l, preferably 2 x 10 ³ 3 moles / l.

IS 2 165 347 T3

The aluminoxane solution can be contacted with water or with the active hydrogen-containing compound, for example, by the following procedures:

(1) A process comprising contacting the aluminoxane solution with a hydrocarbon solvent containing water or the active hydrogen-containing compound.

(2) A process that comprises blowing steam or steam of the active hydrogen-containing compound into the aluminoxane solution, whereby the aluminoxane comes into contact with the water steam or with the steam of the active hydrogen-containing compound.

(3) A process comprising directly contacting the aluminoxane solution with water, ice or with the active hydrogen-containing compound.

(4) A process that comprises mixing the aluminoxane solution with a suspension of a compound containing adsorbed water or with a compound containing water of crystallization in a hydrocarbon, or with a suspension of a compound on which the compound has been adsorbed. compound containing active hydrogen, in a hydrocarbon, whereby aluminoxane comes into contact with the adsorbed water or with the water of crystallization.

The aluminoxane solution may contain other components as long as they do not have adverse effects on the reaction of the aluminoxane with water or with the active hydrogen-containing compound.

The reaction of the aluminoxane solution with water or with the active hydrogen-containing compound is normally carried out at a temperature of -50 to 150^orC, preferably 0 to 120^orC, more preferably 20 to 100^or C. The reaction time is normally 0.5 to 300 hours, preferably approximately 1 to 150 hours, although said reaction time varies fundamentally as a function of the reaction temperature used.

The benzene-insoluble organoaluminum oxy-compound can also be prepared by direct contact of said organoaluminum with water. In this case, the water is used in an amount such that the dissolved organoaluminum atoms in the reaction system do not exceed 20%, based on the total organoaluminum atoms.

The water with which the organoaluminum compound is contacted can be used as a solution or dispersion in a hydrocarbon solvent such as benzene, toluene and hexane, in an ether solvent such as tetrahydrofuran or in an amine solvent such as triethylamine, or It can either be used in the form of water vapor or ice. The water with which the organoaluminum compound is contacted can be water of crystallization of a salt such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and waxy chloride, or it can be water adsorbed on an inorganic compound such as solid, alumina and aluminum hydroxide or on a polymer.

The reaction of the organoaluminum compound with water was normally carried out in a solvent, for example a hydrocarbon solvent. Examples of the solvent used in this case include: aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alichoclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclohexane; petroleum fractions such as gasoline, kerosene, and diesel; or halogenated compounds of said aromatic hydrocarbons, alifaotic hydrocarbons and alichoclic hydrocarbons, in particular chlorides and bromides; and ethers such as ethyl ether and tetrahydrofuran. Among these solvents, aromotic hydrocarbons are particularly preferred.

The concentration of the organoaluminum compound in the reaction system, in terms of aluminum atoms, is conveniently 1 x 10 ³ - 5 g-atoms / l, preferably 1 x 10 ² - 3 g-atoms / l, and the concentration of water in the reaction system is conveniently 1 x 10^-3 - 5 moles / l, preferably 1 x 10^-2 - 3 moles / l. In the aforementioned reaction, the dissolved organoaluminum atoms in the reaction system do not exceed 20%, preferably do not exceed 10% and more preferably represent 0 to 5% based on the total organoaluminum atoms.

The organoaluminum compound can be contacted with water, for example, by the following procedures.

(1) A process comprising contacting the hydrocarbon solution of the organoaluminum with water containing a hydrocarbon solvent.

ES 2 165 347 T3 (2) A process comprising blowing steam into the hydrocarbon solution of the organoaluminum, etc., whereby the organoaluminum comes into contact with the steam.

(3) A process comprising mixing the hydrocarbon solution of the organoaluminum with a suspension of a compound containing adsorbed water or with a compound containing water of crystallization in a hydrocarbon, whereby the organoaluminum is brought into contact with the adsorbed water or with the water of crystallization.

(4) A process comprising directly contacting the hydrocarbon solution of the organoaluminum with iron.

The hydrocarbon solution of the organoaluminum described above may contain other components as long as these do not exert adverse effects on the reaction of the organoaluminum with water.

Said reaction of the organoaluminum with water is carried out at a temperature normally from -100 to 150^orC, preferably -70 to 100^orC, more preferably -50 to 80^orC. The reaction time is usually 1 to 200 hours, preferably 2 to 100 hours, although the reaction time varies greatly depending on the reaction temperature used.

Next, the organoaluminum compound (iii) used in the invention is illustrated.

Examples of the organoaluminum compound (iii) used in this invention include an organoaluminum compound represented by the formula:

R⁶_nAlX3__n where R⁶ is a hydrocarbon group of 1 to 12 carbon atoms, X is halogen or hydrogen and n is 1 to 3.

In the above formula, R⁶ It is a hydrocarbon group of 1 to 12 carbon atoms, for example an alkyl group, a cycloalkyl group or an aryl group. Concrete examples of R⁶ They include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, and tolyl.

Concrete examples of such organoaluminum compounds include:

- trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum and tri-2-ethylhexilaluminio;

- alkenylaluminum compounds such as isoprenylaluminum;

dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide;

- alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;

- alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; Y

- alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

In addition, other organoaluminum compounds represented by the formula can also be used:

R⁶„AlY3_„ where R⁶ defined as above, Y is -OR⁷, -OSiR⁸3, -OAlR⁹2, -NR¹⁰2, -SiRⁿ3, or -N (R¹²) AlR¹³2, n is 1 to 2, R⁷, R⁸, R⁹ and R¹³ are each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, or phenyl, R¹⁰ is hydrogen, methyl, ethyl, isopropyl, phenyl, or trimethylsilyl, R¹¹ and R¹² they are each methyl or ethyl.

The organoaluminum compounds listed above include, in full, the compounds listed below.

(1) Compounds of formula R⁶„Al (OR⁷)₃_ „Such as dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide.

ES 2 165 347 T3 (2) Compounds of formula R⁶nAl (OSiR⁸3)_3-n such as Et2Al (OSiMe3), (iso-Bu)₂Al (OSiMe₃) and (iso-Bu)₂Al (OSiEt₃).

(3) Compounds of formula R⁶nAl (OAlR⁹2)_3-n such as Et₂AlOAlEt₂ e (iso-Bu)₂AlOAl (iso-Bu)₂.

(4) Compounds of formula a R⁶nAl (NR¹⁰2)_3-n such as Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt, Et₂AlN (SiMe₃)₂, (iso-Bu)₂AlN (SiMe₂)₂.

(5) Compounds of formula R⁶nA (SiR¹¹3)_3-n such as (iso-Bu)₂AlSiMe₃.

(6) Compounds of formula R⁶nAl (NAlR¹³2)_3-n such as Et₂AlNAlEt₂ e (iso-Bu)₂AlNAl (iso-Bu)₂.

III

R¹² I Et

Among the organoaluminum compounds exemplified above, those having the formulas are preferred:

R⁶3Al, R⁶„Al (OR⁷) 3_ „and R⁶„Al (OAlR⁹2) 3- „, and in particular those having the above formulas where R⁶ is isoalkyl and n is 2. These organoaluminum compounds can also be used in combination of 2 or more.

The support used for the catalyst component (iv) of the invention is an inorganic or organic solid compound in the form of granules or fine particles having a particle size of 10 to 300 preferably 20 to 200 Among these supports, the porous oxides as inorganic supports. Specific examples of oxide supports include SiO₂, To the₂OR₃, MgO, ZrO₂, Uncle₂, B₂OR₃, CaO, ZnO, BaO, ThO₂ or a mixture of these compounds such as SiO₂-MgO, SiO₂-To the₂OR₃, Yes₂-Uncle₂, Yes₂-V₂OR₅, Yes₂-Cr₂OR₃ and SiO₂-Uncle₂-MgO. Among these supports, those that comprise at least one compound selected from the group consisting of SiO are preferred.₂ and Al₂OR₃ as the main component.

Furthermore, the inorganic oxide (s) mentioned above may also contain a small amount of a carbonate, a sulfate, a nitrate and an oxide, such as Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na2SO₄, Al2 (SO₄) 3, BaSO₄, KNO3, Mg (NO3E AlCNOaja, Na2O, K2O and LiO2.

Although porous inorganic supports have different properties among themselves that depend on the types and methods for their preparation, the supports preferably used in the invention have a specific surface area of ​​50 to 1,000 μm.²/ g, preferably 100 to 700 m²/ g, a pore volume conveniently 0.3 to 2.5 cm²/ g. The supports are prepared, if necessary, by calcination at a temperature of 150 to 1,000^ORC, preferably 200 to 800^ORC.

Furthermore, orgaonic compounds in the form of solid granules or solid fine particles with a particle size of 10 to 300 µm can be mentioned as supports that can be used in the present invention. Examples of these orgaonic compounds include (co) polyomers containing, as the main component, constituent units derived from an α-olefin of 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. or polymers or copolymers containing, as the main component, constituent units derived from vinylcyclohexane or styrene.

In the present invention, it is convenient that, during the preparation of the ethylene copolymers, a catalyst formed by prepolymerization of an olefin is used on the catalytic components (i), (ii), (iii) and (iv).

Before prepolymerization, the catalyst component (i), the catalyst components (i) and (ii), or the catalyst components (i), (ii) and (iii) can be supported on the catalyst component (iv), a support, or the catalytic components can be arbitrarily contacted with each other and mixed and used for prepolymerization.

A spheric olephonic copolymer excellent in particle shape can be obtained in the case that the catahotic component (i) is used, during the prepolymerization, with the transition metal compound (vi) containing ligands each of They have a cyclopentadienyl skeleton and are not linked together.

Concrete examples of the transition metal compound (vi) comprising ligands that have a cyclopentadienyl backbone and that are not bonded to each other include:

ES 2 165 347 T3 bis (cyclopentadienyl) zirconium dichloride bis (methylcyclopentadienyl) zirconium dichloride bis (dimethylcyclopentadienyl) zirconium dichloride bis (ethylcyclopentadienyl) zirconium bis (n-butylcyclopentadienyl) zirconium dichloride bis (n-butylcyclopenedienyl) dichloride bis (n-butylcyclopenedienyl) dichloride dichloride zirconium.

The use ratio of the transition metal compound (vi) to the catalyst component (i) is 0 to 50 mole%, preferably 5 to 40 mole%, more preferably 10 to 30 mole% based on the amount total of components (i) and (vi) defined as 100 mole%.

During the prepolymerization, the olefinic polymer (v) is formed in an amount, based on 1 g of the support, of 0.05 to 100 g, preferably 0.1 to 50 g, more preferably 0.2 to 30 g.

Examples of olefins include ethylene and an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene. Among these, ethylene is preferred.

The prepolymerization was carried out without solvent or in an inactive hydrocarbon solvent. In the prepolymerization process, the organoaluminum compound is used in an amount of 0.2 to 20 mmol, preferably 0.5 to 10 mmol; the organoaluminum oxy-compound in an amount of 1 to 50 mg-atoms, preferably 2 to 20 mg-atoms in terms of Al; and the catalyst component (i) in an amount of 0.02 to 2 atom-mg, preferably 0.05 to 1 atom-mg in terms of the transition metal, all amounts being based on 1 g of the support.

Furthermore, a convenient molecular ratio of the organoaluminum compound (iii) in terms of Al atoms to the oxy-organoaluminum compound (ii) in terms of Al otoms [Al (iii) / Al (ii)] is usually 0, 02 to 3, preferably 0.5 to 1.5. The molecular ratio of the organoaluminum oxy-compound (ii) in terms of Al atom to the catalytic component (i) in terms of transition metal atom (M) [Al (ii) / M] is normally 5 to 250, preferably 10 to 150. When the prepolymerization is carried out in an inactive hydrocarbon solvent, the concentration of the catalyst component (i), in terms of the transition metal, is normally 0.1 to 10 atom-mg / liter, preferably 0.5 to 5 atom-mg / liter. -mg / liter.

Prepolymerization is carried out at a temperature of -20 to 70^orC, preferably -10 to 60^orC, more preferably 0 to 50^orC.

The prepolymerization can be carried out discontinuously or continuously and under reduced pressure, under normal pressure or under the application of pressure. Although a molecular weight modifier, such as hydrogen, may be present during prepolymerization, its amount is suitably limited so that a prepolymer can be prepared having an intrinsic viscosity [η] of not less than 0.2 dl / g, preferably 0.5 to 10 dl / g, measured in decalin at 135^orC.

In the prepolymerization catalyst thus obtained, the catalyst component (i) is supported in an amount in terms of the transition metal atom, based on 1 g of the support, from 0.1 to 50 mg, preferably from 0.3 to 30 mg, more preferably 0.5 to 20 mg. The molecular ratio of the catalytic components (ii) and (iii) in terms of Al atoms to the catalytic component (i) in terms of the transition metal (M) (Al / M) is 5 to 200, preferably 10 to 150, more preferably 15 to 100.

The ethylene copolymers according to the invention are obtained by copolymerizing ethylene with said α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In the present invention, olefin is usually polymerized in the gas phase or in the liquid phase, for example in suspension. In suspension polymerization, an inactive hydrocarbon is used as the solvent.

Specific examples of the hydrocarbon solvent include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; hydrocar

ES 2 165 347 T3 alicyclic bides such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; and petroleum fractions such as gasoline, kerosene, and diesel. Among these hydrocarbons, preferred are aliphatic hydrocarbons, alicyclic hydrocarbons and petroleum fractions.

In the present invention, the suspension polymerization is carried out at a temperature usually from -50 to 100^orC, preferably 0 to 90 ° C.

In the present invention, the gas phase polymerization is carried out at a temperature usually from 0 to 120 ° C, preferably from 20 to 100 ° C.

In the suspension polymerization or gas phase polymerization of the invention, the concentration of the transition metal compound is usually 10 ⁸ to 10 ² g-atoms / liter, preferably 10^-7 to 10 ³ g-atoms / liter, in terms of the transition metal.

Furthermore, in the polymerization of the invention, an aluminum oxy-compound or an aluminum compound similar to those used in the catalyst components (ii) and (iii) can be added. During polymerization, the ratio of aluminum compound in terms of Al atoms to the transition metal atom (M) (Al / M) is 5 to 300, preferably 10 to 200, more preferably 15 to 150.

Polymerization is normally carried out at a pressure between normal pressure and 100 kg / cm², preferably under a pressure of 2 to 50 kg / cm². The polymerization can be carried out batchwise, semi-continuously or continuously.

Furthermore, the polymerization can also be carried out in not less than 2 stages where different reaction conditions are used.

The second process for the preparation of an ethylene copolymer according to the present invention, is illustrated below in a concrete way.

The ethylene copolymer prepared by the second process for the preparation of said copolymer according to the present invention is a random copolymer of ethylene with an α-olefin having 3 to 20 carbon atoms.

The random copolymer of ethylene with α-olefin having 3 to 20 carbon atoms, prepared by the second procedure according to the invention, has the characteristics described above.

In the second procedure for the preparation of an ethylene copolymer according to the invention, a solid catalyst formed from:

(A) a compound of a transition metal of group IVB of the Periodic Table, having, as a ligand, at least two groups having a cyclopentadienyl backbone, at least said two or more groups cross-linked through a group containing carbon and / or silicon; and (B) an organoaluminum oxy-compound;

and the polymerization of the olefin is carried out under the condition that the polymer produced exists in a solid state in the polymerization system.

The transition metal compound (A) used in the second procedure for preparing the ethylene copolymer according to the present invention, is represented by the formula

M¹L¹x where M¹ is a transition metal, L¹ is a ligand that coordinates with the transition metal, having at least two of the L ligands¹ a cyclopentadienyl skeleton and being linked together through a group containing carbon and / or silicon, L¹ other than the ligand having the cyclopentadienyl backbone is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group, an aryloxy, halogen or hydrogen group, and x is the valence of the transition metal.

In the above formula, M¹ is a transition metal and preferred concrete examples of M¹They include zirconium, titanium, hafnium, chromium, and vanadium. Among these, zirconium and hafnium are particularly preferred.

IS 2 165 347 T3

Ligands having a cyclopentadienyl backbone include, for example, cyclopentadienyl, an alkyl-substituted cyclopentadienyl group, such as methylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, dimethylcyclopentadienyl, and pentamethylcyclopentadienyl, 4,5orenyl, 6, and pentamethylcyclopentadienyl.

The ligand other than those having a cyclopentadienyl backbone is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, halogen or hydrogen.

The hydrocarbon group having 1 to 12 carbon atoms includes, for example, an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and concrete examples of these groups are as follows:

an alkyl group such as methyl, ethyl, propyl, isopropyl, and butyl;

a cycloalkyl group such as cyclopentyl and cyclohexyl;

an aryl group such as phenyl and tolyl;

an aralkyl group such as benzyl and neophyl;

an alkoxy group such as methoxy, ethoxy, and butoxy;

an aryloxy group such as phenoxy; and halogen such as fluorine, chlorine, bromine, and iodine.

Said transition metal compound (A) comprising ligands having a cyclopentadienyl backbone, as used in the present invention, and having a transition metal with a valence of 4, can be more concretely represented by the formula

R²R³R⁴R⁵M¹ where M¹ is zirconium, titanium, hafnium or vanadium, at least two of R², R³, R⁴, R⁵, for example R² and R³, are each a group having a cyclopentadienyl backbone, the two mentioned groups being linked to each other, each with a cyclopentadienyl skeleton, through a group containing carbon and / or silicon, such as an alkylene group. (for example, ethylene and propylene), a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group and a substituted silylene group such as dimethylsilylene, R⁴ and R⁵ they are each a group having a cyclopentadienyl backbone, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, halogen or hydrogen.

Specific examples of the transition metal compound (A) having at least two ligands containing a cyclopentadienyl backbone are given below, at least two of said ligands having a cyclopentadienyl backbone being linked together through an alkylene group. , a substituted alkylene group, a silylene group or a substituted silylene group:

Ethylenebis (indenyl) dimethylzirconium,

Ethylenebis (indenyl) diethylzirconium,

Ethylenebis (indenyl) diphenylzirconium monochloride,

Ethylenebis (indenyl) methylzirconium monochloride,

Ethylenebis (indenyl) ethylzirconium monochloride,

Ethylenebis (indenyl) methylzirconium monobromide,

Ethylenebis (indenyl) zirconium dichloride

Ethylenebis (indenyl) zirconium dibromide

Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium,

Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylzirconium monochloride,

Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride,

Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide,

Ethylenebis (4-methyl-l-indenyl) zirconium dichloride,

Ethylenebis (5-methyl-l-indenyl) zirconium dichloride,

Ethylenebis (6-methyl-l-indenyl) zirconium dichloride,

Ethylenebis (7-methyl-l-indenyl) zirconium dichloride,

IS 2 165 347 T3

Ethylenebis (5-methoxy-1-indenyl) zirconium dichloride,

Ethylenebis (2,3-dimethyl-l-indenyl) zirconium dichloride,

Ethylenebis (4,7-dimethyl-l-indenyl) zirconium dichloride,

Ethylenebis (4,7-dimethoxy-1-indenyl) zirconium dichloride,

Isopropylidene (cyclopentadienylfluorenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-2,7-di-tert-butylfluorenyl) zirconium dichloride,

Isopropylidene (cyclopentadienylmethylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride,

Dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, and

Dimethylsilylenebis (indenyl) zirconium dichloride

Transition metal compounds obtained by employing titanium, hafnium or vanadium in place of zirconium can also be used in the zirconium compounds exemplified above.

In the second process for the preparation of an olefinic polymer according to the present invention, a compound similar to the organoaluminum oxy-compound (ii) is used as the organoaluminum oxy-compound (B).

Furthermore, in the second process for the preparation of the ethylene copolymer according to the present invention, an organoaluminum compound (C) can also be used, if necessary, in addition to the transition metal compound (A) and the oxy-compound of organoaluminum (B) as described above, during the preparation of an ethylene copolymer.

For said organoaluminum compound (C), a compound similar to the organoaluminum compound (iii) is used.

The catalytic component used in the second process for the preparation of the ethylene copolymer according to the invention, is in the solid state and said solid catalytic component can be prepared, for example, by supporting the catalytic component (A) on a support (D) or on a solid organoaluminum oxycomposite.

As support (D), a support similar to that described above can be used.

In the preparation of an ethylene copolymer by the second process according to the invention, it is convenient to use a catalyst formed by prepolymerization of olefins on catalytic components that include the catalytic components (A) and (B) and, if necessary, the catalytic component (C) and / or catalytic component (D), all these catalytic components having been previously described.

Before prepolymerization, the catalytic component (A), the catalytic components (A) and (B) or the catalytic components (A), (B) and (C) can be previously supported on a support, or these catalytic components they can only be arbitrarily contacted and mixed.

When a transitional metal compound (E) containing ligands each of which has a cyclopentadienyl backbone is used, said ligands not being linked together, with the catalytic component (A) during the contacting and mixing operation, it is It can prepare a spheric olefinic copolymer with excellent particulate properties.

The transition metal compound (E) used if necessary in the present invention is a compound similar to the transition metal compound (vi) described above that contains ligands each of them with a cyclopentadienyl backbone, not being linked between said ligands only, and are illustrated in more detail below. The transition metal compound (E) is represented by the formula

M²L²x

ES 2 165 347 T3 where M² is a transition metal, L² is a ligand that coordinates with the transition metal, at least one of the L ligands² is a ligand that has a cyclopentadienyl backbone, L² other than the ligand having a cyclopentadienyl backbone is a hydrocarbon group of 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, halogen or hydrogen, and x is the valence of the transition metal.

In the formula indicated above, M² is a transition metal and preferred concrete examples of M²They include zirconium, titanium, hafnium, chromium, and vanadium. Among these, zirconium and hafnium are particularly preferred. Ligands having a cyclopentadienyl backbone include, for example, cyclopentadienyl, an alkyl-substituted cyclopentadienyl group, such as methylcyclopentadienyl, ethylcyclopentadienyl, n-butylcyclopentadienyl, dimethylcyclopentadienyl, and pentamethylcyclopentadienyl, and innylcyclopentadienyl.

At least one, and preferably two ligands each of which has a cyclopentadienyl backbone, as mentioned above, coordinate with the transitional metal M².

The ligand other than those having a cyclopentadienyl backbone is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, halogen or hydrogen.

The hydrocarbon group having 1 to 12 carbon atoms includes, for example, an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and concrete examples of these groups are as follows:

an alkyl group such as methyl, ethyl, propyl, isopropyl, and butyl;

a cycloalkyl group such as cyclopentyl and cyclohexyl;

an aryl group such as phenyl and tolyl;

an aralkyl group such as benzyl and neophyl;

an alkoxy group such as methoxy, ethoxy, and butoxy;

an aryloxy group such as phenoxy; and halogen such as fluorine, chlorine, bromine and iodine

Said transition metal compound (E) containing ligands each of them with a cyclopentadienyl backbone, which is not linked to other cyclopendadienyl backbones, as used in the present invention and which has a transition metal with a valence of 4, maús can be represented concretely by the formula

R²'kR³'1R⁴'mR⁵'nM² where M² is zirconium, titanium, hafnium or vanadium, R² is a group having a cyclopentadienyl backbone, R³ , R⁴ and R⁵ are each a group having a cyclopentadienyl backbone, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, halogen or hydrogen, k is an integer not less than 1 and k + 1 + m + n = 4.

Following are concrete examples of the transition metal compound (E) containing zirconium as M² and ligands each with a cyclopentadienyl backbone that is not linked to other cyclopentadienyl backbones:

Bis (cyclopentadienyl) zirconium monochloride monohydride

Bis (cyclopentadienyl) zirconium monobromide monohydride,

Bis (cyclopentadienyl) methylzirconium hydride,

Bis (cyclopentadienyl) ethylzirconium hydride,

Bis (cyclopentadienyl) phenylzirconium hydride,

Bis (cyclopentadienyl) benzylzirconium hydride,

Bis (cyclopentadienyl) neopentylzirconium hydride,

Bis (methylcyclopentadienyl) zirconium monochloride hydride,

Bis (indenyl) zirconium monochloride monohydride,

Bis (cyclopentadienyl) zirconium dichloride,

Bis (cyclopentadienyl) zirconium dibromide,

Bis (cyclopentadienyl) methylzirconium monochloride,

IS 2 165 347 T3

Bis (cyclopentadienyl) ethylzirconium monochloride,

Bis (cyclopentadienyl) cyclohexylzirconium monochloride,

Bis (cyclopentadienyl) phenylzirconium monochloride,

Bis (cyclopentadienyl) benzylzirconium monochloride,

Bis (methylcyclopentadienyl) zirconium dichloride,

Bis (dimethylcyclopentadienyl) zirconium dichloride,

Bis (n-butylcyclopentadienyl) zirconium dichloride,

Bis (indenyl) zirconium dichloride,

Bis (indenyl) zirconium dibromide,

Bis (cyclopentadienyl) zirconiodimethyl,

Bis (cyclopentadienyl) zirconiodiphenyl, Bis (cyclopentadienyl) zirconiodibenzyl, Bis (cyclopentadienyl) zirconium methoxychloride, Bis (cyclopentadienyl) zirconium ethoxychloride, Bis (methylcyclopentadienyl) bis (methylcyclopentadienyl) cyclopentadienyl cyclopentadienyl (cyclopentadienyl) bis (methylcyclopentadienyl) zirconidechloride ethoxychloride ) zirconium.

Transition metal compounds obtained using titanium, hafnium or vanadium in place of zirconium can also be employed in the above exemplified zirconium compounds.

During the prepolymerization, the olephonic polymer is formed in an amount, based on 1 g of the support, of 0.05 to 100 g, preferably 0.1 to 50 g, more preferably 0.2 to 30 g.

Examples of olefins include ethylene and an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene. Among these, ethylene is preferred.

The prepolymerization was carried out without solvent or in an inactive hydrocarbon solvent. In the prepolymerization process, the organoaluminum compound is used in an amount of 0.2 to 20 mmol, preferably 0.5 to 10 mmol; the organoaluminum oxy-compound in an amount of 1 to 50 mg-atoms, preferably 2 to 20 mg-atoms in terms of Al; and the catalyst component (A) in an amount of 0.02 to 2 mg-atom, preferably 0.05 to 1 mg-atom in terms of the transition metal, all amounts being based on 1 g of the support.

Furthermore, a convenient molecular ratio [Al (C) / Al (B)] of the organoaluminum compound in terms of Al atoms [Al (C)] to the oxy-organoaluminum compound in terms of Al atoms [Al (B) ] is usually 0.02 to 3, preferably 0.05 to 1.5. A convenient molecular ratio [Al (B) / M] of the organoaluminum oxy-compound in terms of Al [Al (B)] atoms to the catalytic component (A) in terms of transition metal (M) atoms is usually 5 to 250, preferably 10 to 150.

When the prepolymerization is carried out in an inactive hydrocarbon solvent, the concentration of the catalyst component (A), in terms of the transition metal, is normally 0.1 to 10 atom-mg / liter, preferably 0.5 to 5 atom-mg. /liter.

Prepolymerization is carried out at a temperature of -20 to 70^ORC, preferably -10 to 60^ORC, more preferably 0 to 50^ORC.

The prepolymerization can be carried out discontinuously or continuously and under reduced pressure, under normal pressure or under pressure application. Although a molecular weight modifier, such as hydrogen, may be present during prepolymerization, its amount is suitably limited so that a prepolymer can be prepared having an intrinsic viscosity [η] of not less than 0.2 dl / g, preferably 0.5 to 10 dl / g, measured in decalin at 135^ORC.

In the prepolymerization catalyst thus obtained, the catalytic component (A) is supported in an amount in terms of transition metal atom, based on 1g of the support from 0.1 to 50 mg,

ES 2 165 347 T3 preferably 0.3 to 30 mg, more preferably 0.5 to 20 mg. The molecular ratio (Al / M) of the catalytic components (B) and (C) in terms of Al atoms to the catalytic component (A) in terms of the transition metal (M) is 5 to 200, preferably 10 to 150, more preferably 15 to 100.

The ethylene copolymers according to the invention are obtained by copolymerizing ethylene with said α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

In the second process for the polymerization of olefins according to the present invention, the olefin is polymerized normally under the condition that the polymer produced exists in the solid state, for example, it is polymerized in the gas phase or in suspension. In suspension polymerization, an inactive hydrocarbon is used as the solvent.

Concrete examples of the hydrocarbon solvent include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; and petroleum fractions such as gasoline, kerosene, and diesel. Among these hydrocarbons, the preferred are aliphatic hydrocarbons, alicyclic hydrocarbons and petroleum fractions.

In the present invention, suspension polymerization is carried out at a temperature typically from -50 to 100^orC, preferably 0 to 90 ° C.

In the present invention, the gas phase polymerization is carried out at a temperature usually from 0 to 120 ° C, preferably from 20 to 100 ° C.

In the suspension polymerization or in the gas phase polymerization of the invention, the concentration of the transition metal compound is normally 10 ⁸ to 10 ² g-atoms / liter, preferably 10^-7 to 10 ³ g-atoms / liter, in terms of the transition metal.

Furthermore, in the polymerization of the invention, an aluminum oxy-compound or an aluminum compound similar to those used in the catalyst components (B) and (C) can be added. During polymerization, the ratio of aluminum compound in terms of Al atoms to the transition metal atom (M) (Al / M) is 5 to 300, preferably 10 to 200, more preferably 15 to 150.

The polymerization is normally carried out at a pressure between a normal pressure and 100 kg / cm², preferably under a pressure of 2 to 50 kg / cm². The polymerization can be carried out batchwise, semi-continuously or continuously.

Furthermore, the polymerization can also be carried out in not less than 2 stages where different reaction conditions are used.

The solid catalyst for the polymerization of ethylene used in the present invention is illustrated below.

The first prepolymerized solid catalyst for olefin polymerization according to the present invention is formed by prepolymerization of the olefin in suspension or in the gas phase in the presence of a solid catalyst comprising:

[A] a fine particulate support;

[B] a transition metal compound (hereinafter referred to as a non-bridged type transition metal compound) comprising ligands having a cyclopentadienyl backbone, the cyclopentadienyl backbones not being linked to each other;

[C] a transition metal compound (hereinafter referred to as a bridged-type transition metal compound) comprising at least two ligands each with a cyclopentadienyl backbone, at least two of said ligands through an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group; ^Y

[D] an oxy-organoaluminum compound.

IS 2 165 347 T3

The second solid prepolymerized catalyst for the polymerization of ethylene used in the present invention is formed from said components [A], [B], [C], [D] and [E] an organoaluminum compound.

The support (iv) described above is used as the fine particle support [A].

As the non-bridged type transition metal compound [B], the same compound can be used as the transition metal compound (E) described above and which comprises ligands having a cyclopentadienyl backbone, the backbones of cyclopentadienyl.

As the bridged-type transition metal compound [C], the same compound described above can be used.

Furthermore, as the organoaluminum oxy-compound [D], the same compound described above can be used.

On the other hand, as the organoaluminum compound [E], the same compound described above can be used.

The prepolymerized solid catalyst for the polymerization of ethylene, used in the invention, is prepared by mixing the fine particulate support [A], the non-bridged type transition metal compound [B], the bridged type transition metal compound [C], the organoaluminum oxy-compound [D] and, without need, the organoaluminum compound [E] in an inactive hydrocarbon solvent, and introducing the olefin for prepolymerization.

Although mixing can be carried out in an arbitrarily selected order, mixing and contacting is preferably carried out in the order of [A] ([E]) [D] ^ [B] olefin [C] olefin or [ A] ([E]) [D] {[B] + [C]} olefin.

The solid prepolymerized catalyst for the polymerization of ethylene according to the invention, can also be prepared by supporting the non-bridged type transition metal compound [B], the bridged type transition metal compound [C], the oxy-compound of organoaluminum [D] and, if necessary, the organoaluminum compound [E], on the support in fine particles [A], introducing the olefin without solvent and carrying out the prepolymerization.

When mixing components [A] to [D] and, if necessary, component [E], component [B] and component [C] are used in a total amount generally of 10^-5 to 5x 10 ³ mol, preferably 5x10^-5 to 10 ³ mol, based on 1 g of component [A], and a total concentration of about 10^-4 to 2x10^-2 mol / l, preferably 2x10^-4 to 10^-2 mol / l. Component [B] is employed in an amount of 5 to 80 mole%, preferably 7 to 70 mole%, more preferably 10 to 60 mole%, based on the amount of component [B] and component [C] of 100 mole% in total.

The atomic ratio [Al / (transition metal)] of aluminum in component [D] to the transition metal in components [B] and [C] is normally 10 to 500, preferably 20 to 200. The ratio atomic (Al_AND / AlD) of aluminum atoms (Al_AND) in the component [E] used, if necessary, to the aluminum atoms (AlD) in the component [D] is usually 0.02 to 3, preferably 0.05 to

1.5. Components [A] to [D] and, if necessary, component [E] are mixed at a temperature of normally -20 to 80^ORC, preferably 0 to 60^ORC, with a contact time of 1 to 200 minutes, preferably 5 to 120 minutes.

Ethylene or an α-olefin having 3 to 20 carbon atoms is prepolymerized in the presence of components [A] to [D] and, if necessary, component [E], described above. The prepolymerization is carried out using the transition metal compounds in an amount normally of 10⁴ to 2x10^-2 mol / l, preferably 5x10^-4 to 10^-2 mol / l at a temperature of -20 to 80^ORC, preferably 0 to 50^ORC, and for a time of 0.5 to 100 hours, preferably 1 to 50 hours.

In the prepolymerized solid catalyst for olefin polymerization used in the invention and obtained as described above, the transition metal is supported in an amount of 5x10^-6 to 5x10^-4 otome-g, preferably 10^-5 to 3x10^-4 g-atoms, and aluminum was supported in an amount of 10^-3 to 10^-1 g-otoms preferably 2x10^-3 to 5x10^-2 g-atoms, all amounts being based on 1 g of component [A].

IS 2 165 347 T3

Furthermore, the polymer is formed during the prepolymerization in an amount based on 1 g of the support in fine particles, from about 0.1 to 500 g, preferably from 0.3 to 300 g, and particularly from 1 to 100 g.

Concrete examples of the inactive hydrocarbon used as a solvent for the preparation of the solid catalyst for the polymerization of ethylene of the invention include alifaotic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures of these hydrocarbons.

In the polymerization of ethylene with said prepolymerized solid catalyst having a prepolymerized olefin as described above, the transition metal compounds [B] and [C] are conveniently employed in an amount (per liter of polymerization volume) of normally 10^-8 to 10 ³ g-otoms preferably 10 ⁷ to 10 ⁴ g-atoms in terms of the transition metal. In the polymerization, an aluminum organo compound and an aluminoxane may be employed if necessary. Examples of the organoaluminum compound used in the polymerization include compounds similar to the organoaluminum compound [E] described above. The organoaluminum compound is employed in an amount of 0 to 500 moles, preferably 5 to 200 moles based on 1 g atom of the transitionon metal. Olefins that can be polymerized with said prepolymerized catalyst include ethylene and α-olefins having 3 to 20 carbon otoms, for example, propylene, 1-butene-1-pentene, -hexene, 4-methyl-1-pentene, 1- octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4, 5,8-dimethane-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. Furthermore, styrene, vinylcyclohexane and dienes can also be used.

In the present invention, the polymerization can be carried out by means of a process for polymerization in the liquid phase such as polymerization in solution and polymerization in suspension, or by a process for polymerization in the gas phase.

In the process for liquid phase polymerization, the same inactive hydrocarbon solvent used in the preparation of the catalyst can be used.

The olefin polymerization was carried out with a catalyst as described above at a temperature normally from -50 to 150^or C, preferably 0 to 100 ° C, at a pressure normally between normal pressure and 100 kg / cm² preferably between normal pressure and 50 kg / cm². The polymerization reaction can be carried out batchwise, semi-continuously or continuously. Furthermore, the polymerization can also be carried out in two or more stages where different reaction conditions are used. The molecular weight of the olephonic polymer produced can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature.

Furthermore, in the present invention, the olefin polymerization catalyst may also contain components which are different from the above-mentioned components and which are useful for olefin polymerization.

The present invention is illustrated below with reference to examples, but it is to be understood that the present invention is in no way limited to such examples.

On the other hand, the melt stress (hereinafter sometimes abbreviated as MT) in this description, is measured by the procedure described below.

Melt tension (MT) is determined by measuring the tension of a molten polymer while it is being drawn at a constant speed. To do this, fine particles of a produced polymer or of a polymer obtained by dissolving the fine particles in decane at once and precipitating the dissolved powder with a methanol / acetone solution (volume ratio 1) are used as samples for the measurement. / 1) in an amount by volume not less than 5 times the amount of decane used, The measurement was then carried out using a MV measuring device (manufactured by Toyoseiki Seisakusho KK) having a nozzle diameter of 2.09 mm and a nozzle length of 8 mm at a resin temperature of 190 ° C, a speed of extrusion of 10 mm / min and a collection speed of 10 to 20 m / minute.

During the melt stress measurement, the ethylene copolymer samples are mixed

ES 2 165 347 T3 previously with 0.1% by weight of 2,6-di-tert-butyl-p-cresol, a crosslinking stabilizer.

Example 1

Preparation of a catalyst component (A)

A 400 ml glass flask, purged with nitrogen, was charged with 20 g of bis (indenyl) ethane and 200 ml of THF. Content cooled to -50^ORC with stirring and, over 50 minutes, 100 ml of a solution of n-BuLi (1.6 M solution) were added. The resulting mixture was then stirred at -50^ORC for 1 hour and allowed to stand to warm to room temperature, whereby the bis (indenyl) ethane became anionic. 100 ml of THF was added to the content to form a homogeneous solution.

Another nitrogen purged 1 L glass flask was charged with 250 ml THF, cooled to -50^ORC and 16.54 g of zirconium tetrachloride were gradually added. The contents of the flask were heated to 60^ORC and stirred for 1 hour. The anionic ligand prepared above was then added dropwise. The resulting mixture was stirred at 60^or C for 3 hours and filtered through a glass filter. The filtrate was condensed to 1/5 of the initial volume at room temperature to precipitate a solid, which was filtered off with the aid of a glass filter, and the solid residue was washed with a solvent mixture of hexane / ether (ratio in 1/1 volume) and dried under reduced pressure to obtain catalyst component (A).

Preparation of a catalyst component (B)

A 400 ml flask purged thoroughly with nitrogen was charged with 37 g of Al₂(SW₄)₃.14H₂O and 125 ml of toluene. The contents of the flask were cooled to 0^ORC and 500 mmol of trimethylaluminum diluted with 125 ml of toluene were added dropwise. The resulting mixture was heated to 40^ORC and the reaction was continued at that temperature for 48 hours. After completion of the reaction, the reaction mixture was subjected to solid-liquid separation by filtration and the toluene was separated from the filtrate, whereby 9.1 g of a white solid catalyst component (B) were obtained.

Preparation of a prepolymerized catalyst

A 400 ml flask purged thoroughly with nitrogen was charged with 1.29 g of silica (F-948M from Fuji Davison KK) which was calcined at 700^ORC for 6 hours before being introduced into the flask and 20 ml of toluene, to form a suspension. 4.51 ml of a triisobutylaluminum decane solution (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 30 minutes. Next, 7.91 ml of a toluene solution of the catalyst component (B) prepared above (Al: 0.95 mol / liter) was added and the mixture was stirred at room temperature for 30 minutes. 72 ml of a toluene solution of the catalyst component (A) prepared above (Zr: 0.00298 mol / liter) were then added and the resulting mixture was stirred for 10 minutes. 52 ml of decane were then added and prepolymerization was carried out at 30^ORC for 4 hours continuously introducing ethylene at normal pressure.

After the prepolymerization, the solvent was separated by decantation and the residue was washed at 60^ORC three times with 200 ml of hexane and additionally washed at room temperature three times with 200 ml of hexane, to thus obtain a prepolymerized catalyst containing 8.5 mg of Zr, 160 of Al and 15 g of polyethylene based on 1 g of silica.

Polymerization

A stainless steel autoclave with a volume of 2 liters and thoroughly purged with nitrogen, was charged with 150 g of sodium chloride (special quality from Wako Junyaku KK) and the contents were dried for 1 hour at 90^ORC under reduced pressure. The system pressure was then returned to normal pressure by introducing a gaseous mixture of ethylene and 1-butene (1-butene content: 6.3 m or%) and the temperature of the system was lowered to 70^ORC.

The prepolymerized catalyst prepared above was then added to the autoclave in an amount of 0.0075 atom-mg in terms of zirconium and 1.13 mmol of triisobutylaluminum.

Then, 50 mlN of hydrogen and the gas mixture of ethylene and 1-butene described above were successively introduced and the polymerization reaction was started at a total pressure of 4 kg / cm²gauges, so that the temperature of the system immediately rose to 80^ORC. Next,

ES 2 165 347 T3 carried out the polymerization at 80^or C for 1 hour while maintaining total pressure at 4 kg / cm²manometers feeding the gaseous mixture only.

After the polymerization was completed, sodium chloride was removed from the reaction mixture by washing with water and the remaining polymer was washed with methanol and dried overnight at 80^orC under reduced pressure, whereby 116 g of a copolymer / 1-butene were obtained containing 8.1% by weight of constituent units of 1-butene and 2.8% by weight of a component soluble in decane at 23^orC, with an MFR value of 2.30 g / 10 minutes measured at 190^orC and under a load of 2.16 kg, a density of 0.915 g / cm³, a melt tension (MT) of 5.3 g and an apparent specific density of 0.31 g / cm³, and showing an endothermic curve that has the maximum peak at 94^orC, measured by a differential scanning calorimeter (DSC).

Example 2

Preparation of a prepolymerized catalyst

To 1.30 g of the same silica used in Example 1 was added 20 ml of decane to form a suspension. 3.24 ml of triisobutylaluminum decane solution (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 30 minutes.

17.1 ml of a toluene solution of oxy-organoaluminum compound (Al: 0.95 mol / liter) synthesized by a procedure similar to that of Example 1 was then added to the suspension, and the resulting mixture was stirred at temperature. environment for 30 minutes.

Next, 1.03 ml of a toluene solution of bis (cyclopentadienyl) zirconium dichloride (Zr: 0.0417 mol / liter) was added to the suspension and the resulting mixture was stirred for 15 minutes. 50 ml of decane were added to the mixture and prepolymerization was carried out at 30^or C for 2 hours introducing ethylene continuously at normal pressure. 100.5 ml of a toluene solution of the catalyst component (A) containing 0.00172 mol / liter of Zr were then added and the prepolymerization was continued at 30^orC for 4 hours. A subsequent operation similar to that of Example 1 was then carried out to obtain a prepolymerized catalyst containing 9.3 mg of zirconium, 190 mg of aluminum and 20 g of polyethylene.

Polymerization

A polymerization procedure similar to that of Example 1 was repeated except that a gaseous mixture containing 3.6 mole% of 1-butene, 10 mlN of hydrogen and the prepolymerized catalyst described above were used in an amount of 0.005 atom-mg in terms of zirconium and 0.75 mmol in terms of triisobutylaluminum, and except that the polymerization was carried out at 70^orC for 2 hours, whereby 88 g of an ethylene / 1-butene copolymer were obtained containing 6.7% by weight of constituent units of 1-butene and 0.25% by weight of a component soluble in decane, having an MFR value of 0.48 g / 10 minutes, a density of 0.922 g / cm³, a melt tension of 11 g and an apparent specific density of 0.35 g / cm³, and showing an endothermic curve (measured by DSC) with the maximum peak at 103^or C.

Example 3

Preparation of a prepolymerized catalyst

To 3.0 g of the same silica used in Example 1 was added 30 ml of decane to form a suspension. 7.45 ml of triisobutylaluminum decane solution (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 25 minutes.

Then 39.4 ml of a toluene solution of oxy-organoaluminum compound (Al: 0.95 mol / liter) synthesized by a procedure similar to that of Example 1 was added to the suspension, and the resulting mixture was stirred at temperature environment for 25 minutes.

Then, 2.14 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr: 0.0465 mol / liter) was added to the suspension and the resulting mixture was stirred for 10 minutes. 100 ml of decane were added to the mixture and prepolymerization was carried out at 25^or C for 2.5 hours introducing ethylene continuously at normal pressure.

IS 2 165 347 T3

166.4 ml of a toluene solution of the catalyst component (A) containing 0.00240 mol / liter of Zr were then added and the prepolymerization was continued at 30^orC for 5 hours. A subsequent operation similar to that of Example 1 is then carried out to obtain a prepolymerized catalyst containing 8.2 mg of zirconium, 150 mg of aluminum and 20 g of polyethylene.

Polymerization

A polymerization procedure similar to that of Example 1 was repeated except that 30 mlN of hydrogen was added and that the prepolymerization catalyst described above was used, whereby 149 g of an ethylene / 1-butene copolymer containing 10.1 % by weight of constituent units of 1-butene and 3.1% by weight of a component soluble in decane, having an MFR value of 1.78 g / 10 minutes, a density of 0.912 g / cm³, a melt tension of 5.3 g and an apparent specific density of 0.36 g / cm³, and showing an endothermic curve (measured by DSC) with the maximum peak at 94^orC.

Example 4

Preparation of a prepolymerized catalyst

To 1.49 g of the same salt used in Example 1, 25 ml of decane was added to form a suspension. 3.72 ml of triisobutylaluminum decane solution (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 45 minutes.

Subsequently, 19.6 ml of a toluene solution of an oxy-organoaluminum compound (Al: 0.95 mol / liter) synthesized by a procedure similar to that of Example 1 was added to the suspension, and the resulting mixture was stirred at temperature. environment for 45 minutes.

Then 2.13 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr: 0.0465 mol / liter) was added to the suspension and the resulting mixture was stirred for 10 minutes. 75 ml of decane were added to the mixture and prepolymerization was carried out at 30^orC for 1.5 hours introducing ethylene continuously at normal pressure.

Then 51.9 ml of a toluene solution of the catalyst component (A) containing 0.00287 mol / liter of Zr prepared in Example 1 were added, and the prepolymerization was continued at 30^orC for 4 hours. Then a subsequent operation similar to that of Example 1 was carried out to obtain a prepolymerized catalyst containing 10.5 mg of zirconium, 190 mg of aluminum and 17 g of polyethylene based on 1 g of salice.

Polymerization

A polymerization procedure similar to that of Example 1 will be repeated except that a gaseous mixture containing 4.4 mole% of 1-butene, 30 mlN of hydrogen and the prepolymerized catalyst described above in an amount of 0.005 atom-mg in terms of zirconium and 0.5 mmol in terms of triisobutylaluminum, whereby 48 g of an ethylene / 1-butene copolymer were obtained containing 6.5% by weight of constituent units of 1-butene and 0.32% by weight of a component soluble in decane, having an MFR value of 3 , 1 g / 10 minutes, a density of 0.922 g / cm³, a melt tension of 4.9 g and an apparent specific density of 0.36 g / cm³, and showing an endothermic curve (measured by DSC) with the maximum peak at 115^orC.

Example 5

Polymerization

A polymerization procedure similar to that of Example 1 was repeated except that a gaseous mixture containing 3.6 mole% of 1-butene, 30 mlN of hydrogen and the prepolymerized catalyst described above in an amount of 0.005 atom-mg in terms of zirconium and 0.75 mmol in terms of triisobutylaluminum, and except that the polymerization is carried out at 70^or C for 1 hour, whereby 95 g of an ethylene / 1-butene copolymer were obtained containing 7.4% by weight of constituent units of 1-butene and 0.18% by weight of a component soluble in decane, having an MFR value of 0.075 g / 10 minutes, a density of 0.920 g / cm³, a melt tension of 42 g and an apparent specific density of 0.24 g / cm³, and showing an endothermic curve (measured by DSC) with the maximum peak at 103^orC.

IS 2 165 347 T3

Comparative Example 1

Preparation of a prepolymerized catalyst

To 3.14 g of the same solid used in Example 1 25 ml of decane was added to form a suspension. To the suspension, 13.1 ml of triisobutylaluminum decane solution (Al: 1 mol / liter) was added and the mixture was stirred at room temperature for 45 minutes.

Subsequently, 36.5 ml of a toluene solution of oxy-organoaluminum compound (Al: 1.79 mol / liter) synthesized by a procedure similar to that of Example 1 was added to the suspension, and the resulting mixture was stirred at temperature. environment for 20 minutes.

Next, 10.9 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr: 0.0480 mol / liter) was added to the suspension and the resulting mixture was stirred for 30 minutes. 100 ml of decane were added to the mixture and prepolymerization was carried out at 30 ° C for

4.5 hours introducing ethylene continuously at normal pressure. A subsequent operation similar to that of Example 1 was then carried out to obtain a prepolymerized catalyst containing 7.6 mg of zirconium, 190 mg of aluminum and 9.7 g of polyethylene based on 1 g of silica.

Polymerization

A polymerization procedure similar to that of Example 1 was repeated except that a gaseous mixture containing 6.1 mol% of 1-butene and the prepolymerized catalyst described above was used in an amount of 0.015 atom-mg in terms of zirconium and 0.75 mmol in terms of triisobutylaluminum, and that the polymerization was carried out for 1 hour at 85 ° C and a total pressure of 8 kg / cm²manometric, whereby 137 g of an ethylene / 1-butene copolymer were obtained containing 7.2% by weight of 1-butene constituent units and 1.1% by weight of a component soluble in decane, having an MFR value of 1.29 g / 10 minutes, a density of 0.920 g / cm³, a melt tension of 1.9 g and an apparent specific density of 0.37 g / cm³, and showing an endotothermic curve (measured by DSC) with the maximum peak at 114 ° C.

Example 6

Polymerization

A polymerization procedure similar to that of Example 1 was repeated except that a polymerization catalyst was used in an amount of 0.003 aotome-mg in terms of zirconium and 0.54 mmol in terms of triisobutylaluminum, and that only polymerization was carried out. of ethylene for 1 hour at 85 ° C and a total pressure of 8 kg / cm² manometric, with which 121 g of an ethylene polymer were obtained with an MFR value of 0.29 g / 10 minutes, a melt tension of 17.5 g and an apparent specific density of 0.32 g / cm³.

Example 7

Polymerization

A procedure similar to that of Example 3 was repeated except that a gaseous mixture containing 3.9 mole% of 1-butene, 50 mlN of hydrogen, and the catalyst prepolymerized in an amount of 0.005 atom-mg in terms of zirconium and 0 , 5 mmol in terms of triisobutylaluminum, and that the polymerization was carried out at a total pressure of 2.5 kg / cm² manometric, with which 119 g of an ethylene / 1-butene copolymer were obtained containing 7.0% by weight of constituent units of 1-butene and 0.35% by weight of a component soluble in decane, having an MFR value 1.97 g / 10 minutes, density 0.920 g / cm³, a melt tension of 4.6 g and an apparent specific density of 0.36 g / cm³, and showing an endotothermic curve (measured by DSC) with the maximum peak at 103^°C.

Example 8

Polymerization

A polymerization procedure similar to that of Example 4 was repeated except that 50

ES 2 165 347 T3 mlN of hydrogen and a prepolymerized catalyst in an amount of 0.75 mmol in terms of triisobutylaluminum, and that the polymerization was carried out at 85^or C and at a total pressure of 7 kg / cm²manometric, with which 141 g of an ethylene / 1-butene copolymer were obtained containing 6.8% by weight of constituent units of 1-butene and 0.67% by weight of a component soluble in decane, having an MFR value 1.99 g / 10 minutes, density 0.920 g / cm³, a melt tension of 6.0 g and an apparent specific density of 0.37 g / cm³.

Example 9

Preparation of a prepolymerized catalyst

To 1.11 g of the same silica used in Example 1 was added 15 ml of toluene to form a suspension. 7.76 ml of triisobutylaluminum toluene solution (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 30 minutes. Subsequently, 13.6 ml of a toluene solution of oxy-organoaluminum compound (Al: 0.95 mol / liter) synthesized by a procedure similar to that of Example 1 was added to the suspension, and the resulting mixture was stirred at temperature. environment for 35 minutes. Subsequently, 162.0 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr: 0.00228 mol / liter) was added to the suspension and the resulting mixture was stirred for 30 minutes. 100 ml of decane were added to the mixture and prepolymerization was carried out at 30^or C for 5 hours introducing ethylene continuously at normal pressure. A subsequent operation similar to that of Example 1 was then carried out to obtain a prepolymerized catalyst containing 20.6 mg of zirconium, 310 mg of aluminum and 27 g of polyethylene based on 1 g of silica.

Polymerization

A glass autoclave with a volume of 1.5 liters and thoroughly purged with nitrogen was charged with 1 liter of decane and a gaseous mixture of ethylene and hydrogen was introduced at a flow rate of 250 liters / hour and 1 liter / hour , respectively. The system temperature was raised to 75^or C and a mixture of 0.5 mmol of triisobutylaluminum and the prepolymerized catalyst described above in an amount of 0.005 atom-mg in terms of zirconium was added to the autoclave. Subsequently, polymerization was carried out at 75^orC under normal pressure for 3 hours, while the above-mentioned gas mixture was fed continuously, whereby the polymerization progressed in a suspended state.

After completion of the polymerization, the resulting polymer was recovered by filtration and dried overnight at 80^or C under reduced pressure to obtain 16.9 g of an ethylene polymer having an MFR value of 1.18 g / 10 minutes and a melt tension of 6.5 g.

Example 10

Preparation of a catalyst

A 100 ml eggplant-type flask, thoroughly purged with nitrogen, was charged with 20 ml of decane, 27.9 ml of a toluene solution of an organoaluminum oxy-compound (Al: 0.716 mol / liter) and 37 , 3 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr: 0.00268 mol / liter), and the contents of the flask were stirred for 5 minutes. Toluene was removed from the mixture by distillation over a period of 2 hours using an evaporator at room temperature under reduced pressure. The resulting precipitated solid product was recovered by filtration, washed with hexane, and dried at room temperature under reduced pressure to obtain a solid catalyst having an Al / Zr atomic ratio of 112.

Polymerization

A polymerization procedure similar to that of Example 1 was repeated except that only the solid catalyst component prepared above was used as the catalyst component, in an amount of 0.005 mg-atoms in terms of zirconium, and that the homopolymerization of ethylene was carried out out to 85^orC for 1 hour at a total pressure of 8 kg / cm² manometric, thereby obtaining 26.4 g of an ethylene homopolymer having an MFR value of 0.42 g / 10 min and a melt tension of 12.0 g.

IS 2 165 347 T3

Example 11

Polymerization

A polymerization procedure similar to that of Example 10 was repeated except that only mlN of hydrogen was added, thereby obtaining 34 g of an ethylene homopolymer having an MFR value of 3.10 g / 10 min and a melt tension of 5.0 g.

Comparative Example 2

Polymerization

A polymerization procedure similar to that of Example 9 was repeated except that toluene was used as solvent and a gaseous mixture of ethylene, 1-butene (both being polymerization monomers) and hydrogen at a flow rate of 285 liters / hour, 15 liters / hour and 2 liters / hour, respectively, and that the copolymerization was carried out for 20 minutes, thereby progressing the polymerization in a state of solution. After completion of the polymerization, the resulting polymer was recovered or precipitated in a large quantity of methanol and dried overnight at 130^orC under reduced pressure, thereby obtaining 33.1 g of an ethylene / 1-butene copolymer containing 6.5% by weight of 1-butene constituent units, having an MFR value of 1.44 g / 10 min, a density of 0.922 g / cm³ and a melt tension of 2.1 g.

Comparative Example 3

Polymerization

A polymerization procedure similar to that of Example 9 was repeated except that the flow rates of ethylene and hydrogen in the gas mixture were altered to 100 liters / hour and 5 liters / hour, respectively, and that, as catalytic components, 3 were used , 42 ml of a toluene solution of the organoaluminum oxy-compound (Al: 1.46 mol / liter) and 0.33 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr: 0.00150 mol / liter) and that the ethylene homopolymerization reaction was carried out for 80 minutes, whereby the polymerization progressed in a cloudy state. After completion of the polymerization, the resulting polymer was recovered by precipitating it in a large quantity of methanol and dried overnight at 80^orC under reduced pressure, thereby obtaining 8.2 g of an ethylene copolymer having an MFR value of 0.72 g / 10 min and a melt tension of 2.9 g.

Example 12

Preparation of a prepolymerized catalyst

An 8 liter flask purged thoroughly with nitrogen was charged with 55.4 g of solid (TG-20643, produced by Fuji Davison KK) that had been calcined at 700^or C for 6 hours before being introduced into the flask, and 1 liter of decane, to form a suspension. To the suspension, 46 mmol of triisobutylaluminum diluted with 50 ml of decane was added, and the mixture was stirred at room temperature for 10 minutes.

Next, 140 ml of a toluene solution of the catalyst component (ii) (produced by Schering Co., Ltd.) prepared above (Al: 1.65 mol / liter) was added, and the mixture was stirred at room temperature for 10 minutes. Then 36.9 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr: 0.05 mol / liter) was added and the mixture was stirred for 15 minutes. The prepolymerization was then carried out at 30^orC for 3.5 hours continuously introducing ethylene at normal pressure.

Then, 2 liters of decane, 279 ml of catalytic component (ii), 2.79 liters of catalytic component (i) (Zr: 0.00264 mol / liter) prepared in Example 1 and 23.4 ml of triisobutylaluminum diluted with 50 ml of decane, and the prepolymerization was carried out at 30^orC for 4 hours.

After the prepolymerization, the solvent was separated by decantation, washed at 60^or C three times with 5 liters of hexane and was washed three times at room temperature with 5 liters of hexane, thereby obtaining a prepolymerized catalyst containing 11 mg Zr, 190 mg of Al and 16 g of polyethylene based on 1 g of solid.

IS 2 165 347 T3

Polymerization

The copolymerization of ethylene with 1-hexene will be carried out using a continuous polymerization installation in the gas phase and fluidized bed at a polymerization temperature of 80^or C and at a total pressure of 20 kg / cm² manometric, continuously feeding the prepolymerization catalyst described above at a rate of 0.1 mmol / hour in terms of zirconium and 15 mmol / hour in terms of triisobutylaluminum, and also continuously supplying ethylene, 1-hexene, hydrogen and nitrogen to keep the following gas composition constant during polymerization: 1-hexene / ethylene volume ratio of 0.015 and H volume ratio₂6.3x10 / ethylene ³. The polymer yield was 6 kg / hour.

The polymer thus obtained contained 10.7% by weight of constituent units of 1-hexene and 0.53% by weight of a component soluble in decane, measured at 23^orC, subject an MFR value of 1.60 g / 10 minutes, a density of 0.922 g / cm³, a melt tension (MT) of 6.6 g and an apparent specific density of 0.38 g / cm³, and showed an endothermic curve (measured by DSC) with the maximum peak at 112.1^orC.

The results are indicated in Tables 1 and 2.

TABLE 1

Polymerization conditions

<td>Example</td><td>Catalytic component (atoms-mg Zr)</td><td>(i-Bu) 3Al (mmol)</td><td>Total pressure (Kg / cm² hand.)</td><td>1-Butene (mol%)</td><td>H2 (mlN)</td><td>Temp. (° C)</td><td>Weather (h)</td><td>Notes</td>

<td> 1</td><td>(Ex. 1) 0.0075</td><td> 1,13</td><td> 4</td><td> 6,3</td><td> 50</td><td> 80</td><td> 1</td><td></td>

<td> 2</td><td>(Ex. 2) 0.0050</td><td> 0,75</td><td> 4</td><td> 3,6</td><td> 10</td><td> 70</td><td> 2</td><td></td>

<td> 3</td><td>(Ex. 3) 0.0075</td><td> 1,13</td><td> 4</td><td> 6,3</td><td> 30</td><td> 80</td><td> 1</td><td></td>

<td> 4</td><td>(Ex. 4) 0.0050</td><td> 0,50</td><td> 4</td><td> 4,4</td><td> 30</td><td> 80</td><td> 1</td><td></td>

<td> 5</td><td>(Ex. 1) 0.0050</td><td> 0,75</td><td> 4</td><td> 3,6</td><td> 30</td><td> 70</td><td> 1</td><td></td>

<td> 6</td><td>(Ex. 1) 0.0030</td><td> 0,54</td><td> 8</td><td> -</td><td> 50</td><td> 85</td><td> 1</td><td></td>

<td> 7</td><td>(Ex. 3) 0.0050</td><td> 0,50</td><td> 2,5</td><td> 3,9</td><td> 50</td><td> 80</td><td> 1</td><td></td>

<td> 8</td><td>(Ex. 4) 0.0050</td><td> 0,75</td><td> 7</td><td> 4,4</td><td> 50</td><td> 85</td><td> 1</td><td></td>

<td> 9</td><td>(Ex. 9) 0.0050</td><td> 0,50</td><td>Normal pressure</td><td> -</td><td>(1 l / h)</td><td> 75</td><td> 3</td><td>Ethylene 250 l / h</td>

<td> 10</td><td>(Ex. 10 0.0050</td><td> -</td><td> 8</td><td> -</td><td> 50</td><td> 85</td><td> 1</td><td></td>

<td> 11</td><td>(Ex. 10) 0.0050</td><td> -</td><td> 8</td><td> -</td><td> 100</td><td> 85</td><td> 1</td><td></td>

<td> 12</td><td>(Ex. 12) (0.1mmol / h)</td><td>(15mmol / h)</td><td> 20</td><td> -</td><td> -</td><td> 80</td><td> -</td><td></td>

<td>Ex Comp. 1</td><td>(Comp. 1) 0.0150</td><td> 0,75</td><td> 8</td><td> 6,1</td><td> 50</td><td> 85</td><td> 1</td><td></td>

<td>Ex Comp. two</td><td>(Ex. 9) 0.0050</td><td> 0,50</td><td>Normal pressure</td><td>(15 l / h)</td><td>(2 l / h)</td><td> 75</td><td> 0,33</td><td>Ethylene 285 l / h</td>

<td>Ex Comp. 3</td><td>(Ex. Comp.3) 0.0005</td><td> 5,00</td><td>Normal pressure</td><td></td><td>(5 l / h)</td><td> 75</td><td> 1,33</td><td>Ethylene 100 l / h</td>

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TABLE 2

Polymerization results

<td>Example</td><td>Performance (g)</td><td>Contained in 1-Butene (% by weight)</td><td>MFR (g / 10 min)</td><td>Density (g / cm³)</td><td>Component soluble in decane (% by weight)</td><td>Molten state voltage ⁽g⁾</td><td>Max DSC Peak Temp (° C)</td><td>Apparent specific density (g / cm³)</td>

<td> 1</td><td> 116</td><td> 8,1</td><td> 2,30</td><td> 0,915</td><td> 2,8</td><td> 5,3</td><td> 94</td><td> 0,31</td>

<td> 2</td><td> 88</td><td> 6,7</td><td> 0,48</td><td> 0,922</td><td> 0,25</td><td> 11</td><td> 103</td><td> 0,35</td>

<td> 3</td><td> 149</td><td> 10,1</td><td> 1,78</td><td> 0,912</td><td> 3,1</td><td> 5,3</td><td> 94</td><td> 0,36</td>

<td> 4</td><td> 48</td><td> 6,5</td><td> 3,10</td><td> 0,922</td><td> 0,32</td><td> 4,9</td><td> 115</td><td> 0,24</td>

<td> 5</td><td> 95</td><td> 7,4</td><td> 0,075</td><td> 0,920</td><td> 0,18</td><td> 42</td><td> 103</td><td> 0,32</td>

<td> 6</td><td> 121</td><td> -</td><td> 0,29</td><td> -</td><td> -</td><td> 17,5</td><td> -</td><td> 0,36</td>

<td> 7</td><td> 119</td><td> 7,0</td><td> 1,97</td><td> 0,920</td><td> 0,35</td><td> 4,6</td><td> 103</td><td> 0,37</td>

<td> 8</td><td> 141</td><td> 6,8</td><td> 1,99</td><td> 0,920</td><td> 0,67</td><td> 6,0</td><td> -</td><td> -</td>

<td> 9</td><td> 16,9</td><td> -</td><td> 1,18</td><td> -</td><td> -</td><td> 6,5</td><td> -</td><td> -</td>

<td> 10</td><td> 26,4</td><td> -</td><td> 0,42</td><td> -</td><td> -</td><td> 12,0</td><td> -</td><td> -</td>

<td> 11</td><td> 34,0</td><td> -</td><td> 3,10</td><td> -</td><td> -</td><td> 5,0</td><td> -</td><td> -</td>

<td> 12</td><td>(6.0 kg / h)</td><td>10.7 (content in 1-hexene)</td><td> 1,60</td><td> 0,922</td><td> 0,53</td><td> 6,6</td><td> 112,1</td><td> 0,38</td>

<td>Ex Comp. 1</td><td> 137</td><td> 7,2</td><td> 1,29</td><td> 0,920</td><td> 1,1</td><td> 1,9</td><td> 114</td><td>_-</td>

<td>Ex Comp. two</td><td> 33,1</td><td> 6,5</td><td> 1,44</td><td> 0,922</td><td> -</td><td> 2,1</td><td> -</td><td> -</td>

<td>Ex Comp. 3</td><td> 8,2</td><td> -</td><td> 0,72</td><td> -</td><td> -</td><td> 2,9</td><td> -</td><td> -</td>

Comparative Example 4

Preparation of a prepolymerized catalyst

Comparative Example 1 was repeated except that 13.1 ml of a toluene solution of bis (cyclopentadienyl) zirconium dichloride (Zr: 0.04 mol / liter) was used in place of the toluene solution of bis (methylcyclopentadienyl dichloride ) zirconium, to obtain a prepolymerized catalyst containing 8.7 mg of zirconium, 290 mg of aluminum and 7.7g of polyethylene based on 1 g of silica.

Polymerization

A polymerization procedure similar to that of Example 1 was repeated except that a gaseous mixture containing 6.7 mole% of 1-butene and the prepolymerized catalyst obtained above were used in an amount of 0.01 aotom-mg in terms of zirconium and 0 , 25 mmol in terms of triisobutylaluminum, and that the polymerization was carried out for 1 hour at 85^or C and at a total pressure of 8 kg / cm² manometric, thereby obtaining 75 g of an ethylene / 1-butene copolymer containing 6.9% by weight of constituent units of 1-butene and 1.5% by weight of a component soluble in decane, which has an MFR value 2.63 g / 10 minutes, density 0.922 g / cm³ and a melt tension of 1.3 g, and showing an endotothermic curve (measured by DSC) with the maximum peak at 114^orC.

Comparative Example 5

Preparation of a prepolymerized catalyst

To 1.05 g of the same solid used in Example 1 was added 20 ml of decane to form a suspension in a 400 ml glass flask. 2.62 ml of a decane solution of triisobutylaluminum (Al: 1 mol / liter) was added to the suspension, and the resulting mixture was stirred at room temperature for 30 minutes.

4.87 ml of a toluene solution of an organoaluminum oxy-compound [prepared by separating toluene from a toluene solution of a methylaluminoxane produced by Schering Co., Ltd. and redissolving the residue in toluene was then added to the suspension. (Al: 1.79 mol / liter)], and the resulting mixture was stirred at room temperature for 35 minutes.

IS 2 165 347 T3

Then 16.2 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr: 0.0108 mol / liter) was added to the suspension and the mixture was stirred for 30 minutes. 75 ml of decane was then added to the mixture and the prepolymerization was carried out at 30^or C for 4 hours continuously introducing ethylene at normal pressure. A subsequent operation similar to that of Example 1 was carried out to obtain a prepolymerized catalyst containing 9.3 mg of zirconium, 150 mg of aluminum and 18 g of polyethylene.

Polymerization

A polymerization procedure similar to that of Example 1 was repeated except that a gaseous mixture containing 6.9 mol% of 1-butene and the prepolymerized catalyst obtained above in an amount of 0.005 aotome-mg in terms of zirconium and 0.5 mmol in terms of triisobutylaluminum, and that the polymerization was carried out for 1 hour at 85^orC and a total pressure of 8 kg / cm² manometric, thereby obtaining 147 g of an ethylene / 1-butene copolymer containing 9.6% by weight of constituent units of 1-butene and 1.5% by weight of a component soluble in decane, which has an MFR value 2.45 g / 10 minutes, density 0.910 g / cm³ and a melt tension of 0.95 g, and showing an endotothermic curve (measured by DSC) with the maximum peak at 109^orC.

Comparative Example 6

A glass autoclave with a volume of 1.5 liters and thoroughly purged with nitrogen was charged with 1 liter of toluene and then ethylene, 1-butene and hydrogen were introduced therein, as a mixture, at a flow rate of 285 liters / hour, 15 liters / hour and 2 liters / hour, respectively. The system temperature was raised to 70^or C and the polymerization was started after introducing 0.5 mmol of triisobutylaluminum and the prepolymerized catalyst prepared in Example 1 in an amount of 0.005 atom-mg in terms of zirconium.

Polymerization was carried out for 20 minutes at 75^or C and normal pressure continuously introducing the gas mixture indicated above, whereby the polymerization progressed while the polymer produced was dissolved in toluene. After completion of the polymerization, the resulting polymer was precipitated by pouring the polymer solution into methanol.

The precipitated polymer was then recovered by filtration and dried overnight at 80^or C under reduced pressure, thereby obtaining 33.1 g of an ethylene / 1-butene copolymer having an MFR value of 1.44 g / 10 minutes, a density of 0.922 g / cm³ and a melt tension of (MT) of 2.1 g.

Comparative Example 7

A glass autoclave with a volume of 1.5 liters and thoroughly purged with nitrogen was charged with 1 liter of toluene and ethylene, 1-butene and hydrogen were introduced in the same, in mixture at a flow rate of 285 liters / hour, 15 liters / hour and 5 liters / hour, respectively. The system temperature was raised to 70^or C and the polymerization was started by introducing the organoaluminum oxy-compound prepared in Example 1 in an amount of 5 aotomes / mg in terms of aluminum and the catalytic component (i) in an amount of 0.0005 aotom-mg in terms of zirconium.

Polymerization was carried out for 20 minutes at 75^or C and normal pressure while the gas mixture described above was continuously introduced, whereby the polymerization progressed at the same time as the product polymer was dissolved in toluene. A subsequent operation similar to that of Comparative Example 4 was repeated to obtain 44.1 g of an ethylene / 1-butene copolymer having an MFR value of 1.08 g / 10 minutes, a density of 0.928 g / cm³, and a melt tension (MT) of 2.0 g.

Example 13

Preparation of a prepolymerized solid catalyst (zirconium catalyst)

A 400 ml glass flask purged thoroughly with nitrogen was charged with 1.38 g of solid (F-498), produced by Fuji Davison KK) which had been calcined at 700^or C for 6 hours before placing it in the flask, and 20 ml of decane, to form a suspension. 3.24 ml were added to the suspension.

ES 2 165 347 T3 of a decane solution of triisobutyaluminum (Al: 1 mol / liter) and the contents were stirred at room temperature for 30 minutes.

18.8 ml of a toluene solution of an organoaluminum oxy-compound (prepared by drying the methylaluminoxane produced by Schering Co., Ltd, and redissolving the residue in toluene Al: 0.864 mol / liter) was added to the suspension, and The mixture was further stirred at room temperature for 30 minutes.

1.03 ml of a toluene solution of bis (cyclopentadienyl) zirconium dichloride (Zr: 0.0417 mol / liter) was then added to the suspension and the mixture was stirred for 10 minutes. Then another 50 ml of decane was added and prepolymerization was carried out at 30^or C for 2 hours continuously introducing ethylene at normal pressure.

100.5 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr: 0.00172 mol / liter) were then added and the prepolymerization was continued at 30^orC for 4 hours.

After the prepolymerization, the solvent was separated by decantation and the residue was washed three times at 60^or C with 250 ml of hexane and then three times at room temperature with 250 ml of hexane, thereby obtaining a prepolymerized solid copolymer containing 9.5 otom-mg of zirconium, 0.66 otom-g of aluminum and 1,750 g of polyethylene .

Polymerization

A stainless steel autoclave with a volume of 2 liters and thoroughly purged with nitrogen was charged with 150 g of sodium chloride (special quality from Wako Junyaku KK) and the contents were dried for 1 hour at 90^or C under reduced pressure. The pressure of the system was then returned to normal pressure by introducing ethylene and the temperature of the system was kept at 70^orC. The autoclave was then charged with a premix of 0.3 mmol triisobutylaluminum and the solid catalyst described above in an amount of 0.003 atom-mg in terms of zirconium.

Then 50 mlN of hydrogen was introduced and then ethylene was again introduced into the autoclave at a system temperature of 70^orC, so that the total pressure would become 8 kg / cm²manometers, and polymerization began.

Polymerization was then carried out at 85^orC for 1 hour while maintaining total pressure at 8 kg / cm² manometers introducing only ethylene. After the polymerization was finished, the sodium chloride was separated from the contents of the autoclave by washing with water. The remaining polymer was washed with methanol and dried overnight at 80^or C under reduced pressure, thereby obtaining 142 g of a polymer having an apparent specific density of 0.43 g / cm³, an MFR value of 0.65 g / 10 minutes measured at 190^orC and under a load of 2.16 kg, a melt tension (MT) of 10 g and an average particle size of 410 pm.

Example 14

To 1.12 g of the same solid used in Example 13 was added 20 ml of decane to form a suspension. 2.8 ml of a decane solution of triisobutylaluminum (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 35 minutes.

10.8 ml of a toluene solution of the same organoaluminum oxy-compound as in Example 13 (Al: 0.864 mol / liter) was then added to the suspension and the mixture was further stirred at room temperature for 25 minutes.

Then 1.34 ml of a toluene solution of bis (cyclopentadienyl) zirconium dichloride (Zr: 0.0417 mol / liter) was added to the suspension and the contents were stirred for 30 minutes. In addition, 50 ml of decane were added and polymerization was carried out at 30^or C for 2 hours continuously introducing ethylene at normal pressure. 71.3 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr: 0.00183 mol / liter) was then added to the reaction mixture and the prepolymerization was continued at 30^or C for 3.5 hours. A subsequent operation similar to that of Example 13 was carried out to obtain a solid catalyst containing 9.6 mg-atoms of zirconium, 0.66 g-atoms of aluminum and 2,100 g of polyethylene based on 100 g of silica.

IS 2 165 347 T3

Polymerization

The procedure of Example 13 was repeated to obtain 88 g of a polymer having an apparent specific density of 0.42 g / cm³, an MFR value of 0.60g / 10 minutes and a mean particle size of 380 pm.

Example 15

Preparation of a solid catalyst (zirconium catalyst)

To 3 g of the same silica used in Example 13 was added 30 ml of decane to form a suspension. 7.45 ml of a triisobutylaluminum decane solution (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 25 minutes.

Then 17.6 ml of a toluene solution of the same organoaluminum oxy-compound as in Example 13 (Al: 2.13 mol / liter) was added to the suspension and the mixture was further stirred at room temperature for 25 minutes.

2.14 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr: 0.0465 mol / liter) was then added to the suspension and the contents were stirred for 5 minutes. In addition, 100 ml of decane were added and polymerization was carried out at 25^ORC for 2.5 hours continuously introducing ethylene at normal pressure. 166.4 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr: 0.0024 mol / liter) were then added to the reaction mixture and the prepolymerization was continued at 30^ORC for 5 hours. A subsequent operation similar to that of Example 13 was carried out to obtain a prepolymerized solid catalyst containing 9 atom-mg of zirconium, 0.55 atom-g of aluminum and 2,000 g of polyethylene based on 100 g of silica.

Polymerization

The polymerization procedure of Example 13 was repeated except that 0.54 mmol of triisobutylaluminum was used and that the catalyst component was injected with ethylene into the autoclave that had an internal pressure of 6.5 kg / cm², thereby obtaining 124 g of a polymer having an apparent specific density of 0.41 g / cm³, an MFR value of 0.58 g / 10 minutes, a melt tension (MT) of 13 g and a mean particle size of 400 pm.

Comparative Example 8

Preparation of a prepolymerized solid catalyst (zirconium catalyst)

To 3.05 g of the same silica used in Example 13 was added 20 ml of decane to form a suspension. 7.61 ml of a triisobutylaluminum decane solution (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 30 minutes.

Then 11.9 ml of a toluene solution of the same organoaluminum oxy-compound as in Example 13 (Al: 2.13 mol / liter) was added to the suspension, the contents were further stirred at room temperature for 30 minutes.

10.9 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr: 0.0465 mol / liter) was then added to the suspension and the mixture was stirred for 30 minutes. Then 100 ml more of decane were added and the polymerization was carried out 30^ORC for 3.5 hours continuously introducing ethylene at normal pressure. A subsequent operation similar to that of Example 13 was repeated, thereby obtaining a solid catalyst containing 12 atom-mg of zirconium, 0.71 atom-g of aluminum and 790 g of polyethylene based on 100 g of silica.

Polymerization

The polymerization procedure of Example 15 was repeated except that the prepolymerized solid catalyst obtained above was used in an amount of 0.015 uatom-mg in terms of zirconium to obtain 70 g of a polymer having an apparent specific density of 0.42 g / cm³ and an MFR value of 0.69 g / 10 minutes.

IS 2 165 347 T3

Comparative Example 9

Preparation of a prepolymerized solid catalyst (zirconium catalyst)

To 1.16 of the same silica used in Example 13 was added 20 ml of decane to form a suspension. 4.05 ml of a decane solution of triisobutylaluminum (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 30 minutes.

3.17 ml of a toluene solution of the same organoaluminum oxy-compound as in Example 13 (Al: 2.13 mol / liter) was then added to the suspension and the contents were stirred at room temperature for 30 minutes.

Then, 80.5 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr: 0.0024 mol / liter) was added to the suspension and the mixture was stirred for 30 minutes. Then 50 ml more of decane and 90 ml of toluene were added and the polymerization was carried out at 30^or C for 3 hours continuously introducing ethylene at normal pressure. A subsequent operation similar to that of Example 13 was repeated, whereby a prepolymerized solid catalyst was obtained containing 8.9 otom-mg of zirconium, 0.56 g-atom of aluminum and 1,000 g of polyethylene based on 100 g of solid. .

Polymerization

The polymerization procedure of Example 15 was repeated to obtain 123 g of a polymer having an apparent specific density of 0.36 g / cm³, an MFR value of 0.44 g / 10 minutes and a mean particle size of 370 pm.

Example 16

Polymerization

The polymerization procedure of Example 13 was repeated except that a gaseous mixture of ethylene and 1-butene (1-butene content: 3.9 mol%) were used instead of ethylene, 30 mlN of hydrogen, 0.75 mmol of triisobutylaluminum and the solid catalyst component prepared in Example 3 in an amount of 0.0075 atom-mg in terms of zirconium, and except that the polymerization temperature and the total pressure used were set at 80^orC and 2.5 kg / cm² manometric, respectively, with which 172 g of a polymer having an apparent specific density of 0.38 g / cm were obtained³, an MFR value of 0.82 g / 10 minutes, a melt tension (MT) of 9 g and a density of 0.918 g / cm³.

Example 17

Preparation of a prepolymerized solid catalyst (zirconium catalyst)

To 1.49 of the same silica from Example 13 was added 25 ml of decane to form a suspension. 3.72 ml of a triisobutylaluminum decane solution (Al: 1 mol / liter) was added to the suspension and the mixture was stirred at room temperature for 45 minutes.

8.09 ml of the same organoaluminum oxy-compound of Example 13 (Al: 2.30 mol / liter) was then added to the suspension and the contents were stirred at room temperature for 45 minutes.

Then, 2.13 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr: 0.0465 mol / liter) was added to the suspension and the contents were stirred for 10 minutes. Then 75 ml more of decane were added, the prepolymerization was carried out at 30^orC for 1.5 hours continuously introducing ethylene at normal pressure. To the reaction mixture, 51.9 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr: 0.00287 mol / liter) were added and the prepolymerization was continued at 30^orC for 4 hours to obtain a solid prepolymerized catalyst containing 11.5 atom-mg of zirconium, 0.71 atom-g of aluminum and 1,700 g of polyethylene based on 100 g of solid.

Polymerization

The polymerization procedure of Example 13 was repeated except that a gaseous mixture of ethylene and 1-butene (1-butene content: 4.4 mol%) was used instead of ethylene, 30 mlN of

ES 2 165 347 T3 hydrogenic, 0.5 mmol of triisobutylaluminum and the prepolymerized solid catalyst component prepared above in an amount of 0.005 aotom-mg in terms of zirconium, thus obtaining 137 g of a polymer having an apparent specific density of 0.39 g / cm³, an MFR value of 0.53 g / 10 minutes, a melt tension (MT) of 12 g and a density of 0.917 g / cm³·