JP3476965B2 - Method for producing ethylene polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid component of a catalyst used for producing an ethylene polymer having a wide molecular weight distribution, a catalyst for producing a polymer containing the solid component, and a method for producing the ethylene polymer.

[0002]

2. Description of the Related Art As a catalyst system using a heterocyclic compound, JP-A-56-15707 and JP-B-60-50367 are known.
No. is known. However, the molecular weight distribution of the ethylene polymer produced by the conventional catalyst system is narrow, and it is difficult to polymerize the ethylene polymer having a relatively wide molecular weight distribution in a single stage. Further, as a means for broadening the molecular weight distribution, vanadium other than titanium atom as a transition metal element,
Zirconium, the polymerization catalyst system used different element such as chromium is known (for example, JP-A-63-260904)
, Polymerization activity, coloring of the ethylene-based polymer produced, L
There is a problem with the stickiness of the product when using LD film.

[0003]

DISCLOSURE OF THE INVENTION The present invention broadens the molecular weight distribution of the ethylene-based polymer produced without using a different metal element other than titanium such as vanadium, zirconium and chromium as the transition metal element, and further increases the molecular weight. Even if the distribution is widened, even if it is made into a film, stickiness does not worsen even when compared to conventional products even in the case of linear low-density polyethylene, a solid component of a catalyst used for producing an ethylene polymer having a wide molecular weight distribution, The purpose of the present invention is to develop a polymerization catalyst containing a solid component and a method for producing an ethylene polymer.

[0004]

[Means for Solving the Problems] As a result of intensive efforts to achieve the above-mentioned object, an ethylene-based polymer which gives a broader molecular weight distribution than an ethylene-based polymer produced by a conventional catalyst system and does not deteriorate stickiness. We have succeeded in developing a new catalyst that allows the polymer to be produced even in a single-stage polymerization. The method for producing the catalyst described above will be described in detail below. That is, the present invention provides [1] at least a magnesium atom, a halogen atom,
Titanium atom, n-membered heterocyclic compound (D ₁ ) and m
A heterocyclic compound (D ₂ ) having a member ring (m is a number of n + 1 or more or n-1 or less) as an essential component, and the sum of the heterocyclic compound D ₁ and the heterocyclic compound D ₂ contained in the catalyst solid component. And a titanium atom (T) in a molar ratio of 0 <[(D ₁ + D ₂ ) / T] <100 and 0 <D ₁ / D ₂ <100. Component, [2] The solid component is at least a magnesium atom, a halogen atom, a titanium atom, or an n-membered heterocyclic compound (D
Solid component (II) obtained by treating solid component (I) containing ₁ ) as an essential component with m-membered heterocyclic compound (D ₂ ).
Alternatively, a catalyst for producing an ethylene polymer, which is a catalyst solid component (IV) obtained by treating the solid component (I) on an inert inorganic compound carrier and treating the solid component (III) with a heterocyclic compound (D ₂ ). Solid component, [3] The solid component is a catalyst solid component (V) obtained by treating the solid component (I) or the solid component (III) with the heterocyclic compound (D ₂ ) and then with the organometallic compound (M). , or
Other solid component (I) or the solid component (III) organometallic compound (M) treated with obtained solid component (VI)
Is further treated with a heterocyclic compound (D ₂ ), which is a solid component of a catalyst for producing an ethylene polymer, which is a solid component (VII) of the catalyst, [4] The solid component is a heterocyclic compound (D ₂ ) and an organic compound. A solid component of a catalyst for producing an ethylene polymer, which is a catalyst solid component obtained by previously reacting a metal compound (M) with the solid component (I) or the solid component (III), and [5] of the n-membered ring The heterocyclic compound (D ₁ ) is a 4- to 8-membered cyclic compound, and is a hydrocarbon group selected from an aliphatic hydrocarbon group having 16 carbon atoms and an aromatic hydrocarbon group or a halogen atom. Solid component of catalyst for producing ethylene-based polymer which is a heterocyclic compound having a substituent, [6] Inert inorganic compound carrier is silica, silica-alumina, silica-titania, silica-zirconia, alumina, phosphoric acid A Solid component of catalyst for producing an a ethylene-based polymer Miniumu, [7] the organometallic compound (M) is, AlR _a X _3-a (where R 12 aliphatic most carbon atoms, alicyclic Or an aromatic hydrocarbon group, X is a hydrogen atom or a halogen atom, and a is a number of 1 to 3), which is an aluminum compound represented by a solid component of a catalyst for producing an ethylene polymer. [8] The catalyst solid components (II), (IV), (V),
A catalyst for ethylene polymer production in which an organoaluminum compound is added to either component (VII) or (VIII), and [9] ethylene is homopolymerized or converted to ethylene using the catalyst for polymer production. The above object was achieved by developing a method for producing an ethylene-based polymer in which an alpha olefin is copolymerized.

(1) Constituent components of solid catalyst component Prepared by using the catalyst solid component (I) in the present invention, the following known magnesium compound, titanium compound, halogen-containing compound and heterocyclic compound (D ₁ ). Made . The magnesium compound is not particularly limited, and those used as a raw material for preparing a highly active catalyst for ordinary olefin polymerization and copolymerization can be used. That is, magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide; alkoxy magnesium such as dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and diphenoxy magnesium; magnesium laurate, magnesium stearate, acetic acid. Examples thereof include carboxylic acid salts such as magnesium; alkyl magnesium such as dimethyl magnesium, diethyl magnesium and butylethyl magnesium. Further, these various magnesium compounds may be used alone or in combination of two or more.
It is preferable to use magnesium halide or alkoxy magnesium, or to form magnesium halide during catalyst formation. Particularly preferably, the halogen is chlorine.

Titanium compounds include titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tribromide, titanium tetraiodide, titanium halides such as titanium triiodide; tetramethoxytitanium, tetrapropoxytitanium, tetra Examples thereof include alkoxytitanium such as butoxytitanium and tetraphenoxytitanium; alkoxytitanium halides such as ethoxytitanium chloride, butoxytitanium chloride, phenoxytitanium chloride, dibutoxytitanium dichloride and tributoxytitanium chloride. Further, these various titanium compounds may be used alone or in combination of two or more. A titanium halide compound is preferable, and titanium trichloride or titanium tetrachloride is particularly preferable. As the halogen-containing compound, halogen is fluorine, chlorine,
It is bromine or iodine, preferably chlorine. Specific compounds actually exemplified depend on the catalyst preparation method, but titanium halides such as titanium tetrachloride and titanium tetrabromide; magnesium halides such as magnesium chloride and magnesium bromide; halogens such as silicon tetrachloride. Silicon halide; phosphorus halide such as phosphorus trichloride and phosphorus pentachloride can be exemplified, but carbon halide, halogen molecule and hydrohalic acid may be used depending on the catalyst preparation method.
Usually, halides are used as the magnesium compound and the titanium compound, so that these are not particularly added in many cases.

The heterocyclic compound (D ₁ ) includes the heterocyclic compound having a substituent on the ring. Examples of this substituent include a carbon hydrogen group and a halogen atom selected from an aliphatic hydrocarbon group and an aromatic hydrocarbon group each having at most 16 carbon atoms. However, the total hydrocarbon group has at most 32 carbon atoms, and a 4-membered to 8-membered heterocyclic compound containing an oxygen atom and / or a nitrogen atom in the ring is preferable. Preferred heterocyclic compounds are oxetane, furan, tetrahydrofuran, 1,3-dioxolane, 2
-Methyloxolane, 2,5-dimethyloxolane, 3
-Methyloxolane, pyran, tetrahydropyran, 2
-Methyloxane, 2,6-dimethyloxane, morpholine, 2,4,6-trimethyloxane, 1,4-dioxane, 2-methyl-1,4-dioxane, benzofuran, coumaran, benzopyran, chroman, isochromene and isoclamane. Such oxygen-containing heterocyclic compounds and nitrogen-containing heterocyclic compounds such as pyridine, pyridazine, pyrimidine, pyrazine, triazinequinoline, isoquinoline, acridine and benzoxazole can be listed. More preferably, 5 such as furan, tetrahydrofuran, pyran and tetrahydropyran
To 6-membered oxygen-containing heterocyclic compounds. The heterocyclic compound (D ₂ ) is a heterocyclic compound having _one or more member rings larger or smaller than the heterocyclic compound (D ₁ ). The heterocyclic compound having a substituent on the ring is also included.
Examples of this substituent include a hydrocarbon group having at most 16 carbon atoms selected from an aliphatic hydrocarbon group and an aromatic hydrocarbon group, a halogen atom and a heterocycle.

When the heterocyclic compound (D ₂ ) is exemplified, the range varies depending on what is selected for the heterocyclic compound (D ₁ ). That is, although when selecting a 5-membered ring as D ₁ is 4-membered ring following compounds or above 6-membered ring compounds as D _2, as D ₂ if you select the 6-membered ring as D ₁ Is a compound having a 5-membered ring or less or a compound having a 7-membered ring or more. D ₂ is preferably D ₁
And a 3- to 22-membered ring excluding the same-membered ring.
For example, oxirane, oxetane, furan, tetrahydrofuran, 1,3-dioxolane, 2-methyloxolane, 2,5-dimethyloxolane, 3-methyloxolane, pyran, tetrahydropyran, 2H-pyran, 4
H-pyran, 3,4-dihydro-2H-pyran, 2-methyloxane, 2,6-dimethyloxane, morpholine, 4H-1,4-oxazine, 2,4,6-trimethyloxane, 1,4- Dioxane, 2-methyl-1,4
-Dioxane, benzofuran, 1,3-dihydroisobenzofuran, anthranil, coumarane, benzopyran,
Chroman, isochromene, isochroman, dibenzofuran, xanthene, phenoxazine, 12-crown-
4,15-crown-5,18-crown-6, dibenzo-18-crown-6, bellhydrodibenzo-18-
Crown-6, Cryptand 22 and Cryptand 2
An oxygen-containing heterocyclic compound such as 22 and pyridine,
Piperidine, pyridazine, pyrimidine, pyrazine, piperazine, 1,3,5-triazine, 1,2,4,5-tetrazine, indole, indoline, isoindole,
Quinoline, isoquinoline, 4H-quinolidine, cinnoline, quinazoline, quinoxaline, phthalazine, 1,8-
Naphthyridine, pteridine, acridine, phenazine,
Among the nitrogen-containing heterocyclic compounds such as phenanthridine, carbazole, 1,10-phenanthroline, phenazone and benzoxazole, those excluding those having the same member ring as D ₁ can be listed.

The magnesium compound and titanium compound used in the catalyst solid component (III) are preferably compounds soluble in a non-aqueous solvent because they must be supported on an inert inorganic compound carrier. The solvent hydrocarbons, ethers, and the like can be used a heterocyclic compound, preferably advantageous to use (D ₁₎ as the heterocyclic compounds (D _1). Examples of the inert inorganic compound carrier used for the catalyst solid component (III) include silica, silica-alumina, silica-titania, silica-zirconia, alumina, aluminum phosphate and the like. Among them, silica, silica-alumina, silica-titania, silica zirconia, and alumina carriers are not limited to amorphous ones, and crystalline compounds may be used. A porous inorganic compound carrier having a large pore size and a large surface area is preferable, and a particle size distribution is particularly preferable, a pore size is large, and a surface area is large. A preferred example is D, which is a porous silica.
Avison 955 type silica gel and Crosf
For example, EP17MS manufactured by Field Co. is used.

The catalyst solid component (I) or the catalyst solid component (III) is prepared by treating the titanium compound and the magnesium compound with the heterocyclic compound (D ₁ ). As the main method, 1) a method of mechanically crushing a titanium compound, a magnesium compound and a heterocyclic compound (hereinafter referred to as "co-milling method"), 2) a method of contacting in an inert solvent, 3) a heterocyclic compound Is used as a solvent, 4) a method in which a titanium compound and a magnesium compound are dissolved in a heterocyclic compound and supported on an inert inorganic carrier, and 1) to 3) are catalyst solid components (I). 4) corresponds to the method for preparing the catalyst solid component (III). The details of each method are shown below.

1) Co-grinding method As the co-grinding method, a commonly used method of co-grinding a titanium compound, a magnesium-halogen compound and a heterocyclic compound (D ₁ ) to produce a solid component of a catalyst for olefin polymerization is applied. do it. At this time, the three components may be co-pulverized at the same time, or may be co-pulverized with the titanium compound and the magnesium compound and then contacted with the heterocyclic compound (D ₁ ). Generally, a crusher such as a ball mill, a vibrating ball mill, an impact crusher, and a colloid mill is used, and co-crushing may be performed at around room temperature under an atmosphere of an inert gas (for example, nitrogen or argon). Usually, it is not necessary to take measures such as cooling, but when the heat generation is remarkable due to this co-pulverization, cooling may be performed for convenience of operation. The crushed state needs to be fine at least until the crushed object can be used, and the crushed object is preferably in a uniform state. Therefore, the co-milling time is generally 5 minutes to 24 hours.

2) Method of contacting in an inert solvent As the method of contacting in an inert solvent, it is desirable to use a dry one containing no water. Further, it is preferable that the titanium compound and the magnesium compound are previously co-pulverized (the co-pulverization method is the same as the above-mentioned co-pulverization method). As an inert solvent,
Aliphatic hydrocarbons (e.g. i-pentane, n-hexane, n-heptane, n-octane etc.) having a boiling point of 10 to 300 [deg.] C., aliphatic cyclic hydrocarbons (e.g. cyclohexane etc.), aromatic hydrocarbons (e.g. benzene, Toluene, xylene, etc.) and halogenated hydrocarbons (carbon tetrachloride,
Trichloroethylene etc.) can be illustrated. Since the contact temperature varies depending on the solvent used, it is not possible to limit the preferable temperature, but when n-hexane is used as a solvent, for example, the temperature is preferably 0 to 150 ° C, more preferably 20 to 100 ° C. . The contact time varies depending on the contact temperature, but is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours, and more preferably 20 to 12 hours. The reaction atmosphere is preferably under an inert gas.
The obtained catalyst solid component (I) may be stored in the form of a slurry or may be dried to give a powder. Examples of the drying method include a method of removing the supernatant and then drying, a method of vaporizing an inert solvent as it is, and the like.

[0013] 3) As the method of contacting with a heterocyclic compound (D ₁₎ a method heterocyclic compound being contacted with the solvent (D ₁₎ as a solvent, the heterocyclic compound of titanium compound and magnesium compound It is preferable that the solubility in (D ₁ ) is low, and it is preferable that the titanium compound and the magnesium compound are previously co-ground. The contact temperature varies depending on the kind of the heterocyclic compound (D ₁ ) used, but it is preferably 0 to bp or 150 ° C, more preferably 20 to bp or 100 ° C. The contact time varies depending on the contact temperature, but is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours, and more preferably 20 to 12 hours. The reaction atmosphere is preferably under an inert gas.

4) Method of dissolving titanium compound and magnesium compound with heterocyclic compound (D ₁ ) and supporting them on an inert inorganic carrier Method of dissolving titanium compound and magnesium compound with heterocyclic compound (D ₁ ). As a titanium compound,
It is preferred that the magnesium compound has high solubility in the heterocyclic compound (D ₁ ). The contact temperature varies depending on the heterocyclic compound used, but is preferably 0 to 1
The temperature is 50 ° C, more preferably 20 to 100 ° C. The time for dissolution is longer than the time required for actual dissolution. The inorganic compound carrier is preferably subjected to a deactivation treatment on the catalyst solid component in advance before supporting the catalyst solid component. The deactivation process here is
This means not only to remove the physically adsorbed water present in the inorganic compound carrier, but also to reduce the chemically adsorbed water present as hydroxyl groups on the surface. Typical examples of the inactivation treatment include heat treatment, treatment with an organometallic compound, treatment with halogen, and the like, and any treatment is preferably combined with heat treatment.

The heat treatment is 110 ° C. under normal pressure.
The above is desirable. As for the upper limit of the temperature, a specific numerical value cannot be stated because it depends on the carrier, but it is preferably lower than the sintering temperature. Speaking of the silica carrier, the preferable heat treatment temperature is 200 ° C to 800 ° C.
℃. More preferably, it is 300 ° C to 700 ° C. The heat treatment time is generally 5 minutes to 24 hours, preferably 10 minutes to 12 hours, and more preferably 20 minutes to 6 hours. Further, of course, the heat treatment may be performed under reduced pressure.

The treatment with the organometallic compound is generally carried out using an inert solvent. The organometallic compound is preferably an organoaluminum compound. Further, it is preferable to perform a heat treatment and a preliminary drying before the treatment with the organometallic compound. The treatment temperature cannot be limited because it varies depending on the organic metal compound and solvent used, but when an organoaluminum compound is used with n-hexane as a solvent, the treatment temperature is preferably 0-15.
The temperature is 0 ° C, more preferably 20 to 100 ° C.
The treatment time varies depending on the contact temperature, but generally 5
Minutes to 24 hours, preferably 10 minutes to 12
Time, and more preferably 20 minutes to 6 hours. Further, of course, the heat treatment may be performed under reduced pressure. For the treatment with halogen, it is preferable to use a fluorine compound as the halogen. Further, it is most preferable to coexist with halogen during the heat treatment to remove the OH group. The treatment temperature and the treatment time are the same as those in the heat treatment.

As a method of dissolving the titanium compound and the magnesium compound in the heterocyclic compound (D ₁ ) and then loading the solution on the inert inorganic compound carrier, there is a method of adding a poor solvent and coprecipitating, but it is preferable. , Heterocyclic compounds (D
₁ ) is vaporized and a titanium compound, a magnesium compound and a heterocyclic compound (D ₁ ) are supported on an inorganic compound carrier. The temperature at which the heterocyclic compound (D ₁ ) is vaporized is preferably at least the boiling point of the heterocyclic compound (D ₁ ). However, when it is performed under reduced pressure, it means the boiling point or higher at that pressure. The preferred temperature varies depending on the type of the heterocyclic compound (D ₁ ) used and the degree of reduced pressure, but when the heterocyclic compound (D ₁ ) is tetrahydrofuran, the temperature is 0 to 150 ° C., and preferably 20 ° C.
~ 100 ° C. The time required for loading depends on the kind of the heterocyclic compound used, the degree of reduced pressure and the temperature at which it is vaporized, but it is generally completed within 48 hours.

The heterocyclic compound (D ₁ ) and titanium atom (T) contained in the obtained catalyst solid component (III).
The molar ratio of is preferably 0.1 <D ₁ / T <30, and it is desirable to determine the end time so that it can be controlled within this range. Of course, it is desirable to determine the end time by drying while analyzing the amount of the heterocyclic compound (D ₁ ) contained in the catalyst solid component (III). The ratio of the titanium compound to 1 mol of the magnesium compound contained in the catalyst solid component (I) or the catalyst solid component (III) is generally 0.02 to 20 mol.

In the co-grinding method and the contact method in an inert solvent, the ratio of the heterocyclic compound (D ₁ ) to 1 mol of magnesium is usually at most 50 mol. In the method of bringing the heterocyclic compound (D ₁ ) into contact with the solvent and the method of dissolving the titanium compound and the magnesium compound in the heterocyclic compound (D ₁ ) and supporting them on an inert inorganic carrier, 1 mol of The ratio of heterocyclic compound (D ₁ ) to magnesium is usually at most 500 mol.

To prepare the catalyst solid component (II) or the catalyst solid component (IV), the catalyst solid component (I) is prepared, respectively.
Alternatively, the catalyst solid component (III) is replaced with the heterocyclic compound (D
Prepared by treating with ₂ ). As a method for treating with a main heterocyclic compound (D ₂ ), there are 1) a co-grinding method and 2) a method of bringing them into contact with each other in an inert solvent. When an inert inorganic compound carrier having a particle diameter of 10 μm or less is used, the co-milling method 1) is not preferable because the morphology cannot be maintained. The method of 1) co-milling and the method of 2) contacting in an inert solvent are the same as the method of treating with the heterocyclic compound (D ₁ ).

[0021] As the charged amount of a heterocyclic compound (D _2), the type of heterocyclic compounds (D _2), the reaction temperature, the preferred amount depending on the reaction conditions will vary, heterocyclic compounds and (D ₂₎ Catalyst solid component (I) or catalyst solid component (I
The molar ratio of titanium atoms (T) contained in II) (D ₂ /
As T), 0.01 <D ₂ / T <1000 is preferable. The heterocyclic compound (D) contained in the catalyst solid component (II) or the catalyst solid component (IV) obtained as a result of the treatment
₁ ), sum of heterocyclic compound (D ₂ ) and titanium atom (T)
Molar ratio of (D ₁ + D ₂ / T) and the heterocyclic compound (D
₁ ) and the heterocyclic compound (D ₂ ) molar ratio (D ₁ / D ₂ ).
Is 0 <D ₁ + D ₂ / T <100, and
Adjust so that 0 <D ₁ / D ₂ <100. Preferably, 0.05 <D ₁ + D ₂ / T <5
0 and 0.05 <D ₁ / D ₂
<70. Particularly preferably, 0.1 <D ₁ + D ₂
/ T <30 and 0.1 <D ₁
/ D ₂ <50.

The organometallic compound (M) for treating the catalyst solid component (I) or the catalyst solid component (III) is mainly an organoboron compound, an organozinc compound, an organomagnesium compound or an organoaluminum compound. . Preferably, an organoaluminum compound represented by the general formula AIR _a X _3-a is used. In the above formula, R is an aliphatic, alicyclic or aromatic hydrocarbon having at most 12 carbon atoms, X is a halogen atom or a hydrogen atom, and a is a number of 1 or more and 3 or less.
Typical examples are triethylaluminum, triisobutylaluminum, trinormalhexylaluminum,
Tri-normal octyl aluminum, diethyl aluminum chloride, di-normal butyl aluminum chloride, di-normal hexyl aluminum chloride, di-normal octyl aluminum chloride, ethyl aluminum dichloride, normal butyl aluminum dichloride, normal hexyl aluminum dichloride, normal octyl dichloride, diethyl aluminum hydride, di Examples thereof include normal butyl aluminum hydride, dinormal hexyl aluminum hydride, and dinormal octyl aluminum hydride. In addition, these various organoaluminum compounds can be used alone or in combination.
It can also be used in combination with more than one type.

To prepare the catalyst solid component (V), the catalyst solid component (I) or the catalyst solid component (III) is treated with the heterocyclic compound (D ₂ ) and further with the organometallic compound (M). To do. Examples of the treatment method include 1) a method of contacting in an inert solvent, 2) a method of contacting using the organometallic compound (M) as a solvent, and a method of contacting in an inert solvent is preferable. Of course, the catalyst solid component (I) or the catalyst solid component (II
I) is treated with the heterocyclic compound (D ₂ ) and then dried once to obtain the catalyst solid component (II) or the catalyst solid component (I).
The above method also includes a method of treating V) and further treating with the organometallic compound (M).

As the inert solvent used as the method of contacting in an inert solvent, it is desirable to use a dry one containing no water. As the inert solvent used in this case, an aliphatic chain hydrocarbon having a boiling point of 10 to 300 ° C. (for example, i-pentane, n-hexane, n-heptane, n-octane, etc.), an aliphatic cyclic hydrocarbon (for example, Examples thereof include cyclohexane), aromatic hydrocarbons (eg benzene, toluene, xylene etc.) and halogenated hydrocarbons (carbon tetrachloride, trichloroethylene etc.). Since the contact temperature varies depending on the solvent used, it is not possible to limit the preferred temperature, but when n-hexane is used as the solvent, it is preferably 0 to 150 ° C, more preferably 20 to 100 ° C.
Is. The contact time depends on the contact temperature,
It is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours, more preferably 20 minutes to 1 hour.
2 hours. The reaction atmosphere is preferably under an inert gas.

[0025] As the charged amount of a heterocyclic compound (D _2), the type of heterocyclic compounds (D _2), the reaction temperature, the preferred amount depending on the reaction conditions will vary, heterocyclic compounds and (D ₂₎ Catalyst solid component (I) or catalyst solid component (I
The molar ratio of titanium atoms (T) contained in II) (D ₂ /
As T), 0.01 <D ₂ / T <1000 is preferable. The molar ratio (D ₁ + D ₂ / T) of the sum of the heterocyclic compound (D ₁ ) and the heterocyclic compound (D ₂ ) contained in the catalyst solid component (V) obtained as a result of the treatment and the titanium atom (T). ) and heterocyclic compounds the molar ratio of (D ₁₎ with a heterocyclic compound _{(D 2) (D 1 /} D 2) _{is, 0 <D 1 + D 2} / T <100
And 0 <D ₁ / D ₂ <1
Adjust to 00. Preferably, 0.05 <
D ₁ + D ₂ / T <50, and 0.
05 <D ₁ / D ₂ <70. Particularly preferably,
0.1 <D ₁ + D ₂ / T <30, and
0.1 <D ₁ / D ₂ <50.

The amount of the organometallic compound (M) charged varies depending on the type of the organometallic compound (M), the reaction temperature and the reaction conditions, but the organometallic compound (M) and the catalyst solid component (I) are different. Or catalyst solid component (II
The molar ratio (M / T) of titanium atoms (T) contained in I) is preferably 0.01 <M / T <100. More preferably, 0.1 <M / T <50. Most of the organic compound (M) is supported on the catalyst solid component (I) or the catalyst solid component (III). The molar ratio of the organic compound (M) and the titanium atom (T) contained in the catalyst solid component (I) or the catalyst solid component (III) obtained as a result of the treatment (M
/ T) is preferably 0.01 <M / T <100
And particularly preferably adjusted so that 0.1 <M / T <50. Further, the solid catalyst component obtained after the reaction may be stored in the form of a slurry or may be dried to give a powder. Examples of the drying method include a method of removing the supernatant and then drying, a method of vaporizing an inert solvent as it is, and the like.

To prepare the solid catalyst component (VII),
First, the catalyst solid component (I) or the catalyst solid component (II
The catalyst solid component (VI) is prepared by treating I) with the organometallic compound (M). As a method of treating the catalyst solid component (I) or the catalyst solid component (III) with the organometallic compound (M), the catalyst solid component (II) or the catalyst solid component (IV) is further treated with the organometallic compound (M). It is similar to the case. The amount of the organometallic compound (M) charged varies depending on the type of the organometallic compound (M), the reaction temperature and the reaction conditions, but the organometallic compound (M) and the catalyst solid component (I) or the catalyst solid Ingredient (II
The molar ratio (M / T) of titanium atoms (T) contained in I) is preferably 0.01 <M / T <100. More preferably, 0.1 <M / T <50. Most of the organometallic compound (M) is supported in the catalyst solid component (I) or the catalyst solid component (III). The molar ratio (M / T) of the organometallic compound (M) and the titanium atom (T) contained in the catalyst solid component (I) or the catalyst solid component (III) obtained as a result of the treatment is preferably 0.01 <M / T <10
0, particularly preferably 0.1 <M / T <50
Adjust so that

The catalyst solid component (V
I) are successively treated with a heterocyclic compound (D ₂ ) to give a catalyst solid component (VII). The obtained catalyst solid component (V
As the method of treating with I) the heterocyclic compound (D ₂ ), there are 1) co-grinding method and 2) contact in an inert solvent. When the catalyst solid component (III) is used,
When an inert inorganic compound carrier having a narrow particle size distribution of 10 μm or more is used, the co-milling method 1) is not preferable because the morphology cannot be maintained. Both 1) the co-milling method and 2) the method of contacting in an inert solvent are
3) The same as the one already described in the method of treating with a heterocyclic compound (D ₁ ).

[0029] As the charged amount of a heterocyclic compound (D _2), the type of heterocyclic compounds (D _2), the reaction temperature, the preferred amount depending on the reaction conditions will vary, heterocyclic compounds and (D ₂₎ Catalyst solid component (I) or catalyst solid component (I
The molar ratio of titanium atoms (T) contained in II) (D ₂ /
As T), 0.01 <D ₂ / T <1000 is preferable. The molar ratio of the sum of the heterocyclic compound (D ₁ ) and the heterocyclic compound (D ₂ ) and the titanium atom (T) contained in the catalyst solid component (VI) obtained as a result of the treatment (D ₁ + D ₂ ) / T and the molar ratio of D ₁ and D ₂ (D ₁ / D ₂ ) is 0 < (D ₁ +
D ₂ ) / T <100, and 0
Adjust so that <D ₁ / D ₂ <100. Preferably, 0.05 < (D ₁ + D ₂ ) / T <50
And 0.05 <D ₁ / D ₂ <7
It is 0. Particularly preferably, 0.1 < (D ₁ + D ₂ ).
/ T <30 and 0.1 <D ₁
/ D ₂ <50. Further, the solid catalyst component obtained after the reaction may be stored in the form of a slurry or may be dried to give a powder. Examples of the drying method include a method of removing the supernatant and then drying, a method of vaporizing an inert solvent as it is, and the like.

To prepare the catalyst solid component (VIII)
Is an organometallic compound (M) and a heterocyclic compound (D
₂ ) Contact. Organometallic compound (M) and heterocyclization
Compound (D ₂ ) As a method of contacting in advance, 1) Method of contact in an inert solvent 2) There is a method of contacting without diluting. 1) Method of contact in an inert solvent For the method of contacting in an inert solvent, see (3)
Cyclic compound (D₁ Already mentioned in the method of processing
It is similar to Organometallic compounds in an inert solvent
(M) and a heterocyclic compound (D₂ ) Is input in any order
This may come first.

2) Method of contacting without dilution The method of contacting without diluting is the same as the method of contacting in an inert solvent of 1) except that it is not diluted with an inert solvent. However, since the reactivity in the case of contact is higher than that in the case of diluting, it is preferable to have a system capable of sufficiently removing the generated heat of reaction. Also,
When the reaction is vigorous, it is preferable to charge the organometallic compound (M) into the heterocyclic compound (D ₂ ), and it is particularly preferable to suppress the charging speed. In any of 1) a method of contacting in an inert solvent and 2) a method of contacting without diluting, the amount of the heterocyclic compound (D ₂ ) and the organometallic compound (M) charged is the heterocyclic compound ( D ₂ ) and the catalyst solid component (I) or the titanium atom (T) contained in the catalyst solid component (III) in a molar ratio (D ₂ / T), and a molar ratio of M to T (M / T).
0.01 <D ₂ / T <1000 and 0.01 <
M / T <100 is preferred.

Then, the catalyst solid component (I) or the catalyst solid component (III) is treated with a reaction mixture in which the organometallic compound (M) and the heterocyclic compound (D ₂ ) are contacted in advance.
As a method of treating the catalyst solid component (I) or the catalyst solid component (III) with a reaction mixture in which the organometallic compound (M) and the heterocyclic compound (D ₂ ) are contacted in advance, 1) in an inert solvent 2) There is a method of contacting without diluting. When the method of contacting without dilution in 1) is adopted, it is preferable to select the method of 1) contacting in an inert solvent.
In any of the methods 1) and 2), the reaction temperature is preferably 0 to
It is 150 ° C., more preferably 20 to 100 ° C. The reaction time is preferably 10 minutes to 24 hours, more preferably 20 minutes to 12 hours. Further, the solid catalyst component obtained after the reaction may be stored in the form of a slurry or may be dried to give a powder. Examples of the drying method include a method of removing the supernatant and then drying, a method of vaporizing an inert solvent as it is, and the like.

These catalyst solid components are used together with an organoaluminum compound to be used as a polymerization catalyst solid component.
As the organoaluminum compound to be added to the catalyst solid component, an organoaluminum compound represented by the general formula AlR _a X _3-a is used. In the above formula, R is an aliphatic, alicyclic or aromatic hydrocarbon having at most 12 carbon atoms, X is a halogen atom or a hydrogen atom, and a is a number of 1 or more and 3 or less.
Typical examples are triethylaluminum, triisobutylaluminum, trinormalhexylaluminum,
Tri-normal octyl aluminum, diethyl aluminum chloride, di-normal butyl aluminum chloride, di-normal hexyl aluminum chloride, di-normal octyl aluminum chloride, ethyl aluminum dichloride, normal butyl aluminum dichloride, normal hexyl aluminum dichloride, normal octyl dichloride, diethyl aluminum hydride, di Examples thereof include normal butyl aluminum hydride, dinormal hexyl aluminum hydride, and dinormal octyl aluminum hydride. In addition, these various organoaluminum compounds can be used alone or in combination.
It can also be used in combination with more than one type.

The catalyst solid component blended with the organoaluminum compound uses ethylene as a polymerization catalyst for homopolymerization or copolymerization of ethylene and alpha olefin.
The alpha olefin used in the case of copolymerizing with ethylene is an alpha olefin having at most 20, preferably at most 12, carbon atoms, such as propylene,
1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like can be mentioned. The proportion of the above-mentioned alpha olefin in the obtained ethylene copolymer is generally preferably 20 mol% or less, and particularly 15
It is preferably not more than mol%. In carrying out the present invention, the polymerization method is not particularly limited, but a liquid phase polymerization method such as slurry polymerization or solution polymerization, a gas phase polymerization method and the like are possible. Further, not only batch polymerization but also continuous polymerization and batch polymerization can be applied. The liquid phase polymerization method is usually carried out in a hydrocarbon solvent, and as the hydrocarbon solvent, propane, butane, isobutane, hexane, octane, decane, cyclohexane, benzene, toluene, xylene and the like inert hydrocarbons alone or A mixture is used.
The polymerization temperature is generally 0 to 300 ° C., and practically 20
~ 200 ° C. The polymerization pressure is from atmospheric pressure to 100 kg /
cm ² G, preferably 3 to 50 kg / cm ² G.
A chain transfer agent such as hydrogen may coexist in the polymerization system to adjust the molecular weight, if necessary.

In this catalyst system, the high load melt flow rate (hereinafter abbreviated as HLMFR) 0.0001 g / 1
It is possible to produce a polymer from 0 min to a melt flow rate (hereinafter abbreviated as MFR) to 1000 g / 10 min and a density (described in Examples) from 0.880 to 0.970 g / cm ³ . Further, an ethylene polymer having a broader molecular weight distribution than that of an ethylene polymer which can be produced by a conventional catalyst system can be provided in a single stage polymerization with good production. It is also possible to produce an ethylene-based polymer having a broader molecular weight distribution by utilizing a process such as multi-stage polymerization, and by controlling the molecular weight distribution using a technique such as a process 1) film ( A balance film is included) 2) Blow 3) It can also be used for pipes and the like. The polyethylene obtained here can utilize the additives and processing methods commonly used for polyolefins. It can also be used as a mixture with other thermoplastic resins.

[0036]

The ethylene-based polymer has a degree of polymerization, a molecular weight distribution, a crystallinity, a density, etc., which are suitable for the processing method and application, and a polymerization catalyst suitable for these ethylene-based polymers has been proposed. A catalyst system using titanium as a transition metal element using a heterocyclic compound is generally said to produce a polymer having a narrow molecular weight distribution, and it has been difficult to produce a single-stage polymer having a wide molecular weight distribution. INDUSTRIAL APPLICABILITY The present invention is a titanium-heterocyclic compound-based catalyst, and even in a single-stage polymerization, an n-membered heterocyclic compound (D ₁ ) and an m-membered ring (m
It has been found that when a heterocyclic compound (D ₂ ) of n + 1 or more or n + 1 or less) is used in combination, a polymer having less stickiness and a wide molecular weight distribution can be produced, though the detailed mechanism thereof is unknown. It is based on.

The reason why the transition metal element is limited to titanium is that vanadium has a problem of coloring black and chromium has a problem of coloring green, and zirconium has a problem of poor copolymerizability and a large amount of sticky components. On the other hand, titanium is excellent in that it has no coloring problem because it is white even when it is deactivated to titanium dioxide. When the polymers produced using the catalyst of the present invention were compared at the same density and the same melt flow rate of commercial products, the stickiness (compared with the hexane extraction amount) was observed despite the fact that the molecular weight was wide. It has not deteriorated.

[0038]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below. The methods for measuring various physical properties of the catalyst and ethylene polymer in the present invention are shown below. Catalyst analysis Metal component analysis: The catalyst was decomposed with a 10% sulfuric acid aqueous solution, and high frequency induction plasma emission spectroscopy (ICP; Japan J
arell-Ash). Analysis of heterocyclic component: The catalyst was extracted with acetone containing an internal standard and measured by gas chromatography (manufactured by Shimadzu Corporation) by the internal standard method. Melt flow rate (MFR) According to JIS K-7210, condition 4 in Table 1, temperature is 1
The measurement was performed under the conditions of 90 ° C. and a load of 2.16 kg. High load melt flow rate (HLMFR) According to JIS K-7210, condition 7 in Table 1, the temperature is 1
The measurement was performed at 90 ° C. and a load of 21.6 kg. It is a numerical value obtained by dividing HLMFR calculated by HLMFR / MFR by MFR calculated by. Density Measured according to JIS K-6760. Hexane extraction amount The obtained ethylene polymer was refluxed in boiling hexane 6
It was extracted for a period of time, and the extracted weight (ΔW) was divided by the weight (W) of the original polymer and multiplied by 100. The weight fraction (wt)
%) Is displayed. Hexane extraction amount (wt%) = ΔW / W × 100

Example 1 [Preparation of Catalyst Solid Component (I)] Anhydrous magnesium chloride (commercial anhydrous magnesium chloride in a nitrogen stream at about 500)
35.0 g of the product obtained by heating and drying at 15 ° C. for 15 hours and 15.0 g of AA type titanium trichloride (manufactured by Toso-Akzo Co., Ltd.) were used for a vibrating ball mill container (stainless steel, cylindrical type, internal volume 1 liter). , And a magnetic ball mill with a diameter of 10 mm was apparently put in 50% by volume).
This was attached to a vibrating ball mill having an amplitude of 6 mm and a frequency of 30 Hz, and co-pulverization was carried out for 8 hours to obtain a uniform co-pulverized product. 5.0 g of this co-ground product was placed in a 500 ml flask. Another 50 ml hexane and 0.
5 g of glycidoxypropyltrimethoxysilane was added, and the mixture was stirred at room temperature for 1 hour. The product was thoroughly washed with hexane (until almost no titanium atom and glycidoxypropyltrimethoxysilane were found in the washing solution). To this treated product was added 100 ml of toluene, and further 12 ml of tetrahydrofuran (TH
F) was added, and the mixture was sufficiently stirred at room temperature for 2 hours.
After thoroughly washing the obtained product with hexane,
Drying was performed under reduced pressure at a temperature of 60 ° C. for 3 hours. As a result, a catalyst solid component (I) was obtained.

[Preparation of catalyst solid component (II)] The catalyst solid component (I) was placed in a 100 ml flask thoroughly replaced with nitrogen.
3.50 g was made into a suspension with 27 ml of hexane. After the temperature of this suspension was raised to 50 ° C., 7.2 ml (73 mmol) of tetrahydropyran (THP) corresponding to 10 times the moles of titanium atoms in the catalyst solid component (I) was added, and the mixture was heated to 50 ° C. The mixture was stirred for 1 hour and reacted. Then 65
The temperature was raised to ℃, and hexane was slowly distilled off under reduced pressure.
The catalyst solid component (II) was dried at 10 ° C for 10 hours.
Got [Polymerization] 2.0 mm of triethylaluminum in a stainless steel autoclave equipped with a stirrer with an internal volume of 1.5 liters.
ol, 1-hexene (92 g) and isobutane (600 ml) were added, the temperature was raised to 85 ° C. with stirring, and the hydrogen partial pressure was 0.1 at the gauge pressure of the pressure gauge installed in the autoclave.
Hydrogen was introduced so that the concentration would be kg / cm ² . 20 mg of the catalyst solid component (II) prepared above was slurried with a small amount of isobutane, then pressurized with ethylene and introduced into an autoclave to start polymerization. Also, the ethylene partial pressure is 5 at the gauge pressure of the pressure gauge installed in the autoclave.
Polymerization was carried out for 30 minutes while continuing the supply of ethylene so as to obtain kg / cm ² . After 30 minutes from the start of the polymerization, the supply of ethylene was stopped, the stirring was stopped, and the unreacted gas in the autoclave was discharged to stop the polymerization. The produced polymer was vacuum dried at 60 ° C. for 4 hours to obtain 90 g of a polymer. Polymerization activity (produced polymer weight divided by catalyst weight, ethylene partial pressure, time) is 1800 g / g x (kg / cm
² ) xh, MFR is 0.51g / 10min, HLM
FR / MFR is 45.3 and density is 0.912 g / cm ^3.
Met.

Comparative Example 1 [Preparation of Catalyst Solid Component (I)] The catalyst solid component (I) of Example 1 was prepared and used in the following polymerization. [Polymerization] Polymerization was carried out under the same conditions and method as in Example 1, except that 15 mg of the catalyst solid component (I) of Example 1 was used. The polymerization results are shown in Table 1.

Example 2 [Preparation of catalyst solid component (III)] 340 g of silica gel were heated in a fluidized bed dehydrator at a temperature of 600 ° C. with nitrogen at a surface gas velocity equal to 3 to 10 times the minimum fluidization velocity. It was dehydrated for 4 hours by passing it through. The silica gel was cooled to room temperature with nitrogen. Following this, dry silica gel was slurried with 2.6 liters of isopentane under a nitrogen atmosphere and 24 ml of triethylaluminum was added while stirring the slurry,
The mixture was stirred at 55 ° C for 1 hour. The mixture was heated to 70 ° C. and isopentane was removed in about 10 hours to obtain a powder product. Next, 2.84 liters of tetrahydrofuran (THF) and 33 g of anhydrous magnesium chloride were put in another container, and 22.9 g of AA type titanium trichloride was added while stirring the obtained mixture under a nitrogen atmosphere, 3 at 60 ° C
Stir for hours. This reaction solution was added to the above powder product and stirred at 55 ° C. for 1 hour, and then under reduced pressure at 70 ° C. for about 20 minutes.
The catalyst solid component (III) was obtained by drying for an hour.

[Preparation of catalyst solid component (IV)] A catalyst solid component (II
I) 3.36 g was made into a suspension with 26 ml of hexane.
After the temperature of this suspension was raised to 50 ° C., the catalyst solid component (II
Tetrahydropyran (THP) (0.90 ml, 9.2 mmol), which was 10 times the mole number of titanium atoms in I), was added, and the mixture was reacted by stirring at 50 ° C. for 1 hour. Then 65
The temperature was raised to ℃, and hexane was slowly distilled off under reduced pressure.
The catalyst solid component (IV) was dried at 10 ° C for 10 hours.
Got [Polymerization] Polymerization was carried out under the same conditions and method as in Example 1, except that 96 mg of the catalyst solid component (IV) of Example 2 was used. The polymerization results are shown in Table 1.

Example 3 [Preparation of catalyst solid component (III)] The catalyst solid component (III) of Example 2 was used for preparation of the following catalyst solid component (IV). [Preparation of catalyst solid component (IV)] 1 fully substituted with nitrogen
The catalyst solid component (III) 2.45 in a 00 ml flask.
g was made into a suspension with 20 ml of hexane. After the temperature of this suspension was raised to 50 ° C., 0.74 ml (6.7 mmol) of N-methylmorpholine, which was 10 times the molar amount of titanium atoms in the catalyst solid component (III), was added, and the mixture was heated at 50 ° C. 1
The reaction was allowed to stir for hours. Thereafter, the temperature was raised to 65 ° C., hexane was slowly distilled off under reduced pressure, and drying was performed at 65 ° C. for 10 hours to obtain a catalyst solid component (IV). [Polymerization] Polymerization was carried out under the same conditions and method as in Example 1, except that 99 mg of the catalyst solid component (IV) in Example 3 was used. The polymerization results are shown in Table 1.

Comparative Example 2 [Preparation of Catalyst Solid Component (III)] The catalyst solid component (III) was prepared in the same manner as in Example 2 and used in the following polymerization. [Polymerization] 71 mg of the catalyst solid component (III) of Example 2
Polymerization was carried out under the same conditions and methods as in Example 1, except that the amount used and the amount of hydrogen introduced used in the polymerization shown in Table 1 were used. The polymerization results are shown in Table 1.

Comparative Examples 3 to 5 [Preparation of Catalyst Solid Component (III)] The catalyst solid component (III) was prepared in the same manner as in Example 2 and used for the preparation of the following catalyst solid component (IV). [Preparation of Catalyst Solid Component (IV)] In place of the tetrahydropyran of Example 2, thiophene (Comparative Example 3), furan (Comparative Example 4) and 2,5-dimethyltetrahydrofuran (Comparative Example 5) were used. Otherwise, the catalyst solid component (IV) was prepared in the same manner as in Example 2 and used in the following polymerization. [Polymerization] The catalyst solid component (IV) obtained in each Comparative Example was 88 mg in Comparative Example 3 and 110 m in Comparative Example 4.
Polymerization was carried out under the same conditions and method as in Example 1, except that 104 mg was used in Comparative Example 5 and the amounts of triethylaluminum used for polymerization and the amount of hydrogen introduced were used as shown in Table 1, respectively. . The polymerization results are shown in Table 1.

[0047]

[Table 1]

Examples 4 to 5 [Preparation of catalyst solid component (III)] The catalyst solid component (III) was prepared in the same manner as in Example 2 and used for the preparation of the catalyst solid component (IV) below. [Preparation of catalyst solid component (IV)] In the preparation of the catalyst solid component (IV) of Example 2, tetrahydropyran was used in an amount of 2 or 5 times the mol of titanium atom mol of the catalyst solid component (III). Were all prepared in the same manner as in Example 2 to prepare a catalyst solid component (IV). [Polymerization] Using the catalyst solid component (IV) obtained above, and the amount of triethylaluminum used in the polymerization,
Polymerization was carried out under the same conditions and methods as in Example 1, except that the amounts of hydrogen introduced were used as shown in Table 2. The polymerization results are shown in Table 2.

[0049]

[Table 2]

Examples 6 to 9 [Preparation of catalyst solid component (III)] The catalyst solid component (III) was prepared in the same manner as in Example 2 and used for the preparation of the catalyst solid component (IV) below. [Preparation of Catalyst Solid Component (IV)] The catalyst solid component (IV) was prepared in the same manner as in Example 3 and used for the following polymerization. [Polymerization] Polymerization was carried out under the same conditions and methods as in Example 1, except that the amounts of triethylaluminum and hydrogen introduced used in the polymerization were used as shown in Table 3, respectively. The polymerization results are shown in Table 3.

[0051]

[Table 3]

Example 10 [Preparation of catalyst solid component (III)] The catalyst solid component (III) was prepared in the same manner as in Example 2 and used for the preparation of the catalyst solid component (IV) below. [Preparation of catalyst solid component (VIII)] Catalyst solid component (III) 2.
45 g was made into a suspension with 20 ml of hexane. In another 100 ml flask sufficiently replaced with nitrogen, 10 times the number of moles of titanium atom in the catalyst solid component (III)
4-dioxane (0.58 ml, 6.7 mmol) and 5-fold molar triethylaluminum were added, and the mixture was stirred at 50 ° C. for 1 hour. This was added to the above-mentioned suspension and stirred at 50 ° C. for 1 hour to react. After that, the temperature was raised to 65 ° C., hexane was slowly distilled off under reduced pressure, and the solid was dried at 65 ° C. for 10 hours to obtain a catalyst solid component (VIII). [Polymerization] Except that the catalyst solid component (VIII) of Example 10 was used, and the amounts of triethylaluminum and hydrogen introduced used in the polymerization were the amounts shown in Table 4, respectively,
Polymerization was carried out under the same conditions and methods as in Example 1. The polymerization results are shown in Table 4.

Examples 11 to 13 [Preparation of catalyst solid component (III)] The catalyst solid component (III) was prepared in the same manner as in Example 2 and used for the preparation of the catalyst solid component (IV) below. [Preparation of catalyst solid component (VIII)] In the preparation of the catalyst solid component (VIII) of Example 10, Table 4 shows the contact time between 1,4-dioxane and triethylaluminum and the treatment time with the catalyst solid component (III). All were carried out in the same manner as in Example 10 except for the conditions shown. [Polymerization] Catalyst solid component (VIII) obtained in each example
Was used, and the amounts of triethylaluminum used for polymerization and the amount of hydrogen introduced were used as shown in Table 4, respectively. Polymerization was carried out under the same conditions and methods as in Example 1.
The polymerization results are shown in Table 4.

[0054]

[Table 4]

Example 14 [Preparation of catalyst solid component (III)] Prepared in the same manner as the catalyst solid component (III) of Example 2 and used for preparation of the following catalyst solid component (V). [Preparation of Catalyst Solid Component (V)] 10
2.03 g of catalyst solid component (III) in a 0 ml flask
Was suspended in 16 ml of hexane. 5 this suspension
After the temperature was raised to 0 ° C., 0.54 ml (5.5 mmol) of tetrahydropyran (THP) in an amount 10 times the molar amount of titanium atoms in the solid catalyst component (III) was added, and
The reaction was allowed to stir at 0 ° C. for 30 minutes. Thereafter, diethyl aluminum chloride was added in an amount twice the molar amount of titanium atoms in the catalyst solid component (III), and the amount was further 30
After stirring for 1 minute, the temperature was raised to 65 ° C., hexane was slowly distilled off under reduced pressure, and drying was performed at 65 ° C. for 10 hours to obtain a catalyst solid component (V). [Polymerization] Other than using the catalyst solid component (V) obtained in Example 14 and using the amounts of triethylaluminum and hydrogen introduced used in the polymerization shown in Table 5, respectively.
Polymerization was carried out under the same conditions and methods as in Example 1. The polymerization results are shown in Table 5.

Example 15 [Preparation of catalyst solid component (III)] The catalyst solid component (III) was prepared in the same manner as in Example 2 and used for the preparation of the catalyst solid component (V) below. [Preparation of Catalyst Solid Component (V)] In the same manner as in Example 14, except that ethylaluminum dichloride was used in place of diethylaluminum chloride in the preparation of the catalyst solid component (V) of Example 14, a catalyst solid was prepared. Ingredient (V) was prepared. [Polymerization] All the same as in Example 1 except that the catalyst solid component (V) obtained in each Example was used, and the amount of triethylaluminum used for polymerization and the amount of hydrogen introduced were used as shown in Table 5. Polymerization was performed under various conditions and methods. The polymerization results are shown in Table 5.

Example 16 [Preparation of catalyst solid component (III)] Prepared in the same manner as the catalyst solid component (III) of Example 2 to prepare the following catalyst solid component (VI) and catalyst solid component (VII). used. [Preparation of catalyst solid component (VI)] 3 fully substituted with nitrogen
Catalyst solid component (III) 20.3 in a 00 ml flask
g was made into a suspension with 160 ml of hexane. After the temperature of this suspension was raised to 50 ° C., 1.3 g (11 mmol) of triethylaluminum, which was twice the mole of titanium atoms in the catalyst solid component (III), was added and stirred for 1 hour.
Then, the temperature was raised to 65 ° C., hexane was slowly distilled off under reduced pressure, and the solid was dried at 65 ° C. for 10 hours to obtain a catalyst solid component (VI). [Preparation of catalyst solid component (VII)] Catalyst solid component (VI) 2.20 was placed in a 100 ml flask that had been sufficiently purged with nitrogen.
g was suspended with 18 ml of hexane. The temperature of this suspension was raised to 50 ° C., and 0.5 ml (5.1 mmol) of tetrahydropyran, which was 10 times the molar amount of titanium atoms in the catalyst solid component (VI), was added and stirred for 1 hour.
Then, the temperature was raised to 65 ° C., hexane was slowly distilled off under reduced pressure, and the solid was dried at 65 ° C. for 10 hours to obtain a catalyst solid component (VII). [Polymerization] All the same as in Example 1 except that the catalyst solid component (VII) obtained above was used, and the amounts of triethylaluminum and hydrogen introduced used in the polymerization were the amounts shown in Table 5, respectively. Polymerization was carried out under the conditions and methods.
The polymerization results are shown in Table 5.

Comparative Example 6 [Preparation of Catalyst Solid Component (III)] The catalyst solid component (III) was prepared in the same manner as in Example 2 and used for the preparation of the following catalyst solid component (VI). [Preparation of Catalyst Solid Component (VI)] The catalyst solid component (VI) was prepared in the same manner as in Example 17 and used for the following polymerization. [Polymerization] Except that the catalyst solid component (VI) obtained in Example 7 was used and the amounts of triethylaluminum and hydrogen introduced used in the polymerization were used as shown in Table 5, respectively,
Then, polymerization was carried out under the same conditions and method as in Example 1. The polymerization results are shown in Table 5.

[0059]

[Table 5]

[0060]

The catalyst containing a solid component for the catalyst for producing an ethylene polymer of the present invention is an ethylene-based catalyst having a broad molecular weight distribution without using any other element other than titanium as a transition metal element. The polymer can be provided with good productivity by single-stage polymerization. In particular, when linear low-density polyethylene, which is a copolymer of ethylene and propylene, 1-butene, 4-methyl-1-pentene, 1-octene, etc., is produced, the melt flow rate is wide despite the wide molecular weight distribution. Even if the rate is lowered, the processability is good, and when the film is formed, a polymer having excellent performance without stickiness is obtained.

[Brief description of drawings]

FIG. 1 is a flow chart showing an ethylene-based polymerization catalyst of the present invention, a method for producing the same, and a method for producing an ethylene-based polymer using the same.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shintaro Inazawa, Oita City, Oita Prefecture 2 Nakanosu, Oita Research Institute, Showa Denko Co., Ltd. (56) Reference JP-A-56-149405 (JP, A) JP-A-56-151707 (JP, A) JP 3-7703 (JP, A) JP 4-117411 (JP, A) JP 6-166716 (JP, A) JP 6-248019 (JP, A) 58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (9)

(57) [Claims] 1. A heterocyclic compound having at least a magnesium atom, a halogen atom, a titanium atom, an n-membered ring heterocyclic compound (D ₁ ) and an m-membered ring (m is a number of n + 1 or more or n-1 or less) ( D ₂ ) is an essential component, the molar ratio of the sum of D ₁ and D ₂ contained in the catalyst solid component and the titanium atom (T) is 0 <[(D ₁ + D ₂ ) / T] <100, and Solid component of a catalyst for producing an ethylene-based polymer in which 0 <D ₁ / D ₂ <100. 2. A solid component (I) containing at least a magnesium atom, a halogen atom, a titanium atom, and a heterocyclic compound (D ₁ ) having an n-membered ring as an essential component. The solid component (II) obtained by treating with (D ₂ ) or the solid component (III) obtained by supporting the solid component (I) on an inert inorganic compound carrier is used as a heterocyclic compound (D).
_The solid component of the catalyst for producing an ethylene polymer according to claim 1, which is the catalyst solid component (IV) treated with ₂ ). 3. The solid component is a catalyst solid component (V) obtained by treating the solid component (I) or the solid component (III) with the heterocyclic compound (D ₂ ) and then with the organometallic compound (M), Or solid component (I) or solid component (II
The ethylene-based polymer according to claim 1, which is a catalyst solid component (VII) obtained by further treating a solid component (VI) obtained by treating I) with an organometallic compound (M) with a heterocyclic compound (D ₂ ). Solid component of the catalyst for the production of. 4. A catalyst solid component (VIII ) obtained by reacting a heterocyclic compound (D ₂ ) with an organometallic compound (M) in advance, and treating the solid component (I) or solid component (III) with the solid component. ) Is a solid component of the catalyst for producing an ethylene polymer according to claim 1. 5. The n-membered heterocyclic compound (D ₁ ) is 4
To a 8-membered cyclic compound, which is a heterocyclic compound having a hydrocarbon group selected from an aliphatic hydrocarbon group and an aromatic hydrocarbon group having at most 16 carbon atoms or a substituent of a halogen atom. Item 4. A solid component of a catalyst for producing an ethylene polymer according to items 1 to 4. 6. The inert inorganic compound carrier is silica, silica-alumina, silica-titania, silica-zirconia, alumina or aluminum phosphate.
The solid component of the catalyst for producing the ethylene polymer described. 7. The organometallic compound (M) is AlR _a X
_3-a (wherein R is an aliphatic, alicyclic or aromatic hydrocarbon group having at most 12 carbon atoms, X is a hydrogen atom or a halogen atom, and a is a number of 1 to 3) .)
The solid component of the catalyst for producing an ethylene-based polymer according to claim 3, which is an aluminum compound represented by: 8. A catalyst solid component (II), (IV), (V), (VII) or (V) according to any one of claims 2 to 4.
A catalyst for producing an ethylene polymer, which comprises any of the components of III) and an organoaluminum compound. 9. A method for producing an ethylene-based polymer, which comprises homopolymerizing ethylene or copolymerizing ethylene and an alpha-olefin using the catalyst according to claim 8.