JP2812566B2 - Method for producing olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing an olefin polymer, particularly an ethylene polymer, and more particularly to a process for producing a novel ethylene polymer having excellent melt tension and a narrow composition distribution in a copolymer. About the method.

[0002]

BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The characteristics required for the ethylene copolymer differ depending on the molding method and application. For example, when molding an inflation film at a high speed, select an ethylene copolymer that has a high melt tension for its molecular weight in order to stably perform high-speed molding without bubble fluctuation or tearing. Must. Similar properties are required to prevent sagging or tearing in blow molding or to minimize width drop in T-die molding.

The high-pressure low-density polyethylene has a higher melt tension than an ethylene copolymer produced using a Ziegler-type catalyst, and is used for applications such as films and hollow containers. However, the high-pressure low-density polyethylene as described above is inferior in mechanical strength such as tensile strength, tear strength or impact strength, and also inferior in heat resistance and stress crack resistance.

On the other hand, a method for improving the moldability by improving the melt tension and expansion ratio (die swell ratio) of an ethylene polymer obtained using a Ziegler type catalyst, particularly a titanium catalyst, is disclosed in No. 90810 or JP-A-6
No. 0-106806.

[0005] However, in general, ethylene-based polymers, particularly low-density ethylene-based copolymers, obtained with a titanium-based catalyst have a problem that the composition distribution is wide and molded articles such as films are sticky.

[0006] For this reason, if an ethylene polymer having an excellent melt tension and a narrow composition distribution appears, its industrial value is extremely large. The present inventors have proposed a transition metal compound belonging to Group IVb of the Periodic Table having a compound having a structure in which at least two groups having a cyclopentadienyl skeleton are crosslinked by a carbon and / or silicon-containing group as a ligand. An organic aluminum oxy compound as an essential catalyst component,
Under certain conditions, olefins, especially ethylene or ethylene and α-olefins having 3 to 20 carbon atoms, can be (co) polymerized by ethylene copolymers having excellent melt tension and a narrow composition distribution in the copolymer. Have been obtained, and the present invention has been completed.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems in the prior art, and to provide an ethylene polymer having an excellent melt tension and a narrow composition distribution in a copolymer. It is intended to provide a manufacturing method.

[0008]

SUMMARY OF THE INVENTION According to the present invention, there is provided a method for producing an olefin polymer, comprising: (A) at least one olefin polymer having a cyclopentadienyl skeleton;
Using a solid catalyst formed from a transition metal compound of Group IVb of the Periodic Table and a (B) organoaluminum oxy compound having as a ligand a compound having a structure in which two groups are crosslinked by carbon and / or silicon-containing groups. And ethylene and α-olefin having 3 to 20 carbon atoms under the condition that the formed polymer exists in a solid state in the polymerization system.
A ) 55 to 99% by weight of a structural unit derived from ethylene
%, A structure derived from an α-olefin having 3 to 20 carbon atoms.
The formed units in a proportion of 1 to 45 wt%, b) a density of 0.86~0.95g / cm ³ range near
Ri, c) is in the range MFR of from 0.001 to 100 g / 10 min at 2.16kg load at 190 ° C., d) a melt tension (MT) and MFR of at log MT> -0.66log MFR + 0.5 meet the relationship indicated, e) an endothermic song was measured by a differential scanning calorimeter (DSC)
It is characterized by obtaining an ethylene / α-olefin copolymer in which the temperature (T) and the density at the maximum peak position in the line satisfy T <400d-250 . The ethylene / α-olefin copolymer
The merging was further performed at 23 ° C. in terms of the fraction of n-decane soluble components.
It is preferable that (W) and the density (d) satisfy the relationship expressed by log W <−50d + 46.6 . (A) at least having a cyclopentadienyl skeleton
Also have two groups bridged by carbon and / or silicon containing groups
Periodic Table IV with compounds having bridged structures as ligands
The group b transition metal compound is, for example, a transition metal represented by the following formula.
A transfer metal compound; M ¹ L ¹ _x (wherein, M ¹ is a transition metal, L ¹ is coordinated to the transition metal
And at least two L ¹ are cyclopentenes
A ligand having a tadienyl skeleton and a carbon and / or
Is linked through a silicon-containing group,
L ¹ other than the ligand having a dienyl skeleton has 1 to 1 carbon atoms.
2 hydrocarbon group, alkoxy group, aryloxy group, halo
X is the valence of the transition metal.
You. In the present invention, a transition metal compound represented by the following formula:
(E) is preferably used in combination with the transition metal compound (A).
Good. M ² L ² _x (wherein, M ² is a transition metal, and L ² is coordinated with the transition metal
And at least one L ² is cyclopentene
A ligand having a tadienyl skeleton;
L ² other than the ligand having a cyclopentadienyl skeleton having 1 to 12 carbon atoms
Hydrocarbon, alkoxy, aryloxy, halogen
X is the valence of the transition metal. )

[0009]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing an olefin polymer according to the present invention will be specifically described. The olefin polymer, particularly the ethylene polymer, produced by the present invention is an ethylene homopolymer or ethylene and a C3 to C3 polymer.
It is a random copolymer with 20 α-olefins.

The ethylene copolymer has a density of 0.86 to 0.95 g / cm ³ , preferably 0.87 to 0.95 g / cm ³ .
0.94 g / cm ³ , more preferably 0.88 to 0.93
g / cm ³ .

The density is 2.16 k at 190 ° C.
Strand obtained at the time of MFR measurement with g load is 120
After heat treatment at 1 ° C. for 1 hour and cooling to room temperature over 1 hour, measurement was carried out using a density gradient tube.

In such an ethylene copolymer, the constituent units derived from ethylene are present in an amount of 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 70 to 96% by weight. The structural unit derived from the α-olefin of the formulas 3 to 20 is 1 to 45% by weight, preferably 2 to 45% by weight.
Desirably, it is present in an amount of up to 35% by weight, more preferably 4 to 30% by weight.

The composition of the copolymer is usually 10 mmφ.
^13C -NM of a sample in which about 200 mg of the copolymer was uniformly dissolved in 1 ml of hexachlorobutadiene in a sample tube of
The R spectrum was measured at a measurement temperature of 120 ° C. and a measurement frequency of 25.
It is determined by measuring under measurement conditions of 05 MHz, a spectrum width of 1500 Hz, a pulse repetition time of 4.2 sec, and a pulse width of 6 μsec.

The C 3-20 α- used in the present invention.
As olefins, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like are used.

Further, the ethylene polymer according to the present invention comprises M
FR is 0.001 to 100 g / 10 min, preferably 0.0
It is desirable to be in the range of 1 to 50 g / 10 minutes. The MFR is 19 in accordance with ASTM D1238-65T.
It is measured under the condition of 0 ° C. and a load of 2.16 kg.

Further, the melt tension (MT) and MFR of the ethylene polymer produced according to the present invention are log MT> −0.66 log MFR + 0.5, preferably log MT> −0.66 log MFR + 0.6, more preferably log MT> −0.66 log MFR + 0.7 Particularly preferably, the relationship represented by log MT> −0.66 log MFR + 0.8 is satisfied.

Thus, the ethylene polymer produced by the present invention has excellent melt tension (MT) and good moldability. The melt tension (MT) is determined by measuring the stress when the molten polymer is stretched at a constant speed. That is, once the produced polymer powder or the powder is melted in decane, a polymer precipitated in a methanol / acetone (1/1) solution at least 5 times the amount of decane is used as a measurement sample, and manufactured by Toyo Seiki Seisaku-sho, Ltd. Using an MT measuring machine, resin temperature 190 ° C., extrusion speed 10 mm /
Min, winding speed 10-20m / min, nozzle diameter 2.09m
The measurement was performed under the conditions of mφ and a nozzle length of 8 mm. When measuring the melt tension, 0.1% by weight of 2,6-di-t-butylparacresol as a crosslinking stabilizer was previously blended with the ethylene copolymer.

In the ethylene copolymer produced according to the present invention, the temperature (T) and the density (d) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC) are as follows: T < 400d-250 Preferably, T <450d-297, more preferably, T <500d-344, and particularly preferably, the relationship represented by T <550d-391 is satisfied.

The DSC measurement was performed using a DSC-7 apparatus manufactured by PerkinElmer. The temperature (T) at the maximum peak position in the endothermic curve was determined by packing about 5 mg of a sample in an aluminum pan, heating the sample to 200 ° C. at 10 ° C./min,
After maintaining the temperature at 0 ° C. for 5 minutes, the temperature is lowered to room temperature at 20 ° C./min, and then determined from an endothermic curve when the temperature is raised at 10 ° C./min.

The ethylene copolymer produced according to the present invention has an n-decane soluble component fraction (W) and a density (d) at 23 ° C. of log W <−50d + 46.6, preferably log W <−50d + 46.5, more preferably log W <−50d + 46.4, and particularly preferably satisfy the relationship represented by log W <−50d + 46.3.

Thus, the relationship between the temperature (T) and the density (d), the fraction (W) of the n-decane soluble component, and the density (d)
Therefore, it can be said that the ethylene-based copolymer according to the present invention has a narrow composition distribution.

The amount of n-decane-soluble components is determined as follows. To measure the amount of n-decane-soluble component of the copolymer (the smaller the amount of soluble component, the narrower the composition distribution) is to add about 3 g of the copolymer to 450 ml of n-decane, dissolve at 145 ° C, and then to 23 ° C. After cooling, filtration was carried out to remove the n-decane-insoluble portion, and then turning the n-decane-soluble portion from the filtrate.

The ethylene polymer having the above-mentioned properties includes: (A) at least two polymers having a cyclopentadienyl skeleton
Using a solid catalyst formed from a transition metal compound of Group IVb of the Periodic Table and a (B) organoaluminum oxy compound having as a ligand a compound having a structure in which two groups are crosslinked by carbon and / or silicon-containing groups. In addition, it can be produced by polymerizing an olefin under the condition that the produced polymer exists in a solid state in a polymerization system.

The transition metal compound (A) used in the present invention has the following formula: M ¹ L ¹ _X (where M ¹ is a transition metal, and L ¹ is a ligand coordinated to the transition metal; At least two L ¹ are ligands having a cyclopentadienyl skeleton and are bonded via a carbon and / or silicon-containing group, and L ¹ other than the ligand having a cyclopentadienyl skeleton is Carbon number 1
To 12 hydrocarbon groups, alkoxy groups, aryloxy groups,
Is halogen or hydrogen, and x is the valence of the transition metal. ).

In the above formula, M ¹ is a transition metal, specifically, preferably zirconium, titanium or hafnium, chromium or vanadium,
Of these, zirconium and haunium are particularly preferred.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, dimethylcyclopentadienyl group. Examples thereof include an alkyl-substituted cyclopentadienyl group such as an enyl group and a pentamethylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group.

The ligand other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, halogen or hydrogen.
Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Specifically, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group, and the like.Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.Examples of the aryl group include a phenyl group and a tolyl group, and an aralkyl group includes a benzyl group. A neofil group is exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group, and examples of the aryloxy group include a phenoxy group.

As the halogen, fluorine, chlorine, bromine,
Examples include iodine. The transition metal compound (A) containing a ligand having a cyclopentadienyl skeleton used in the present invention has, for example, a transition metal valence of 4
Is more specifically represented by the following formula . R ² R ³ R ⁴ R ⁵ M ^{1 In the} formula, M ¹ is zirconium, titanium, hafnium or vanadium, and at least two of R ² , R ³ , R ⁴ and R ⁵ , for example, R ² and R ³ are cycloalkyl. A group having a pentadienyl skeleton, wherein the two groups having a cyclopentadienyl skeleton are a carbon- and / or silicon-containing group, for example, an alkylene group such as ethylene and propylene, and a substituted alkylene group such as isopropylidene and diphenylmethylene. Groups, a silylene group, a substituted silylene group such as dimethylsilylene, and the like. This place
If R ⁴ and R ⁵ are cyclopentadienyl skeleton group having an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom or hydrogen.

Hereinafter, at least two ligands having a cyclopentadienyl skeleton of (A) wherein M ¹ is zirconium, and the ligand having at least two cyclopentadienyl skeletons are alkylene Specific examples of the transition metal compound bonded through a group, a substituted alkylene group, a silylene group, and a substituted silylene group will be described. Ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium monochloride, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) ethyl zirconium monochloride, ethylene bis (indenyl) ) Methyl zirconium monobromide, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibromide, ethylene bis (4,5,6,7-tetrahydro-1-indenyl)
Dimethyl zirconium, ethylene bis (4,5,6,7-tetrahydro-1-indenyl)
Methyl zirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl)
Zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl)
Zirconium dibromide, ethylene bis (4-methyl-1-indenyl) zirconium dichloride, ethylene bis (5-methyl-1-indenyl) zirconium dichloride, ethylene bis (6-methyl-1-indenyl) zirconium dichloride, ethylene bis (7 -Methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methoxy-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1) -Indenyl) zirconium dichloride, ethylenebis (4,7-dimethoxy-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t) -Butyl fluoronyl) zircon Umujikurorido, isopropylidene (cyclopentadienyl - methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (methylcyclopentadienyl)
Zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, In such a zirconium compound, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal or vanadium metal can also be used.

The organoaluminum oxy compound (B) used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound discovered by the present inventors. Good.

The aluminoxane as described above can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution. (2) A method in which an organic aluminum compound such as trialkylaluminum is directly allowed to act on water, ice or steam in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover as a hydrocarbon solution.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in the solvent.

As the organoaluminum compound used for producing the solution of aluminoxane, specifically,
Trimethyl aluminum, Triethyl aluminum, Tripropyl aluminum, Triisopropyl aluminum, Tri n-butyl aluminum, Triisobutyl aluminum, Tri sec-butyl aluminum, Tri tert-butyl aluminum, Tripentyl aluminum, Trihexyl aluminum, Trioctyl aluminum, Tridecyl Aluminum, tricyclohexyl aluminum,
Trialkyl aluminum such as tricyclooctyl aluminum; dialkyl aluminum halide such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride; dialkyl aluminum hydride such as diethyl aluminum hydride and diisobutyl aluminum hydride; dimethyl aluminum methoxide; diethyl Dialkyl aluminum alkoxides such as aluminum ethoxide; and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

Of these, trialkylaluminum is particularly preferred. Further, as the organoaluminum compound, represented by the following general formula _{(i-C 4 H 9)} X Al y (C 5 H 10) Z (x, y, z are each a positive number, the z ≧ 2x) Isoprenyl aluminum can also be used.

The organoaluminum compound as described above is
Used alone or in combination. Examples of the solvent used for the solution of aluminoxane 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 methylcyclopentane; petroleum fractions such as gasoline, kerosene, and gas oil; and the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and halides of alicyclic hydrocarbons, especially , Chlorinated compounds, brominated compounds and the like. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of not more than 10%, preferably not more than 5%, particularly preferably not more than 2% in terms of Al atom. And insoluble or slightly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is determined by comparing the organoaluminum oxy compound, which corresponds to 100 milligram atoms of Al, with 10
After suspending in 0 ml of benzene and mixing at 60 ° C. for 6 hours with stirring, the mixture was filtered while hot at 60 ° C. using a G-5 glass filter equipped with a jacket, and the solid part separated on the filter was removed by 60 ° C. After washing four times with 50 ml of benzene at 50 ° C., the amount of Al atoms present in the total filtrate (x
Mmol) (x%).

When the above-mentioned benzene-insoluble organoaluminum oxy compound is analyzed by infrared spectroscopy (IR), the absorbance at around 1220 cm ^-1 (D
₁₂₂₀ ) and the absorbance (D ₁₂₆₀ ) around ₁₂₆₀ cm ⁻¹ (D ₁₂₆₀ / D ₁₂₂₀ ) are 0.09 or less;
Preferably 0.08 or less, particularly preferably 0.04 to 0.0.
07 is desirable.

The infrared spectroscopic analysis of the organic aluminum oxy compound is performed as follows. First, in a nitrogen box, an organic aluminum oxy compound and nujol are ground in an agate mortar to form a paste.

Next, the paste-like sample is sandwiched between KBr plates, and an IR spectrum is measured in a nitrogen atmosphere by IR-810 manufactured by JASCO Corporation. FIG. 1 shows the IR spectrum of the organoaluminum oxy compound used in the present invention.

From the IR spectrum thus obtained, D ₁₂₆₀ / D ₁₂₂₀ is obtained. The value of D ₁₂₆₀ / D ₁₂₂₀ is obtained as follows. (A) The local maximum points near 1280 cm ^-1 and 1240 cm ^-1 are connected, and this is defined as a baseline L ₁ . (B) Transmittance at the minimum absorption point near 1260 cm ^-1 (T
%) And a perpendicular to the wave number axis (horizontal axis) is drawn from this minimum point, the transmittance (T ₀ %) at the intersection of the perpendicular and the baseline L ₁ is read, and the absorbance (D near 1260 cm ⁻¹ ) is determined. ₁₂₆₀ = log T ₀ / T) is calculated. (C) Similarly bear maximum point in the vicinity of 1280 cm ^-1 and near 1180 cm ^-1, which is the baseline L _2. (D) The transmittance (T ′) at the minimum absorption point near 1220 cm ⁻¹
%) And a perpendicular to the wave number axis (horizontal axis) is drawn from this minimum point, and the transmittance (T ₀ '%) at the intersection of the perpendicular and the base line L ₂ is read, and the absorbance around 1220 cm ⁻¹ ( D ₁₂₂₀ = log T ₀ '/ T'). (E) D ₁₂₆₀ / D ₁₂₂₀ is calculated from these values.

FIG. 2 shows the IR spectrum of a conventionally known benzene-soluble organoaluminum oxy compound.
As can be seen from FIG. 2, the benzene-soluble organoaluminum oxy compound has a D ₁₂₆₀ / D ₁₂₂₀ value of approximately 0.10 to 0.13, and the benzene-insoluble organoaluminum oxy compound used in the present invention. The compounds are clearly different from the conventionally known benzene-soluble organoaluminum oxy compounds in D ₁₂₆₀ / D ₁₂₂₀ values.

The benzene-insoluble organoaluminum oxy compound as described above is represented by the following formula:

[0045]

Embedded image

(Wherein R ¹ is a hydrocarbon group having 1 to 12 carbon atoms). In the above alkyloxyaluminum unit, R ¹ is specifically a methyl group,
Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl, cyclooctyl and the like. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The benzene-insoluble organoaluminum oxy compound has the following formula:

[0048]

Embedded image

(Wherein R ¹ is a hydrocarbon group having 1 to 12 carbon atoms), in addition to the alkyloxyaluminum unit [i] represented by the following formula:

[0050]

Embedded image

(Wherein, R ² represents a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms,
Aryloxy group, hydroxyl group, halogen or hydrogen. R ² and R ¹ in the alkyloxyaluminum unit [i] represent different groups. )) May be contained. In that case, the alkyloxyaluminum unit [i] is at least 30 mol%, preferably at least 50 mol%,
Particularly preferred is an organoaluminumoxy compound having an alkyloxyaluminum unit containing at least 70 mol%.

Next, a method for producing the benzene-insoluble organoaluminum oxy compound as described above will be specifically described. This benzene-insoluble organoaluminum oxy compound is obtained by contacting a solution of aluminoxane with water or an active hydrogen-containing compound.

As the active hydrogen-containing compound, 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 are used. Of these, alcohols and diols are preferred, and alcohols are particularly preferred.

The water or active hydrogen-containing compound to be brought into contact with the aluminoxane solution is dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene and hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or It can be used in vapor, solid or solid form.

Examples of water include water of crystallization of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate and cerous chloride, and inorganic compounds or polymers such as silica, alumina and aluminum hydroxide. Adsorbed water or the like adsorbed on the water may be used.

The contact reaction between the solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out in a solvent such as a hydrocarbon solvent. As the solvent used in this case, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane, cyclohexane , Cyclooctane, methylcyclohexane and other alicyclic hydrocarbons; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene and gas oil, and the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbon halides And halogenated hydrocarbons such as chlorinated products and brominated products, and ethers such as ethyl ether and tetrahydrofuran.

Of these media, aromatic hydrocarbons are particularly preferred. The water or active hydrogen-containing compound used in the catalytic reaction is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, based on Al atoms in the aluminoxane solution. The concentration in the reaction system is usually in the range of 1 × 10 ^{−3 to} 5 g atom / l, preferably 1 × 10 ^{−2 to} 3 g atom / l, in terms of aluminum atom. The concentration of water in the system is usually 2 × 10 ^{−4 to} 5 mol / L, preferably 2 × 10 ^{−4 to} 5 mol / L.
It is desirable that the concentration be from × 10 ^{−3 to} 3 mol / l.

The contact of the aluminoxane solution with water or an active hydrogen-containing compound may be carried out specifically as follows. (1) A method in which a solution of aluminoxane is brought into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound. (2) A method in which water or an active hydrogen-containing compound vapor is blown into a solution of aluminoxane to bring the aluminoxane into contact with the vapor. (3) A method in which a solution of aluminoxane is brought into direct contact with water, ice or an active hydrogen-containing compound. (4) Aluminoxane solution is mixed with a hydrocarbon suspension of a compound containing adsorbed water or a water of crystallization or a hydrocarbon suspension of a compound to which an active hydrogen-containing compound is adsorbed. And contacting the water with the adsorbed water or water of crystallization.

The aluminoxane solution as described above may contain other components as long as the reaction between the aluminoxane and water or an active hydrogen-containing compound is not adversely affected.

The contact reaction between the solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out at -50 to 150
° C, preferably 0 to 120 ° C, more preferably 20 to 1 ° C.
It is performed at a temperature of 00 ° C. The reaction time varies greatly depending on the reaction temperature, but is usually 0.5 to 300 hours.
Preferably, it is about 1 to 150 hours.

The benzene-insoluble organoaluminum oxy compound can also be obtained directly by bringing the above-mentioned organoaluminum into contact with water. In this case, water is used in such an amount that the amount of the organic aluminum atoms dissolved in the reaction system is 20% or less based on all the organic aluminum atoms.

The water to be brought into contact with the organoaluminum compound is dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene, hexane, etc., an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or in the state of steam or ice. be able to. As water, it was adsorbed on water of crystallization of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerous chloride, or on inorganic compounds or polymers such as silica, alumina and aluminum hydroxide. Adsorbed water or the like can also be used.

The contact reaction between the organoaluminum compound and water is usually performed in a hydrocarbon solvent. Examples of the hydrocarbon 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; cyclopentane , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclohexane; petroleum fractions such as gasoline, kerosene, and light oil; and halides, especially chlorinated compounds of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons And hydrocarbon solvents such as bromides. In addition, ethers such as ethyl ether tetrahydrofuran can be used. Of these media, aromatic hydrocarbons are particularly preferred.

The concentration of the organoaluminum compound in the reaction system is usually in the range of 1 × 10 ^{−3 to} 5 g atoms / l, preferably 1 × 10 ^{−2 to} 3 g atoms / l in terms of aluminum atoms. The concentration of water in the reaction system is usually 1 × 10 ^{−3 to} 5 mol / l, preferably 1 × 10 ^{−2 to} 3 mol / l. At this time, the organic aluminum atoms dissolved in the reaction system are desirably 20% or less, preferably 10% or less, more preferably 0 to 5% based on all the organic aluminum atoms.

The contact between the organoaluminum compound and water may be carried out specifically as follows. (1) A method in which a hydrocarbon solution of an organic aluminum is brought into contact with a hydrocarbon solvent containing water. (2) A method in which water vapor is blown into a hydrocarbon solution of organic aluminum to bring the organic aluminum into contact with water vapor. (3) A method in which a hydrocarbon solution of an organic aluminum is mixed with a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization, and the organic aluminum is brought into contact with the adsorbed water or the water of crystallization. (4) A method in which ice is brought into contact with a hydrocarbon solution of an organic aluminum.

The hydrocarbon solution of organoaluminum as described above may contain other components as long as the reaction between the organoaluminum and water is not adversely affected. The contact reaction between the organoaluminum compound and water is usually -100.
C. to 150.degree. C., preferably -70 to 100.degree. C., more preferably -50 to 80.degree. Although the reaction time varies greatly depending on the reaction temperature, it is usually 1 to 20.
It is 0 hour, preferably about 2 to 100 hours.

In the present invention, when producing an olefin polymer, (C) an organoaluminum compound may be used, if necessary, in addition to (A) the transition metal compound and (B) the organoaluminum oxy compound as described above. Can be.

As the organoaluminum compound (C),
For example, the following formula R ⁶ _n AlX _3-n (wherein, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms;
Is halogen or hydrogen, and n is 1 to 3).

In the above formula, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group Isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

As such organoaluminum compounds, the following compounds are specifically used. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminumchloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquichloride; Le aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, alkylaluminum hydrides such as diisobutylaluminum hydride.

As the organoaluminum compound, the following formula: R ⁶ _n AlY _3-n (wherein R ⁶ is the same as above, Y is —OR ⁷ group,
OSiR ⁸ ₃ group, -OAlR ⁹ ₂ group, -NR ¹⁰ ₂ group, -S
iR ¹¹ ₃ group or -N (R ¹²⁾ is AlR ¹³ ₂ group, n
Is 1 to 2, R ⁷ , R ⁸ , R ⁹ and R ¹³ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ¹⁰ is a hydrogen, a methyl group, an ethyl group. , An isopropyl group, a phenyl group, a trimethylsilyl group and the like, and R ¹¹ and R ¹² are a methyl group,
And an ethyl group. ) Can also be used.

As such an organoaluminum compound, specifically, the following compounds are used. _{^{(1) R 6 n Al (}} OR 7) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (2) R 6 n Al}} (OSi R 8 3) a compound represented by _3-n, e.g., Et ₂ Al (OSi Me _3), such as _{(iso-Bu) 2 Al (} OSi Me 3) (iso-Bu) 2 Al (OSi Et 3), (3) R 6 n Al (OAlR ⁹ ₂₎ a compound represented by _3-n, e.g., Et ₂ such _{AlOAlEt 2 (iso-Bu) 2} AlOAl (iso-Bu) 2, (4) R 6 n Al (NR 10 2) 3-n A compound represented by
For example _{Me 2 AlNEt 2 Et 2 AlNHMe Me} 2 AlNHEt Et 2 AlN (SiMe 3) 2 such as _{(iso-Bu) 2 AlN (} SiMe 3) 2, (5) R 6 n Al (Si R 11 3) in _3-n A compound represented, for example, (iso-Bu) ₂ Al (SiMe ₃ ),

[0073]

Embedded image

[0074] As the organoaluminum compounds mentioned above, the following _{^{formula, R 6 3 Al, R 6}} n Al (OR 7) 3-n, R 6 n Al (OAlR 9 2) an organoaluminum compound represented by _3-n And R ⁶ is an isoalkyl group, and n =
Two are particularly preferred. These organoaluminum compounds can be used as a mixture of two or more kinds.

The catalyst component used in the present invention is solid. Such a solid catalyst component is prepared, for example, by supporting the catalyst component (A) on a carrier (D) or a solid organic aluminum oxy compound. Can be prepared.

The carrier (D) used in the present invention includes:
An inorganic or organic compound having a particle size of 10 to 30
Granular or particulate solids of 0 μm, preferably 20-200 μm, are used. Among them, a porous oxide is preferable as the inorganic carrier, and specifically, SiO ₂ , Al
₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , Ca
O, ZnO, BaO, ThO _{2 and the} like or a mixture thereof, for example, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ ,
SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr
Examples thereof include ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. Among them, a carrier containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component is preferable.

The above inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO
₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg
(NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li
_It may contain carbonate, sulfate, nitrate and oxide components such as ₂ O.

Although the properties of the porous inorganic carrier differ depending on the kind and the production method, the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 1 to 1000 m ² / g.
100 to 700 m ² / g, and the pore volume is 0.3 to 2.5.
cm ³ / g is desirable. The carrier is, if necessary, 150 to 1000 ° C, preferably 200 to 800 ° C.
It is used after firing.

Further, examples of the carrier which can be used in the present invention include a granular or fine solid of an organic compound having a particle size of 10 to 300 μm. Examples of these organic compounds include (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and vinylcyclohexane and styrene. A polymer or copolymer as a component can be exemplified.

In the present invention, when an ethylene polymer is produced, an olefin is added to the above-mentioned catalyst component (A) and (B), if necessary, to the catalyst component comprising (C) and / or (D). It is desirable to use a catalyst formed by pre-polymerization.

Prior to the prepolymerization, the catalyst component (A), or the catalyst components (A) and (B), or the catalyst components (A), (B) and (C) were previously supported on a carrier. Alternatively, the catalyst components may be subjected to preliminary polymerization simply by arbitrarily contacting and mixing the catalyst components.

At this time, when a transition metal compound (E) containing a ligand having a cyclopentadienyl skeleton which is not bonded to each other is used in combination with the catalyst component (A), a spherical olefin copolymer excellent in particle properties is obtained. Coalescence can be manufactured.

If necessary, the transition metal compound (E) used in the present invention is represented by the following formula: M ² L ² _X (where M ² is a transition metal, and L ² is coordinated to the transition metal) At least one L ² is a ligand having a cyclopentadienyl skeleton, and L ² other than the ligand having a cyclopentadienyl skeleton has 1 to 20 carbon atoms.
Is a hydrocarbon group, alkoxy group, aryloxy group, halogen or hydrogen, and x is the valence of the transition metal. )
It is represented by

In the above formula, M ² is a transition metal, and specifically, is preferably zirconium, titanium or hafnium, chromium or vanadium,
Of these, zirconium and hafnium are particularly preferred.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, dimethylcyclopentadienyl group. Examples thereof include an alkyl-substituted cyclopentadienyl group such as an enyl group and a pentamethylcyclopentadienyl group, an indenyl group, and a fluorenyl group.

One or more ligands having such a cyclopentadienyl skeleton are coordinated to the transition metal M ² , preferably two. Ligands other than those having a cyclopentadienyl skeleton have 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, halogen or hydrogen.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. Specifically, the alkyl group includes a methyl group and an ethyl group. , A propyl group, an isopropyl group, a butyl group, etc. are exemplified.As the cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc. are exemplified.As the aryl group, a phenyl group, a tolyl group, etc. are exemplified. Examples include a benzyl group and a neophyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group, and examples of the aryloxy group include a phenoxy group.

As the halogen, fluorine, chlorine, bromine,
Examples include iodine. The transition metal compound containing a ligand having a cyclopentadienyl skeleton which is not bonded to each other and which is used in the present invention (E) is more specifically when the valence of the transition metal is 4, for example. Is a compound represented by the following formula: R ^{2 ′} _k R ^{3 ′} _l R ^{4 ′} _m R ^{5 ′} _n M ² (where M ² is zirconium, titanium, hafnium or vanadium, etc., and R ^{2 ′} is a cyclopentadienyl skeleton) R ^{3 ′} , R ^{4 ′} and R ^{5 ′} are groups having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group,
An aryloxy group, a halogen atom or hydrogen, k is an integer of 1 or more, and k + 1 + m + n = 4).

Specific examples of the transition metal compound (E) containing a ligand having a cyclopentadienyl skeleton which is not bonded to each other, wherein M ² is zirconium, are shown below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride, bis ( Cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride hydride, bis (indenyl) zirconium Monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium 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) zirconium dimethyl, bis (cyclohexyl) Pentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (methylcyclopentadienyl) zirconium ethoxychloride, Bis (cyclopentadienyl) zirconium phenoxycyclolide, bis (fluorenyl) zirconium dichloride.

In the above zirconium compound, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal or vanadium metal can also be used.

In the prepolymerization, the olefin polymer is added in an amount of 0.05 to 100 g, preferably 0.1 to 100 g per 1 g of the carrier.
It is desirable that the prepolymerization be performed in an amount of from 50 to 50 g, more preferably from 0.2 to 30 g.

The olefins include ethylene and α-olefins having 3 to 20 carbon atoms, for example, propylene,
-Butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and the like. Of these, ethylene is preferred.

The prepolymerization is carried out without solvent or in an inert hydrocarbon medium. In prepolymerization, the organoaluminum compound is used in an amount of 0.2 to 20 mmol, preferably 0.5 to 10 mmol, based on 1 g of the carrier, and the organoaluminum oxy compound is 1 to 50 mg atom as aluminum atom, Preferably, it is used in an amount of 2 to 20 milligram atoms, and the catalyst component (A) is used in an amount of 0.02 to 2 milligram atoms, preferably 0.05 to 1 milligram atom as a transition metal atom.

The molar ratio Al (C) / Al (B) between the aluminum atom (Al (C)) as the organic aluminum compound and the aluminum atom (Al (B)) as the organic aluminum oxy compound is usually 0. .02-3,
It is preferably 0.05 to 1.5, and the molar ratio of the aluminum atom Al (B) as the organic aluminum oxy compound to the transition metal atom (M) of the catalyst component (A) [Al
(B) / M] is usually 5 to 250, preferably 10 to 15
Desirably, it is in the range of 0. The concentration of the transition metal atom as the catalyst component (A) when carried out in an inert hydrocarbon medium is usually in the range of 0.1 to 10 milligram atoms / liter, preferably in the range of 0.5 to 5 milligram atoms / liter. It is desirable that

The prepolymerization temperature ranges from -20 ° C to 70 ° C, preferably from -10 ° C to 60 ° C, more preferably from 0 ° C to 50 ° C. The prepolymerization may be carried out in a batch system or a continuous system, and may be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization, a molecular weight regulator such as hydrogen may be coexisted, but the intrinsic viscosity [η] measured in decalin at 135 ° C. is at least 0.1.
It is desirable to suppress the amount to a level that can produce a prepolymer of 2 dl / g or more, preferably 0.5 to 10 dl / g.

In the thus obtained prepolymerized catalyst, the transition metal atom as the catalyst component (A) per 0.1 g of the carrier is 0.1 to 50 mg, preferably 0.3 to 30 mg, more preferably 0 to 30 mg. And a molar ratio (Al / M) of aluminum atoms derived from the catalyst components (B) and (C) to the transition metal atom (M) as the catalyst component (A) is 5 to 20 milligrams. ~ 200,
Preferably 10 to 150, more preferably 15 to 100
Is desirably within the range.

The ethylene-based polymer according to the present invention can be prepared in the presence of the above-mentioned catalyst in the presence of ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl
-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-
It is obtained by polymerizing tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

In the present invention, the polymerization of the olefin is carried out under the condition that the produced polymer exists in a solid state, for example, in a gas phase or a slurry. In slurry polymerization,
The inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.

Specific examples of the hydrocarbon medium include butane,
Isobutane, pentane, hexane, octane, decane,
Aliphatic hydrocarbons such as dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; gasoline, kerosene, And petroleum fractions such as light oil. Among these hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

In the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. In the present invention, when performing the gas phase polymerization method, the polymerization temperature is usually 0 to 120
° C, preferably in the range of 20 to 100 ° C.

When the present invention is carried out by a slurry polymerization method or a gas phase polymerization method, the transition metal compound is generally used in a concentration of 10 ^-8 to 10 as a concentration of the transition metal atom in the polymerization reaction system.
It is desirable to use it in an amount of ^-2 gram atoms / liter, preferably 10 ^-7 to 10 ^-3 gram atoms / liter.

In the main polymerization, the catalyst component (B)
And the same organoaluminum oxy compound or organoaluminum compound as used in preparing (C) may be added to the reaction system. At this time, the atomic ratio (Al / M) between the aluminum compound and the transition metal atom (M) is 5 to 3
00, preferably 10-200, more preferably 15-
The range is 150.

The polymerization pressure is usually from normal pressure to 100 kg.
/ Cm ² , preferably under a pressurized condition of ^{2 to} 50 kg / cm ² , and the polymerization can be carried out in any of a batch system, a semi-continuous system, and a continuous system.

Further, the polymerization can be carried out in two or more stages under different reaction conditions.

[0106]

According to the present invention, the olefin is polymerized by using a specific catalyst, so that it has excellent melt tension,
In addition, an ethylene polymer having a narrow composition distribution can be obtained in the copolymer.

[0107]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0108]

Example 1 [Preparation of catalyst component (A)] A nitrogen-substituted 400 ml glass flask was charged with 20 g of bis (indenyl) ethane and 200 ml of THF, and cooled to −50 ° C. with stirring. This is n-Bu
After 100 ml of Li (1.6 M solution) was added dropwise over 50 minutes, the mixture was stirred at −50 ° C. for 1 hour, and then naturally heated to room temperature to anionize bis (indenyl) ethane. Further, 100 ml of THF was added to make a uniform solution.

In another 1-liter glass flask purged with nitrogen, 250 ml of THF was charged and cooled to -50 ° C., and 16.54 g of zirconium tetrachloride was gradually added. Thereafter, the temperature was raised to 60 ° C., and the mixture was stirred for 1 hour. The ligand anionized as described above was added dropwise thereto, and 6
After stirring at 0 ° C. for 3 hours, the mixture was filtered with a glass filter. When the filtrate was concentrated at room temperature to about the first 1/5 volume, a solid precipitated. The precipitated solid was filtered through a glass filter, washed with a mixed solvent of hexane / ether (1/1), and dried under reduced pressure to obtain ethylene bis
(Indenyl) zirconium dichloride (catalyst component
(A)) was obtained. [Preparation of catalyst component (B)] Al was placed in a 400 ml flask sufficiently purged with nitrogen.
37 g of ₂ (SO ₄ ) ₃ .14H ₂ O and 125 ml of toluene were charged, and after cooling to 0 ° C., 500 mmol of trimethylaluminum diluted with 125 ml of toluene was added dropwise. Next, the temperature was raised to 40 ° C., and the reaction was continued at that temperature for 48 hours. After completion of the reaction, the solid-liquid separation by filtration, further was to remove the toluene from the filtrate, the organic white solid
Aluminum Muokishi compound (catalyst component (B)) 9.1 g
was gotten. The preliminary polymerization catalyst was prepared by re-dissolving in toluene. [Preparation of Preliminary Polymerization Catalyst] In a 400 ml flask sufficiently purged with nitrogen, 1.29 g of silica (Fuji Devison F-948) calcined at 700 ° C. for 6 hours and 20 ml of toluene were added to form a suspension. 4.51 ml of a decane solution of triisobutylaluminum (Al; 1 mol / l) was added thereto, and the mixture was stirred at room temperature for 30 minutes. Subsequently, 7.91 ml of a toluene solution (Al; 0.95 mol / l) of the catalyst component (B) prepared above was added, and the mixture was further stirred at room temperature for 30 minutes. Next, a toluene solution of the catalyst component (A) prepared above (Zr; 0.00298 mol / L) 72 m
was added and stirred for 10 minutes. Further, 52 ml of decane was added, and preliminary polymerization was carried out at 30 ° C. for 4 hours while continuously introducing ethylene gas (normal pressure).

After the completion of the prepolymerization, the solvent was removed by decantation, and the resultant was washed with 200 ml of hexane by heating (60 ° C.).
3 times, and further washed with 200 ml of hexane (room temperature) for 3 times.
I went there. By this operation, a prepolymerized catalyst containing 8.5 mg of Zr, 160 mg of Al and 15 g of polyethylene per 1 g of silica was obtained. [Polymerization] Sodium chloride (Wako Pure Chemicals special grade) 150 in a 2-liter stainless steel autoclave sufficiently purged with nitrogen.
g, and dried under reduced pressure at 90 ° C. for 1 hour. Thereafter, the pressure was returned to normal pressure by introducing a mixed gas of ethylene and 1-butene (1-butene content: 6.3 mol%), and the system was heated to 70 ° C.

Next, the prepolymerized catalyst prepared as described above was used in an amount of 0.0075 milligram atoms in terms of zirconium atoms, and triisobutylaluminum in 1.1 parts.
The mixture was mixed in an amount of 3 mmol and added to the autoclave.

Thereafter, 50 N ml of hydrogen was introduced, and a mixed gas of the above-mentioned ethylene and 1-butene was introduced, and the polymerization was started at a total pressure of 4 kg / cm ² -G. The temperature in the system immediately rose to 80 ° C. Thereafter, only the mixed gas was supplied, and the polymerization was carried out at 80 ° C. for 1 hour while maintaining the total pressure at 4 kg / cm ² -G.

After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with methanol.
It dried under reduced pressure at ℃ overnight. As a result, the 1-butene content was 8.1.
MFR measured under a load of 2.16 kg at 190 ° C. is 2.30 g / 10 min, and the density is 0.915.
g / cm ³ , the temperature at the maximum peak position in the endothermic curve measured by DSC is 94 ° C., the amount of decane-soluble components at 23 ° C. is 2.8% by weight, and the melt tension (MT)
Was 5.3 g, and 116 g of an ethylene / 1-butene copolymer having a bulk specific gravity of 0.31 g / cm ³ was obtained.

[0114]

Example 2 [Preparation of Prepolymerization Catalyst] To 1.30 g of the same silica as in Example 1, 20 ml of decane was added to make a suspension, and a decane solution of triisobutylaluminum (Al; 1 mol / l) was added. 24 ml was added and the mixture was stirred at room temperature for 30 minutes.

Next, 17.1 ml of a toluene solution (Al; 0.95 mol / l) of an organoaluminum oxy compound synthesized in the same manner as in Example 1 was added to the suspension, and the mixture was further stirred at room temperature for 30 minutes. did.

Thereafter, 1.03 ml of a toluene solution of bis (cyclopentadienyl) zirconium dichloride (Zr; 0.0417 mol / l) was added to the suspension, and the mixture was stirred for 15 minutes, and 50 ml of decane was further added. In addition, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was performed at 30 ° C. for 2 hours. Thereafter, the catalyst component (A) prepared in Example 1 and having a Zr concentration of 0.00172 mol / liter.
Was added and further prepolymerization was continued at 30 ° C. for 4 hours. The subsequent operation was performed in the same manner as in Example 1, to obtain a prepolymerized catalyst containing 9.3 mg of zirconium, 190 mg of aluminum and 20 g of polyethylene per 1 g of silica. [Polymerization] In the polymerization of Example 1, a mixed gas having a 1-butene content of 3.6 mol% was used, the hydrogenation amount was adjusted to 10 Nml, and the prepolymerized catalyst obtained above was converted to 0.0 in terms of zirconium atoms.
The procedure was the same except that the polymer was polymerized at 70 ° C. for 2 hours, using triisobutylaluminum in an amount of 0.75 mmol in an amount of 0.05 mg atom, the 1-butene content was 6.7% by weight, and the MFR was 0.7. 48 g / 10 min, density 0.9
22 g / cm ³ , the temperature at the maximum peak position in the DSC endothermic curve was 103 ° C., the amount of decane-soluble components was 0.25% by weight, the melt tension was 11 g, and the bulk specific gravity was 0.35 g / cm ^3. As a result, 88 g of an ethylene / 1-butene copolymer having a mass of cm ³ was obtained.

[0117]

Example 3 [Preparation of prepolymerization catalyst] 30 g of decane was added to 3.0 g of the same silica as in Example 1 to make a suspension, and a decane solution of triisobutylaluminum (Al; 1 mol / l) was added. 45 ml was added and the mixture was stirred at room temperature for 25 minutes.

Next, 39.4 ml of a toluene solution (Al; 0.95 mol / l) of an organic alnium oxy compound synthesized in the same manner as in Example 1 was added to the suspension, and further added at room temperature for 25 minutes. Stirred.

Thereafter, 2.14 m of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 0.0465 mol / l) was added to the suspension.
After stirring for 10 minutes, decane 100
and continuously introduce ethylene gas (normal pressure).
Preliminary polymerization was carried out at 2.5 ° C. for 2.5 hours.

Thereafter, 166.4 ml of a toluene solution as a catalyst component (A) having a Zr concentration of 0.00240 mol / l prepared in Example 1 was added, and prepolymerization was further continued at 30 ° C. for 5 hours. Subsequent operations were carried out in the same manner as in Example 1 to obtain a prepolymerized catalyst containing 8.2 mg of zirconium, 150 mg of aluminum and 20 g of polyethylene per 1 g of silica. [Polymerization] In the polymerization of Example 1, the same procedure as in Example 1 was carried out except that the amount of hydrogenation was 30 Nml and the above-mentioned prepolymerized catalyst was used, and the content of 1-butene was 10.1% by weight. MFR is 1.78 g / 10 min and density is 0.91
2 g / cm ³ , the temperature at the maximum peak position in the DSC endothermic curve was 94 ° C., and the amount of decane-soluble components was 3.
149 g of an ethylene / 1-butene copolymer having 1% by weight, a melt tension of 5.3 g, and a bulk specific gravity of 0.36 g / cm ³ was obtained.

[0121]

EXAMPLE 4 [Preparation of Prepolymerization Catalyst] To 1.49 g of the same silica as in Example 1, 25 ml of decane was added to form a suspension, and a decane solution of triisobutylaluminum (Al; 1 mol / l) was added. 72 ml was added and the mixture was stirred at room temperature for 45 minutes.

Next, 19.6 ml of a toluene solution (Al; 0.95 mol / l) of an organoaluminum oxy compound synthesized in the same manner as in Example 1 was added to the suspension, and the mixture was further stirred at room temperature for 45 minutes. did.

Thereafter, 2.13 m of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 0.0465 mol / l) was added to the suspension.
1 and then stirred for 10 minutes.
and ethylene gas (normal pressure) is continuously introduced, and 30 ° C.
For 1.5 hours.

Thereafter, 51.9 ml of a toluene solution as a catalyst component (A) having a Zr concentration of 0.00287 mol / l prepared in Example 1 was added, and further prepolymerization was continued at 30 ° C. for 4 hours. Subsequent operations were performed in Example 1.
As a result, a prepolymerized catalyst containing 10.5 mg of zirconium, 190 mg of aluminum and 17 g of polyethylene per 1 g of silica was obtained. [Polymerization] In the polymerization of Example 1, a mixed gas having a 1-butene content of 4.4 mol% was used, the hydrogenation amount was 30 Nml, and the above prepolymerized catalyst was 0.005 mg atom in terms of zirconium atom. , Triisobutylaluminum to 0.5
When carried out in the same manner as in Example 1 except that it was used in an amount of mmol, the 1-butene content was 6.5% by weight, the MFR was 3.1 g / 10 min, and the density was 0.922 g / cm ^3. The temperature at the maximum peak position in the DSC endothermic curve was 115 ° C., the amount of decane-soluble components was 0.32% by weight, the melt tension was 4.9 g, and the bulk specific gravity was 0.36 g /
48 g of an ethylene / 1-butene copolymer having a volume of cm ³ was obtained.

[0125]

[Example 5] [Polymerization] In the polymerization of Example 1, a mixed gas having a 1-butene content of 3.6 mol% was used, the hydrogenation amount was 30 Nml, and zirconium was added in an amount of 0.005 milligram atom. Isobutyl aluminum was used in an amount of 0.75 mmol and 70
The same procedure as in Example 1 was carried out except that the polymerization was carried out at 1 ° C. for 1 hour. The result was that the 1-butene content was 7.4% by weight and the MFR was 0.1%.
075 g / 10 min and a density of 0.920 g / cm ³
The temperature at the maximum peak position in the DSC endothermic curve was 103 ° C., and the amount of the decane-soluble component was 0.18% by weight.
The melt tension is 42 g and the bulk specific gravity is 0.24 g
/ Cm ³ of 95 g of an ethylene / 1-butene copolymer.

[0126]

Comparative Example 1 [Preparation of Prepolymerization Catalyst] To 3.14 g of the same silica as in Example 1, 25 ml of decane was added to form a suspension, and a decane solution of triisobutylaluminum (Al; 1 mol / liter) was added. 1 ml was added and the mixture was stirred at room temperature for 45 minutes.

Next, 36.5 ml of a toluene solution (Al; 1.79 mol / l) of an organoaluminum oxy compound synthesized in the same manner as in Example 1 was added to the suspension, and the mixture was further stirred at room temperature for 20 minutes. did.

Thereafter, 10.9 m of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr; 0.0480 mol / l) was added to the suspension.
After stirring for 30 minutes, decane 100
ml and continuously introduce ethylene gas (normal pressure).
Prepolymerization was carried out at 4.5 ° C. for 4.5 hours. Thereafter, the same washing operation as in Example 1 was performed to obtain a prepolymerized catalyst containing 7.6 mg of zirconium, 190 mg of aluminum and 9.7 g of polyethylene per 1 g of silica. [Polymerization] In the polymerization of Example 1, a mixed gas having a 1-butene content of 6.1 mol% was used, and the prepolymerized catalyst obtained above was treated with 0.015 mg atom of zirconium atom and triisobutylaluminum. 0.75 mmol total pressure 8
except that polymerization was carried out at 85 ° C. for 1 hour under kg / cm ² -G.
When carried out in the same manner as in Example 1, the 1-butene content was 7.
2% by weight, MFR is 1.29 g / 10 min,
The density was 0.920 g / cm ³ , the temperature at the maximum peak position in the DSC endothermic curve was 114 ° C., the amount of decane-soluble components was 1.1% by weight, the melt tension was 1.9 g, Ethylene / 1- having a specific gravity of 0.37 g / cm ³
137 g of a butene copolymer was obtained.

[0129]

REFERENCE EXAMPLE 1 [Polymerization] In the polymerization of Example 1, zirconium was 0.003 mg atom, and triisobutylaluminum was 0.54 mg.
Total pressure 8 kg / cm ² for 1 hour at 85 ° C. using mmol amount
GFR was 0.29 g / 10 min, except that the homopolymerization of ethylene was performed with G.
Melt tension is 17.5g, bulk specific gravity is 0.32g / c
121 g of an ethylene polymer having a m of ³ was obtained.

[0130]

Example 6 [Polymerization] In the polymerization of Example 3, a mixed gas having a 1-butene content of 3.9 mol% was used, the hydrogenation amount was set to 50 Nml, 0.005 mg atom of zirconium, and triisobutylaluminum. Used in an amount of 0.5 mmol, total pressure 2.5 k
g / cm ² -G, except that the polymerization was carried out in the same manner as in Example 3, except that the 1-butene content was 7.0% by weight and the MF
R is 1.97 g / 10 min and density is 0.920 g / c
m ³ , the temperature at the maximum peak position in the DSC endothermic curve was 103 ° C., the amount of decane-soluble components was 0.35% by weight, the melt tension was 4.6 g, and the bulk specific gravity was 0.1%.
Ethylene / 1-butene copolymer 11 of 36 g / cm ³
9 g were obtained.

[0131]

Example 7 [Polymerization] In the polymerization of Example 4, the hydrogenation amount was 50 Nml, triisobutylaluminum was used in an amount of 0.75 mmol, the polymerization temperature was 85 ° C., and the total pressure was 7 kg / cm ² -G.
Except that the polymerization was carried out in the same manner as in Example 4.
The 1-butene content is 6.8% by weight and the MFR is 1.99.
g / 10 min, the density is 0.920 g / cm ³ ,
141 g of an ethylene / 1-butene copolymer having a decane-soluble component amount of 0.67% by weight, a melt tension of 6.0 g, and a bulk specific gravity of 0.37 g / cm ³ was obtained.

[0132]

[Reference Example 2] [Preparation of Preliminary Polymerization Catalyst] To 1.11 g of the same silica as in Example 1, 15 ml of toluene
To make a suspension, into which 7.76 m of a toluene solution of triisobutylaluminum (Al; 1 mol / l) was added.
and stirred at room temperature for 30 minutes. Next, 13.6 ml of a toluene solution (Al; 0.95 mol / l) of an organoaluminum oxy compound synthesized in the same manner as in Example 1 was added to the suspension, and the mixture was further stirred at room temperature for 35 minutes. Thereafter, 162.0 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr; 0.00228 mol / l) prepared in Example 1 was added to the suspension, and the mixture was stirred for 30 minutes and further decanted. 100 ml was added, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was performed at 30 ° C. for 5 hours. Subsequent operations were performed in the same manner as in Example 1 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] 1 liter of decane was charged into a 1.5-liter glass autoclave sufficiently purged with nitrogen, and a mixed gas of ethylene and hydrogen (250 liter / h and 1 liter / h, respectively) was passed. . After the temperature of the system was raised to 75 ° C., triisobutylaluminum was mixed in an amount of 0.5 mmol, and the prepolymerized catalyst prepared as described above was mixed in an amount of 0.005 mg atom in terms of zirconium atom.
Added to autoclave. Thereafter, the polymerization was carried out at 75 ° C. for 3 hours under a normal pressure while continuously supplying the mixed gas, and the polymerization proceeded in a slurry state.

After completion of the polymerization, the polymer was recovered by filtration, and dried at 80 ° C. overnight under reduced pressure. As a result, 16.9 g of an ethylene polymer having an MFR of 1.18 g / 10 min and a melt tension of 6.5 g was obtained.

[0134]

Reference Example 3 [Catalyst preparation] 20 ml of decane and 27.9 ml of a toluene solution of an organic aluminum oxy compound (Al; 0.716 mol / l) in a 100 ml eggplant-shaped flask sufficiently purged with nitrogen.
Then, 37.3 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr; 0.00268 mol / l) was added, and after stirring for 5 minutes, toluene was distilled off under reduced pressure at room temperature using an evaporator. It took 2 hours during this time. Thereafter, the precipitated solid product was recovered by filtration, washed with hexane, and dried under reduced pressure at room temperature to obtain a solid catalyst component having an Al / Zr molar ratio of 112. [Polymerization] In the polymerization of Example 1, the solid catalyst component prepared above was used as the catalyst component in an amount of only 0.005 mg atom in terms of zirconium atom, at 85 ° C. for 1 hour, and a total pressure of 8 kg.
Example 1 except that ethylene was homopolymerized at 1 / cm ² -G
As a result, an ethylene polymer 2 having an MFR of 0.42 g / 10 min and a melt tension of 12.0 g was used.
6.4 g were obtained.

[0135]

In the polymerization of Reference Example 4] [Polymerization] Reference Example 3, except that the 100Nml hydrogen addition amount was conducted in the same manner as in Reference Example 3, MFR is 3.10 g / 10 min, the melt tension 5 As a result, 34.0 g of an ethylene polymer was obtained.

[0136]

Comparative Example 2 [Polymerization] In the polymerization of Reference Example 2 , toluene was used as a solvent.
A mixed gas of ethylene, 1-butene and hydrogen (285 liter / h and 15 liter /
h, 2 liters / h) with the exception that polymerization co 20 minutes was carried out in the same manner as in Reference Example 2, polymerization was proceeded in a solution state. After completion of the polymerization, the polymer was precipitated and recovered in a large amount of methanol, and then dried at 130 ° C. overnight under reduced pressure.
As a result, the 1-butene content was 6.5% by weight and the MFR
Is 1.44 g / 10 min and the density is 0.922 g / cm
³ and 33.1 g of an ethylene / 1-butene copolymer having a melt tension of 2.1 g were obtained.

[0137]

Comparative Example 3 [Polymerization] In the polymerization of Reference Example 2 , the mixed gas flow rate of ethylene and hydrogen was changed to 100 L / h and 5 L / h, respectively, and a toluene solution of an organoaluminum oxy compound as a catalyst component ( Al; 1.46 mol / liter)
3.42 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (Zr; 0.0015
(0 mol / l) The polymerization was carried out in the same manner as in Reference Example 2 except that ethylene was homopolymerized for 80 minutes using 0.33 ml, and the polymerization proceeded in a cloudy state. After the polymerization was completed, the polymer was precipitated and recovered in a large amount of methanol.
It dried under reduced pressure at ℃ overnight. As a result, the MFR was 0.72 g /
For 10 minutes, 8.2 g of an ethylene copolymer having a melt tension of 2.9 g was obtained.

[0138]

Example 8 [Preparation of Preliminary Polymerization Catalyst] 55.4 g of silica (TG-20643 manufactured by Fuji Devison Co., Ltd.) calcined at 700 ° C. for 6 hours in an 8 liter flask sufficiently purged with nitrogen and 1 liter of decane were added. Was added to form a suspension. 46 mmol of triisobutylaluminum diluted with 50 ml of decane was added thereto, and the mixture was stirred at room temperature for 10 minutes.

Subsequently, the catalyst component ( B ) prepared above
140 ml of a toluene solution (Al; 1.65 mol / l) of (SCHERING) was added, and the mixture was further stirred at room temperature for 10 minutes. Next, a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr;
(0.05 mol / l) and stirred for 15 minutes. Thereafter, preliminary polymerization was carried out at 30 ° C. for 3.5 hours while continuously introducing ethylene gas (normal pressure).

Thereafter, 2 liters of decane was added, 279 ml of the catalyst component ( B ), and the catalyst component ( A ) prepared in Example 1 (Zr; 0.00264 mol / liter) were added.
2.79 liters and 23.4 ml of tributylaluminum diluted with 50 ml of decane were added successively and the prepolymerization was continued at 30 ° C. for 4 hours.

After the completion of the prepolymerization, the solvent was removed by decantation, and the resultant was washed with 5 liters of hexane (60 ° C.).
3 times and further with 5 liters of hexane (room temperature) for 3 times
I went there. By this operation, 1 g of Zr was added to 1 g of silica.
A prepolymerized catalyst containing 1 mg, 190 mg of Al and 16 g of polyethylene was obtained. [Polymerization] Total pressure 20 kg / cm ^2- using a continuous fluidized bed gas phase polymerization apparatus
G. Copolymerization of ethylene and 1-hexene was carried out at a polymerization temperature of 80 ° C. Ethylene in order to maintain a constant gas composition during the continuous fed polymerized at a rate of prepolymerized catalyst the terms of zirconium atom by 0.1 mmol / h, tributyl aluminum 15 mmol / h of the above prepared 1- hexene, hydrogen, nitrogen was continuously supplied (gas composition; 1-hexene / ethylene = 0.015, H ₂ / ethylene = 6.3 ×
10 ^-3 ). The polymer yield was 6.0 kg / h.

The polymer thus obtained had a 1-hexene content of 10.7% by weight and an MFR of 1.60 g /
10 minutes, the density is 0.922 g / cm ³ ,
The temperature at the maximum peak position in the endothermic curve measured by SC is 112.1 ° C., the amount of decane-soluble component at 23 ° C. is 0.53% by weight, the melt tension (MT) is 6.6 g, The bulk specific gravity was 0.38 g / cm ³ .

[0143]

Comparative Example 4 [Preparation of Preliminary Polymerization Catalyst] Instead of bis (methylcyclopentadienyl) zirconium dichloride in Comparative Example 1, a toluene solution of bis (cyclopentadienyl) zirconium dichloride (Zr; 0.04 mol) was used. (L / l) The procedure of Comparative Example 1 was repeated except that 13.1 ml was used, to obtain a prepolymerized catalyst containing 8.7 mg of zirconium, 290 mg of aluminum and 7.7 g of polyethylene per 1 g of silica. [Polymerization] In the polymerization of Example 1, a mixed gas having a 1-butene content of 6.7 mol% was used, and the prepolymerized catalyst obtained above was converted to 0.01 mg of zirconium atom and triisobutylaluminum. 0.25 mmol, total pressure 8
When the same procedure as in Example 1 was carried out except that the polymerization was carried out at 85 ° C. for 1 hour under kg / cm ² -G, the 1-butene content was 6.9.
%, The MFR was 2.63 g / 10 min, the density was 0.922 g / cm ³ , the temperature at the maximum peak position in the DSC endothermic curve was 114 ° C., and the amount of decane-soluble components was 1. 75 g of an ethylene / 1-butene copolymer having a melt tension of 1.3 g and a bulk specific gravity of 0.38 g / cm ³ was obtained.

[0144]

Comparative Example 5 [Preparation of Preliminary Polymerization Catalyst] To 1.05 g of the same silica as in Example 1, 20 ml of decane was placed in a 400 ml glass flask to form a suspension.
2.62 ml of a decane solution of triisobutylaluminum (Al; 1 mol / l) was added to the suspension, followed by stirring at room temperature for 30 minutes.

Next, an organoaluminum oxy compound (a solution obtained by removing toluene from a toluene solution of methylaluminoxane manufactured by SCHERING and re-dissolving it in toluene (Al; 1.79 g atom / liter)) was added to this suspension.
4.87 ml was added, and the mixture was further stirred at room temperature for 35 minutes.

Thereafter, a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr; 0.0108 g atom / l) was added to the suspension.
After adding 16.2 ml and stirring for 30 minutes, 75 ml of decane was further added and prepolymerization was carried out at 30 ° C. for 4 hours while continuously introducing ethylene gas (normal pressure). Subsequent operations were performed in the same manner as in Example 1 to obtain a prepolymerized catalyst containing 9.3 mg of zirconium, 150 mg of aluminum, and 18 g of polyethylene based on 1 g of silica. [Polymerization] In the polymerization of Example 1, a mixed gas having a 1-butene content of 6.9 mol% was used, and the prepolymerized catalyst obtained above was treated with 0.005 mg atom of zirconium atom and triisobutylaluminum. 0.5 mmol, total pressure 8
The same procedure as in Example 1 was carried out except that the polymerization was carried out at 85 ° C. for 1 hour under kg / cm ² -G, and the 1-butene content was 9.6.
%, The MFR is 2.45 g / 10 min, the density is 0.910 g / cm ³ , the temperature at the maximum peak position in the DSC endothermic curve is 109 ° C., and the amount of decane-soluble components is 1. 5% by weight, a melt tension of 0.95 g and a bulk specific gravity of 0.37 g / cm ^3.
147 g of a butene copolymer was obtained.

The above results are shown in Tables 1 and 2.

[0148]

[Table 1]

[0149]

[Table 2]

[0150]

Example 9 [Polymerization] In the polymerization of Example 8 , 1-butene was used in place of 1-hexene, and the following points were changed. The prepolymerization catalyst was continuously supplied at a rate of 0.11 mmol / h in terms of zirconium atoms and triisobutylaluminum at a rate of 16.5 mmol / h. Butene, hydrogen and nitrogen were continuously supplied (gas composition; 1-butene / ethylene = 0.094, H ₂ /
Ethylene = 1.8 × 10 ⁻³ , ethylene partial pressure 38 mol%). The polymer yield was 6.2 kg / h. The polymer thus obtained has a 1-butene content of 14.
0% by weight, an MFR of 6.1 g / 10 min, a density of 0.905 g / cm ³ , a temperature at a maximum peak position in an endothermic curve measured by DSC of 94 ° C.,
The decane-soluble component amount at 3 ° C. is 9.5% by weight, the melt tension (MT) is 2.5 g, and the bulk specific gravity is 0.40 g / c.
m ³ .

[0151]

Example 10 In the polymerization of Example 1, ethylene and 1-
Polymerization was carried out in the same manner as in Example 1 except that a mixed gas of ethylene and propylene (a propylene content of 4.5 mol%) was used instead of the mixed gas of butene, and the results are shown in Table 3.

[0152]

Example 11 [Polymerization] One liter of hexane and 1-decene 10 were placed in a 2-liter stainless steel autoclave sufficiently purged with nitrogen.
ml, and the inside of the system was replaced with ethylene. Subsequently, after the temperature in the system was raised to 10 ° C., 1 mmol of triisobutylaluminum and 0.005 mg of the prepolymerized catalyst prepared in Example 1 were added in terms of zirconium atoms. Then, while continuously supplying a mixed gas of ethylene and hydrogen (hydrogen content: 0.3 mol%), the total pressure was 4 kg /
Polymerization was performed at 80 ° C. for 1 hour at a temperature of 80 cm ² -G. After the completion of the polymerization, the polymer was recovered by filtration and dried under reduced pressure at 80 ° C. overnight. The results are shown in Table 3.

[0153]

Example 12 A catalyst was prepared in the same manner as in Example 1 except that ethylene bis (indenyl) zirconium dichloride was used instead of ethylene bis (indenyl) zirconium dichloride in preparing the prepolymerized catalyst of Example 1. Polymerization was carried out in the same manner as in Example 1 except that was synthesized. Table 3 shows the results
Shown in

[0154]

[Table 3]

[Brief description of the drawings]

FIG. 1 is an IR spectrum of an organoaluminum oxy compound according to the present invention.

FIG. 2 shows a conventionally known organic aluminum oxy compound I
It is an R spectrum.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-74415 (JP, A) JP-A-2-218706 (JP, A) JP-A-1-101315 (JP, A) JP-A-2- 22307 (JP, A) JP-A-63-295607 (JP, A) JP-A-61-130314 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4 / 60-4 / 70 C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00-210/18

Claims (4)

(57) [Claims] (A) at least two compounds having a cyclopentadienyl skeleton
Using a solid catalyst formed from a transition metal compound of Group IVb of the Periodic Table and a (B) organoaluminum oxy compound having as a ligand a compound having a structure in which two groups are crosslinked by carbon and / or silicon-containing groups. , Under the condition that the produced polymer exists in a solid state in the polymerization system
Ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized, and a) 55 to 99% by weight of a structural unit derived from ethylene
%, A structure derived from an α-olefin having 3 to 20 carbon atoms.
The formed units in a proportion of 1 to 45 wt%, b) a density of 0.86~0.95g / cm ³ range near
Ri, c) is in the range MFR of from 0.001 to 100 g / 10 min at 2.16kg load at 190 ° C., d) a melt tension (MT) and MFR of at log MT> -0.66log MFR + 0.5 meet the relationship indicated, e) an endothermic song was measured by a differential scanning calorimeter (DSC)
A method for producing an olefin polymer, characterized in that an ethylene / α-olefin copolymer having a temperature (T) and a density at a maximum peak position in a line satisfying T <400d-250 is obtained. 2. The ethylene / α-olefin copolymer further has an n-decane soluble component fraction (W) and a density (d) at 23 ° C. represented by log W <−50d + 46.6. The method for producing an olefin polymer according to claim 1, wherein the relationship is satisfied. 3. A transition of Group IVb of the Periodic Table having as a ligand (A) a compound having a structure in which at least two groups having a cyclopentadienyl skeleton are cross-linked by carbon and / or silicon-containing groups. The method for producing an olefin polymer according to claim 1, wherein the metal compound is a transition metal compound represented by the following formula: M ¹ L ¹ _x (where M ¹ is a transition metal, and L ¹ is A ligand coordinating to a transition metal, wherein at least two L ¹ are ligands having a cyclopentadienyl skeleton, which are bonded via a carbon and / or silicon-containing group, and L ¹ other than the ligand having a skeleton has 1 to 1 carbon atoms.
2 is a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen or hydrogen, and x is a valence of a transition metal. ) 4. The method according to claim 1 , wherein a transition metal compound (E) represented by the following formula is used in combination with said transition metal compound (A).
M ² L ² _x (wherein M ² is a transition metal, L ² is a ligand coordinated to the transition metal, and at least one L ² is a ligand having a cyclopentadienyl skeleton, L ² other than the ligand having a cyclopentadienyl skeleton having 1 to 12 carbon atoms
Is a hydrocarbon group, alkoxy group, aryloxy group, halogen or hydrogen, and x is the valence of the transition metal. )