JPH03234718A - Production of ethylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in properties, blocking resistance and heat resistance by forming an ethylene polymer in a specified multistage process using a catalyst comprising a specified transition metal compound and an organoaluminumoxy compound. CONSTITUTION:The purpose composition is obtained by performing a multistage process comprising a polymerization step (a) of forming an ethylene copolymer I having a density of 0.91g/cm<3> or below and an intrinsic viscosity eta of 0.5-6dl/g by using a catalyst comprising a transition metal compound having a ligand containing a cycloalkadienyl skeleton and an organoaluminumoxy compound and a polymerization step (b) of forming an ethylene polymer II having a density higher than that of polymer I and an intrinsic viscosity of 0.5-6dl/g by using a catalyst comprising a Ti catalyst component comprising Ti, Mg and halogen and an organoaluminum compound and/or an organoaluminumoxy compound in such a way that, for example, step (a) is performed, before step (b) is performed in the presence of copolymer I and that 10-1000 pts.wt. polymer II is formed per 100 pts.wt. copolymer I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an ethylene polymer composition, and more particularly to a method for producing an ethylene polymer composition by a multi-stage polymerization method, and more particularly, it relates to a method for producing an ethylene polymer composition by a multi-stage polymerization method, and more particularly, it The present invention relates to a method for producing an ethylene polymer composition which has a small amount of hydrogen soluble in a solvent and therefore has excellent blocking resistance and heat resistance.

Technical background of the invention In recent years, as a new Ziegler type olefin polymerization catalyst,
A method for producing an olefin polymer using a catalyst consisting of a zirconocene compound and an aluminoxane was disclosed in JP-A-58-
No. 19309, No. 80-35007, No. 61
-221208, etc., and these publications report that ethylene polymers with narrow molecular weight distribution and composition distribution and excellent transparency can be obtained. However, since polymers, especially copolymers, obtained using the above-mentioned olefin polymerization catalysts have low melting points and poor heat resistance, improvement in heat resistance is desired depending on the application.

On the other hand, an ethylene copolymer obtained using a titanium catalyst system consisting of a titanium catalyst and an organoaluminum compound is
Although it has excellent heat resistance, when the density is reduced, the amount of hydrocarbon solvent soluble is large, resulting in poor blocking resistance.

Purpose of the Invention The present invention has been made in view of the prior art as described above, and provides a method for producing an ethylene polymer composition that maintains its original excellent properties and has excellent blocking resistance and heat resistance. is intended to provide.

Summary of the Invention The method for producing an ethylene polymer composition according to the present invention includes: Polymerization step (a): a transition metal compound [A] containing a ligand having a cycloalkadienyl skeleton and an organoaluminumoxy compound [B] An olefin polymerization catalyst consisting of [
I], ethylene and other α-olefins are copolymerized to produce an ethylene copolymer having a density of 0.91 g/cm or less and an intrinsic viscosity [η] of 0.5 to 6 dfl/g. Step of forming coalescence [I] and polymerization step (b): titanium catalyst component [C] containing titanium, magnesium and halogen as essential components, organoaluminum compound [D] and/or organoaluminumoxy compound [El and An olefin polymerization catalyst consisting of [
I1 is used to polymerize or copolymerize ethylene or ethylene and other α-olefins to obtain a polymer having a higher density than the above ethylene copolymer [I] and an intrinsic viscosity of 0.5 to 0.5.
After carrying out the polymerization step (a), a multi-stage process consisting of the step of forming an ethylene polymer [II] with a concentration of 6 dl/g is carried out in the presence of the obtained ethylene copolymer [I]. b), or after performing the polymerization step (b), perform the polymerization step (a) in the presence of the obtained ethylene polymer [I] so that the amount of polymerization in both steps is equal to or lower than the ethylene polymer. By adjusting the ratio of the ethylene polymer [II] to 100 parts by weight of the polymer [I] to be 10 to 1000 parts by weight, the density can be adjusted to 0.87 to 0.93.
g/cm3, and the intrinsic viscosity [η] is 0.5 to 6 d
The method is characterized in that an ethylene polymer composition having a ratio of N/g is obtained.

According to the method for producing an ethylene polymer composition according to the present invention, it is possible to obtain an ethylene polymer that has low density but excellent pro-knocking resistance and heat resistance.

DETAILED DESCRIPTION OF THE INVENTION The method for producing the ethylene polymer composition according to the present invention will be specifically described below.

FIGS. 1(a) and 1(b) are explanatory diagrams showing the manufacturing process of the ethylene polymer composition according to the present invention.

The method for producing an ethylene polymer composition according to the present invention includes a polymerization step (a) and a polymerization step (b).

In the polymerization step (a), an olefin polymerization catalyst [I] consisting of a transition metal compound [A] containing a ligand having a cycloalkagenyl skeleton and an organoaluminumoxy compound [B] is used.

First, the transition metal compound [A] containing a ligand having a cycloalkagenyl skeleton will be explained.

A transition metal compound containing a ligand having a cycloalkagenyl skeleton has the formula MLx (where M is a transition metal, L is a ligand that coordinates to the transition metal, and at least one L is When the ligand has a cycloalkagenyl skeleton and contains at least two or more ligands having a cycloalkagenyl skeleton, the ligand having at least two cycloalkagenyl skeletons is an alkylene group. , a substituted alkylene group, a silylene group, or a substituted silylene group, and L other than the ligand having a cycloalkagenyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, or an aryloxy group. , halogen or hydrogen, and X is the valence of the transition metal.

In the above formula, M is a transition metal, specifically,
Zirconium, titanium, hafnium, chromium, and vanadium are preferred, and among these, zirconium and hafnium are particularly preferred.

Examples of the ligand having a cycloalkagenyl skeleton include a cyclopentagenyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, a t-butylcyclopentagenyl group, a dimethylcyclopentagenyl group, Examples include alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl groups, indenyl groups, and fluorenyl groups.

Two or more of the above-mentioned ligands having a cycloalkagenyl skeleton may be coordinated to a transition metal, and in this case, at least two ligands having a cycloalkagenyl skeleton may be used. may be bonded via an alkylene group, substituted alkylene group, silylene group, or substituted silylene group.

Examples of the alkylene group include a methylene group, ethylene group, trimethylene group, and tetramethylene group; examples of the substituted alkylene group include an isopropylidene group and a tetramethylethylene group; examples of the substituted silylene group include:
Examples include dimethylsilylene group, ethylmethylsilylene group, and diphenylsilylene group.

The ligand other than the ligand having a cycloalkagenyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen, or hydrogen.

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. , isopropyl group, butyl group, etc.; cycloalkyl groups include cyclopentyl group, cyclohexyl group; aryl groups include phenyl group, tolyl group, etc.; aralkyl groups include benzyl group, Examples include a neophyll group.

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

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

Hereinafter, specific examples of transition metal compounds containing a ligand having a cycloalkagenyl skeleton in which M is zirconium will be exemplified.

Bis(cyclopentagenyl)zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium monopromide monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis (cyclopentagenyl) phenylzirconium hydride, bis(cyclopentagenyl)penzylzirconium hydride, bis(cyclopentagenyl)neopentylzirconium hydride, bis(methylcyclopentagenyl)zirconium monochloride hydride, bis(indenyl) ) Zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)zirconium dibromi
bis(cyclopentagenyl)methylzirconium monochloride, bis(cyclopentagenyl)ethylzirconium monochloride, bis(cyclopentagenyl)cyclohexylzirconium monochloride, bis(cyclopentagenyl)phenylzirconium monochloride, Bis(cyclopentagenyl)benzylzirconium monochloride, Bis(methylcyclopentagenyl)zirconium dichloride, Bis(dimethylcyclopentagenyl)zirconium dichloride Bis(n-butylcyclopentagenyl)zirconium dichloride Bis(indenyl)zirconium Dichloride, bis(indenyl)zirconium dichloride, bis(cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium diphenyl, bis(cyclopentagenyl)zirconium dibenzyl, bis(cyclopentagenyl)zirconium methoxychloride , Bis(cyclopentagenyl)zirconium ethoxychloride, Bis(methylcyclopentagenyl)zirconium ethoxychloride, Bis(cyclopentagenyl)zirconium phenoxychloride, Bis(fluorenyl)zirconium dichloride, Ethylenebis(indenyl)dimethylzirconium, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium monochloride, Ethylenebis(indenyl)methylzirconium monochloride, Ethylenebis(indenyl)ethylzirconium monochloride, Ethylenebis(indenyl)methylzirconium monopromide, Ethylene Bis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(4,5,8,7-tetrahydro- l-indenyl) methylzirconium monochloride, ethylenebis(4,5,8,7-tetrahydro-l-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-l-indenyl)zirconium dichloride, ethylene Bis(4-methyl-1-indenyl)zirconium dichloride, Ethylenebis(5-methyl-1-indenyl)zirconium dichloride, Ethylenebis(6-methyl-I-indenyl)zirconium dichloride, Ethylenebis(7-methyl-I- indenyl) zirconium dichloride, ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyltoindenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-l-indenyl)zirconium dichloride, Ethylenebis(4,7-dimethoxy-l-indenyl)
Zirconium dichloride.

Isopropylidene (cyclopentagenyl-fluorenyl) zirconium dichloride isopropylidene bis(indenyl) zirconium dichloride dimethylsilylene bis(cyclopentagenyl) zirconium dichloride dimethylsilylene bis(methylcyclopentagenyl)
Zirconium dichloride dimethylsilylene bis(indenyl) zirconium dichloride Furthermore, in the above-mentioned zirconium compounds, transition metal compounds in which zirconium metal is replaced with titanium metal, hafnium metal, or vanadium metal can also be used.

Next, the organoaluminumoxy compound [B] will be explained.

The organoaluminumoxy compound [B] may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminumoxy compound discovered by the present inventors.

The above aluminoxane can be produced, for example, by the following method.

(1) Compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of adding organoaluminum compounds such as trialkyl aluminum to a hydrocarbon medium suspended in water, causing a reaction, and recovering a hydrocarbon solution.

(2) A method in which water, ice, or steam is directly applied to an organoaluminum compound such as trialkylaluminium in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a hydrocarbon solution.

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

Specifically, the organoaluminum compounds used in producing the aluminoxane solution include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trinium
-butylaluminum, triisobutylaluminum,
tri-5ee-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum,
Trialkyl aluminum such as tricyclooctyl aluminum, dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethylaluminium bromide, diisobutyl aluminum chloride, dialkyl aluminum hydride such as diethyl aluminum hydride, diisobutyl aluminum hydride, dimethyl aluminum methoxide, Examples include dialkyl aluminum alkoxides such as diethylaluminum ethoxide, dialkyl aluminum alkoxides such as diethylaluminium phenoxide, and the like.

Among these, trialkylaluminum is particularly preferred.

Moreover, isoprenyl aluminum represented by the general formula %) can also be used as an organoaluminum compound.

The organoaluminum compounds described above may be used alone or in combination.

Solvents used for aluminoxane solutions include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, and ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

Furthermore, the benzene-insoluble organic aluminum oxy compound used in the present invention is an AI compound that is soluble in benzene at 60°C.
The acid component is 10% or less, preferably 5% or less, particularly preferably 2% or less, in terms of Al atoms, and is insoluble or poorly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is determined by suspending the organoaluminum oxy compound corresponding to 100 milligram atoms of Ag in 100 ml of benzene, and then mixing at 60° C. for 6 hours with stirring. Using a jacketed G-5 glass filter, 60
After performing hot filtration at ℃ and washing the solid portion separated on the filter 4 times with 50 ml of benzene at 60 ℃, the abundance (x mmol) of A, 17 atoms present in the total filtrate was measured. (X%).

Furthermore, when the above-mentioned benzene-insoluble organoaluminumoxy compound is analyzed by infrared spectroscopy (IR),
Absorbance (D) near 1220 cm-1,
The ratio (D / D > 1
2H12601220 0.09 or less, preferably 0.08 or less, particularly preferably 0
．． It is desirable that it be in the range of 0.04 to 0.07.

Infrared spectroscopic analysis of organoaluminumoxy compounds is
Do it as follows.

First, in a nitrogen box, the organoaluminumoxy compound and Nujol are ground into a paste using an agate needle.

Next, the paste-like sample is sandwiched between KBr plates, and an IR spectrum is measured using IR-810 manufactured by JASCO Corporation under a nitrogen atmosphere.

I of the organoaluminumoxy compound used in the present invention
The R spectrum is shown in FIG.

From the IR spectrum obtained in this way, D
/D is calculated, but this D /D12B0
1220 12110 1220 The value is determined as follows.

(a) Connect pole 1 near 1280cm and 1240cm-' and define this as baseline L1.

(b) Transmittance of absorption minimum point near 1260 cm-' (T
%), draw a perpendicular line from this minimum point to the wavenumber axis (horizontal axis), and calculate the transmittance at the intersection of this perpendicular line and the baseline L (
To%) was read and the absorbance around 1 1260cITl (D -1ogT
/1280.

Calculate T).

ml (c) Similarly around 1280cm and 1180cm-'
Connect nearby maximum points and use this as the baseline L2.

(d) Transmittance of absorption minimum point near 1220 cm-' (
T' %), draw a perpendicular line from this minimum point to the wavenumber axis (horizontal axis), read the transmittance (T' %) at the intersection of this perpendicular line and baseline L2, and calculate the absorbance (D -1og
T'.

220 /T°).

(e) Calculate D/D from these values.

1260 1220 The IR spectrum of a conventionally known benzene-soluble organoaluminumoxy compound is shown in FIG. As can be seen from FIG. 3, the benzene-soluble organoaluminumoxy compound has a D1□6°/D value of about 0.
The benzene-insoluble organoaluminumoxy compound used in the present invention has a D1□6°/D value of between 10 and 0.13, which is clearly different from conventionally known benzene-soluble organoaluminumoxy compounds. There is.

220 Benzene-insoluble organic aluminum 91 as above,
R1 is a hydrocarbon group having 1 to 12 carbon atoms].

In the above alkyl oxydialuminum unit, R1
Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group, cyclooctyl group, etc. It is. Among these, methyl group and ethyl group are preferred, and methyl group is particularly preferred.

This benzene-insoluble organoaluminumoxy oxydialuminum unit [where R1 is the same as above, R2 is a hydrocarbon group having 1 to 12 carbon atoms, 1 to 12 carbon atoms,
12 alkoxy groups, aryloxy groups having 6 to 20 carbon atoms, hydroxyl groups, herogen or hydrogen, and R and R2 may contain groups representing mutually different groups. In that case, an organoaluminumoxy compound having an alkyloxydialuminum unit in an amount of 1% or more, particularly preferably 70% by mole or more, is preferred.

Next, a method for producing the benzene-insoluble organoaluminumoxy compound as described above will be specifically explained.

This benzene-insoluble organoaluminumoxy 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 isoprobal, diols such as ethylene glycol and hydroquinone, and organic acids such as acetic acid and propionic acid are used.

Among these, alcohols and diols are preferred, and alcohols are particularly preferred.

The water or active hydrogen-containing compound contacted with the solution of aluminoxane can be a hydrocarbon solvent such as benzene, toluene, hexane, an ether solvent such as tetrahydrofuran,
It can be used by dissolving or dispersing it in an amine solvent such as triethylamine, or in a vapor or solid state.

Also, as water, magnesium chloride, magnesium sulfate,
Crystal water of salts such as aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerous chloride, or adsorbed water adsorbed on inorganic compounds or polymers such as silica, alumina, and aluminum hydroxide, etc., can also be used.

The catalytic reaction between a solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out in a solvent, for example a hydrocarbon solvent. Solvents used at this time include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, pentane, hexane, heptane, octane,
Aliphatic hydrocarbons such as decane, dodecane, hexadecane, and octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclohexane, hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene, and gas oil, or the above aromatic substances. group hydrocarbons, aliphatic hydrocarbons,
It is also possible to use halogenated alicyclic hydrocarbons, particularly halogenated hydrocarbons such as chlorides and bromides, and ethers such as ethyl ether and tetrahydrofuran. Among these media, aromatic hydrocarbons are particularly preferred.

The amount of water or active hydrogen-containing compound used in the catalytic reaction is 0.1 per Al atom in the aluminoxane solution.
It is used in an amount of ~5 mol, preferably 0.2-3 mol.

The concentration in the reaction system is usually 1X10-3 to 5 gram atoms/g, preferably 1X10'' in terms of aluminum atoms.
-” to 3 gram atoms/g is desirable;
The concentration of water in the reaction system is usually 2X10-' to 5 moles/II, preferably 2X10-' to 3 moles/g.

Specifically, the aluminoxane solution may be brought into contact with water or an active hydrogen-containing compound in the following manner.

(1) A method of bringing a solution of aluminoxane into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound.

(2) A method of bringing aluminoxane and steam into contact by, for example, blowing water or steam of an active hydrogen-containing compound into a solution of aluminoxane.

(3) A method in which a solution of aluminoxane is brought into direct contact with water, ice, or an active hydrogen-containing compound.

(4) A solution of aluminoxane is mixed with a hydrocarbon suspension of an adsorbed water-containing compound or crystal water-containing compound, or a hydrocarbon suspension of a compound to which an active hydrogen-containing compound has been adsorbed, and the aluminoxane is A method of contacting adsorbed water or crystallized water with water.

Note that the aluminoxane solution as described above may contain other components as long as they do not adversely affect the reaction between the aluminoxane and water or the active hydrogen-containing compound.

The contact reaction between the aluminoxane solution and water or the active hydrogen-containing compound is usually carried out at -50 to 150°C, preferably at 0°C.
It is carried out at a temperature of 120°C to 120°C, more preferably 20 to 100°C. The reaction time varies greatly depending on the reaction temperature, but is usually 0.5 to 300 hours, preferably 1 to 15 hours.
It takes about 0 hours.

Furthermore, a benzene-insoluble organoaluminumoxy compound can also be directly obtained by bringing the above organoaluminum into contact with water.

In this case, water contains 20% of the organic aluminum atoms dissolved in the reaction system based on the total organic aluminum atoms.
It is used in amounts such that:

The water to be brought into contact with the organoaluminum compound contains benzene,
It can be used by dissolving or dispersing it in a hydrocarbon solvent such as toluene or hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or in the form of water vapor or ice. Also, as water,
Crystallized water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerous chloride, or adsorbed water adsorbed on inorganic compounds or polymers such as silica, alumina, and aluminum hydroxide. It can also be used.

The contact reaction between an organoaluminum compound and water is usually carried out in a hydrocarbon solvent. Hydrocarbon solvents used at this time include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, pentane, hexane,
Aliphatic hydrocarbons such as heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclohexane; petroleum distillates such as gasoline, kerosene, and light oil; and the above-mentioned aromas. Examples include hydrocarbon solvents such as halides of group hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorides and brominates. others,
Ethers such as ethyl ether tetrahydrofuran can also be used. Among these media, aromatic hydrocarbons are particularly preferred.

The concentration of the organoaluminum compound in the reaction system is usually 1X10-” to 5 g atoms/in terms of aluminum atoms.
The concentration of water in the reaction system is usually 1 x 10-3 to 5 mol/g, preferably 1 x 10-2 to 5 mol/g.
A concentration of 3 mol/g is desirable. At this time, the amount of organoaluminum atoms dissolved in the reaction system is 20% or less, preferably 10% of the total organoaluminum atoms.
Below, it is more preferably 0 to 5%.

Specifically, the organic aluminum compound and water may be brought into contact as follows.

(1) A method of bringing a hydrocarbon solution of an organoaluminum into contact with a hydrocarbon solvent containing water. (2) A method of bringing an organoaluminium and water vapor into contact by, for example, blowing water vapor into a hydrocarbon solution of an organoaluminium. .

(3) A method of mixing a hydrocarbon solution of an organoaluminum and a hydrocarbon suspension of an adsorbed water-containing compound or a crystal water-containing compound, and bringing the organoaluminum into contact with the adsorbed water or crystal water.

(4) A method of bringing an organic aluminum hydrocarbon solution into contact with ice.

Note that the hydrocarbon solution of organoaluminum as described above may contain other components as long as they do not adversely affect the reaction between organoaluminum and water.

The contact reaction between an organoaluminum compound and water is usually -1
It is carried out at a temperature of 00 to 150°C, preferably -70 to 100°C, more preferably -50 to 80°C. The reaction time also varies greatly depending on the reaction temperature, but is usually 1 to 2
00 hours, preferably about 2 to 100 hours.

Further, the olefin polymerization catalyst used in the present invention may contain an organoaluminum compound, if necessary.

Such organoaluminum compounds include, for example, RAgX (wherein R6 is carbon number n
3-n is a hydrocarbon group of 1 to 12, or is a halogen or hydrogen, and n is 1 to 3).

In the above formula, R6 is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. , pentyl group,
Examples include hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Specifically, the following compounds are used as such organoaluminum compounds.

Dryalkyl aluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, trihexylaluminum and the like.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkyl aluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide.

Alkylaluminum sesqui7X rides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide.

Alkylaluminum cybarides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dichloride.

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

ANY (In the formula, R6 is the same as above, Y is -n R7R8R and R13 are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., and R10 is hydrogen, methyl group, ethyl group , isopropyl group, phenyl group, trimethylsilyl group, etc., and R11 and R12 are methyl group, ethyl group, etc.) can also be used.

Specifically, the following compounds are used as such organoaluminum compounds.

7 (i) RAD (OR), n Dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc., 6.8 (it) RAD (O5IR) n 3 3-n E t A R (OS iM e 3 )(1so-
B u)2Aρ (OS i M e a ) (iso
-Bu) AI (OSI Et 3), etc., 9 (ii) RAN (OAN R) n 2 3-n Et,, AD On Et 2 (1so-Bu) ADOA j? (1so-
B u) 2 etc., 6 t.

(iV) RAII (NR) R23-n M e 2 A I N E t 2 E t 2 A 1) N HM e M e 2 A (IN HE t E t A D N (M e s S i) 2 (i
so-Bu) AN N (Me Si)2, etc., 31311 (V)RAN(SiR) R33-n (jso-Bu)2 Aρ iMe, etc. As the above organoaluminum compounds, A ,Q(
Preferred examples include organic Al 3-n miniram compounds represented by OAJIIR), where R6 is an isoalkyl group and n-2 is particularly preferred. Two or more of these organoaluminum compounds can also be used in combination.

In addition, the above-mentioned olefin polymerization catalysts include silica,
It can also be supported on solid inorganic compounds such as alumina, magnesium oxide, and magnesium chloride, or solid organic compounds such as polyethylene, boria pyrene, and polystyrene.

In the polymerization step (a), ethylene and another α-olefin are copolymerized using the olefin polymerization catalyst [I] as described above, so that the density is 0.91 g/d or less, preferably 0.91 g/d or less.
86~0.905g/cm3, more preferably 0.87~
0.90 g/cm3, and the intrinsic viscosity [η] is 0.5 to
An ethylene copolymer [I] having a concentration of 6 dl/g, preferably 0.7 to 4 dl/g is formed.

The α-olefin other than ethylene that can be used in the polymerization step (a) of the present invention includes α-olefins having 3 to 20 carbon atoms.
-Olefins, such as propylene, 1-butene, -1
Pentene, l-hexene, 4-methyl-i-pentene,
l-octene, 1-decene, l-dodecene, l-tetradecene, l-hexadecene, t-octadecene, l-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2- Methyl-1,4゜5.8-dimethano-1,
Examples include 2,3,4,4a, 5,8.8a-octahydronaphthalene.

Furthermore, styrene, vinylcyclohexane, diene, etc. can also be used.

This polymerization step (a) can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Among these, solution polymerization is particularly preferred.

The polymerization temperature of olefin using such an olefin polymerization catalyst [I] is usually in the range of -50 to 200°C, preferably 0 to 150°C.

The polymerization pressure is usually normal pressure to 100 kg/cd, preferably normal pressure to 50 kg/cj, and the polymerization reaction can be carried out in any of the batch, semi-continuous, and continuous methods. can. The molecular weight of the resulting olefin polymer can be controlled by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

When polymerizing an olefin using the olefin polymerization catalyst [I] as described above, the transition metal compound [A] containing a ligand having a cycloalkagenyl skeleton is
The amount of organoaluminumoxy compound [B] is usually 0.01 to 10 mmol, preferably 0.02 to 5 mmol, per 1 g of reaction volume. The organoaluminum compound is preferably used in an amount of usually 0 to 10 mmol, preferably 0.1 to 5 mmol.

In addition, in the present invention, the olefin polymerization catalyst [I1] can contain other components useful for olefin polymerization in addition to the above-mentioned components.

In the polymerization step (b), an olefin polymerization catalyst [II] consisting of a titanium catalyst component [C] containing titanium, magnesium and a halogen as essential components, and an organoaluminum compound [D] and/or an organoaluminumoxy compound [E] is used. ] is used.

First, we will explain the titanium catalyst component [C] which has titanium, magnesium and halogen as essential components.This titanium catalyst component [C] has titanium, magnesium and halogen as essential components, and further contains an electron donor as necessary. Contains.

Such a titanium catalyst component [Cl is prepared by contacting a magnesium compound, a titanium compound, and, if necessary, an electron donor as described below.

In the present invention, the titanium compound used for preparing the titanium catalyst component [Cl is, for example, TI(OR) g
X4-g (R is a hydrocarbon group, X is)\rogen atom, 0
Examples include tetravalent titanium compounds represented by ≦g≦4). More specifically, TI CfI - TI B
Tet4 titanium halides such as r STi I4: Ti(QC)I)(13, Ti(OCR) CII 3, 5 Ti(On-CH) CI g, 9 T1(OC2H5)Br3, Ti(Oiso CH ) Tril\roge, 49 alkoxytitanium such as Br 3; dihalogenated 2 such as Ti(OCH) Cl12, 2 Ti(QCH) CN2, 52 TI(OrrCH) CF2, 92 TI(OCR) Br 2 5 2 dialkoxy titanium: TI(OCH8) 3CL).

T t (o C2H5)3 CJ7, T I (On-
C4H9) 3CD-T1(OC2H5)3B"mono-halogenated trialkoxytitanium such as TI(OCH3)4, Ti(OC2H5)t, Ti(On-C4H9)4 Ti(O1so-C4H9)4 Examples include tetraalkoxytitanium such as Ti(0-2-ethylhexyl)4.

These titanium compounds may be used alone or in combination of two or more. Furthermore, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used in the preparation of the titanium catalyst component [Cl] include magnesium compounds with reducing properties and magnesium compounds without reducing properties.

Here, as a magnesium compound having reducing properties,
For example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specific examples of magnesium compounds having such reducing properties include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Examples include amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium halide. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described below. Further, these magnesium compounds may be limbs or solids.

Specific examples of non-reducing magnesium compounds include magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, etc.; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, Alkoxymagnesium/halides such as butoxymagnesium chloride, octoxymagnesium chloride; alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium,
butoxymagnesium, n-octoxymagnesium,
Examples include alkoxymagnesiums such as 2-ethylhexoxymagnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate.

These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds or compounds derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound can be derived from a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. All you have to do is bring it into contact with a compound.

In addition, in the present invention, the magnesium compound includes not only the above-mentioned magnesium compounds having reducing properties and non-reducing properties, but also complex compounds, composite compounds, or other metal compounds of the above-mentioned magnesium compounds and other metals. It may also be a mixture with a compound. Furthermore, a mixture of two or more of the above compounds may be used.

In the present invention, among these, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride,
Allyloxymagnesium chloride is preferably used.

When preparing the titanium catalyst component [C], it is preferable to use an electron donor, and examples of the electron donor include alcohols, amines, amides, ethers, ketones, esters, nitriles, phosphines, stipines, arsines, phosphoramides, thioethers, thioesters, acid anhydrides, acid halides, aldehydes,
Examples include alcoholates, alkoxy(aryloxy)silanes, and organic acids. Among these, alcohols, amines, ethers, esters, acid anhydrides, alkoxy(aryloxy)silanes, and organic acids are preferably used.

The titanium catalyst component [C] can be produced by contacting the above-described magnesium compound (or metal magnesium), a titanium compound, and, if necessary, an electron donor. To produce the titanium catalyst component,
A known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and, if necessary, an electron donor can be employed. In addition, the above ingredients are
For example, contact may be made in the presence of other reactive agents such as silicon, phosphorous, aluminum, etc.

Several examples of methods for producing these titanium catalyst components will be briefly described below.

In addition, in the manufacturing method of titanium catalyst component [C] described below, an example using an electron donor will be described, but this electron donor does not necessarily have to be used.

(1) A method of reacting a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor with a titanium compound in a liquid phase. In this reaction, each component may be pretreated with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. In this case, the electron donor is used at least once.

(2) a liquid magnesium compound that does not have reducing properties;
A method in which a solid magnesium-titanium complex is precipitated by reacting a wavy titanium compound in the presence of an electron donor.

(3) A method in which the reaction product obtained in (2) is further reacted with a titanium compound.

(4) The reaction product obtained in (1) or (2),
A method for further reacting an electron donor and a titanium compound.

(5) A solid material obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with either a halogen, a halogen compound, or an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Also,
A magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, then pretreated with a reaction aid, and then treated with a halogen or the like. Note that examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds.

Note that in this method, an electron donor is used at least once.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound, or an aromatic hydrocarbon.

(7) A method of contacting a contact reaction product of a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol with an electron donor and a titanium compound.

(8) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium with an electron donor, a titanium compound, and/or a halogen-containing hydrocarbon.

(9) Magnesium compound and alkoxytitanium and/
Alternatively, a method in which a catalyst component in a hydrocarbon solution containing at least an electron donor such as alcohol or ether is reacted with a halogen-containing compound such as a titanium compound and/or a halogen-containing silicon compound.

((0) A method of reacting a non-reducing magnesium compound with an organic aluminum compound to precipitate a solid magnesium-aluminum complex, and then reacting with a titanium compound.

Among the methods for preparing the titanium catalyst component [C] listed in (1) to (IO) above, methods (1) to (4) and (10) are preferably used.

Furthermore, a mixed solution of a non-reducing magnesium compound and a titanium compound overnight can also be used.

The amount of each of the above-mentioned components used in preparing the titanium catalyst component [C] varies depending on the preparation method and cannot be unconditionally defined, but for example, the amount of electron donor per mol of magnesium compound is about 0.01 to In an amount of 20 mol, preferably 0.05 to 10 mol, the titanium compound is about 0.0 mol.
It is used in an amount of 1 to 500 mol, preferably 0.05 to 300 mol.

The titanium catalyst component thus obtained contains magnesium, titanium, halogen, and, if necessary, an electron donor as essential components.

In this titanium catalyst component [C], the halogen/titanium (atomic ratio) is about 4-200, preferably about 5-100, and the electron donor/titanium (molar ratio) is about 0.1-200.
50, preferably about 0.2 to about 25, and the magnesium/titanium (atomic ratio) is about 1 to 100, preferably about 2
-50 is desirable.

When this titanium catalyst component [C] is in a solid state, it contains magnesium halide with a smaller crystal size compared to commercially available magnesium halides, and usually has a specific surface area of about 10rd/g or more, preferably about 30 to 1000
0/g, more preferably about 50 to 800 rrl'/g. In this solid titanium catalyst component [C], the above components are integrated to form a catalyst component, so
The hexane wash does not substantially change its composition.

Regarding the preparation method of such highly active titanium catalyst component [C], for example, JP-A-50-108385,
5Q-126590, 51-20297, 51-28189, 51-84586, 51-2885, 51-136825
No. 52-87489, No. 52-1005
Publication No. 96, Publication No. 52-147888, Publication No. 52-1
No. 04593, No. 53-2580, No. 53-
No. 40093, No. 53-40094, No. 53
-43094, 55-135102, 55-135103, 55-152710, 5B-811, 56-11908, 5B-18 [I06, 5g-83006, 5g-138705, 58-1387
Publication No. 06, Publication No. 58-138707, Publication No. 58-1
No. 38708, No. 58-138709, No. 5
No. 8-138710, No. 58-138715, No. 60-23404, No. 60-195108, No. 61-21109, No. 61-37802
This method is disclosed in Japanese Patent Publication No. 131-37803, etc.

Usually, the titanium catalyst component [C] has an ethylene polymerization activity of 200 g-polymer/mmol-TiXhXatm, preferably 500 g-
Polymer/mmol-TiX h X atI of 11 or more is desirable.

As the organoaluminum compound [D] used in the present invention, for example, RAj? Examples include organoaluminum compounds represented by the formula .

In the above formula, R6 is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. , pentyl group,
They are hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

As such an organoaluminum compound [D],
Specifically, the following compounds are used.

Trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkyl aluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride 1, dimethylaluminum bromide.

Alkylaluminum sesqui/helides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide.

Alkylaluminum hydrides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dichloride.

Alkylaluminum hydride such as diethylaluminum chloridide and diisobutylaluminum chloridide.

Further, as the organoaluminum compound [D], 8 Y is -OR group, -0SI R group, -0AgIQ
, 11R9 group, NR2 group, S
I R3 group or R7R8R9 and R13 are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., and RlO is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc. , R11 and R12 are a methyl group or an ethyl group. ) can also be used.

(The following is a blank space) As such an organoaluminum compound CD], specifically, the following compounds are used.

7 (i) RAil (OR) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc., 8 (i) RAil (OSIR) n 3 3-n E t A (1 (OS i Me 3 )(lso-
Bu) 2Ag (OS i Me 3) (iso-Bu)
AN (O3i Et 3') etc., 9 (i) RAN (OANR) n 2 ! 1-nEt AD
OAREt 2 (iso-Bu)2AN OAj! (iso-Bu
)2, etc., 0 (IV) R6nAN (NR) 3-n M e A D N E t 2 E t 2 A D N HM e M e 2 A I) N HE t E t AM N (Me S i)23 (iso-Bu) AII N (Me St)
2, etc., 3 (V)R6 n I (SIRll) -n The above-mentioned organoaluminum compounds [D] and organoaluminum compounds can be cited as suitable examples, and in particular, R6 is an isoalkyl group, and n-2 Preferably. Two or more of these organoaluminum compounds can also be used in combination.

As the organoaluminumoxy compound [E], a compound similar to the organoaluminumoxy compound [B] used in the polymerization step (a) is used.

Further, when carrying out the polymerization step (b), the above titanium catalyst component [C] and the organoaluminum compound [D]
and/or organoaluminumoxy compound [E]
In addition to the above, an olefin polymerization catalyst [II] containing an electron donor as described above can also be used.

In the polymerization step (b), ethylene is homopolymerized using the above-mentioned olefin polymerization catalyst [R1, or ethylene and another α-olefin are copolymerized to form the olefin in the polymerization step (a). The above ethylene copolymer [I]
The density is higher than that, preferably the density is 0190 to 0.9
4g/cm3, preferably 0.91 to 0.93g/c
m3 and has an intrinsic viscosity of 0.5 to 6 dρ/g, preferably 0.7 to 4 dN/g [II
]. Moreover, this ethylene polymer [II] is
The n-decane soluble component at 23°C is preferably 0.1 to 10%.

α other than ethylene that can be used in the polymerization step (b)
- Examples of the olefin include those exemplified in the polymerization step (a).

This polymerization step (b) can be carried out by any liquid phase polymerization method such as solution polymerization or suspension polymerization, or by a gas phase polymerization method. Among these, solution polymerization is particularly preferred.

The polymerization temperature of olefin using such an olefin polymerization catalyst [II] is usually in the range of 0°C to 250°C, preferably 50 to 200°C. The polymerization pressure is usually normal pressure to 100 kg/cJ, preferably normal pressure to 50 kg/c'
- The polymerization reaction can be carried out in any of the batch, semi-continuous and continuous methods. The molecular weight of the resulting olefin polymer can be controlled by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

When olefin polymerization is carried out using the olefin polymerization catalyst [II] as described above, the titanium catalyst component [C
] is the polymerization volume I! Usually about 10-4 to 0.5 mmol per Ti atom, preferably about 10-3 to 0.5 mmol per Ti atom.
The organoaluminum compound [D] is used in an amount such that the aluminum atom is usually 1 to 2000 mol, preferably 5 to 500 mol, per 1 mol of titanium atom. Compound [E] is used in an amount such that aluminum atoms are usually 4 to 2000 mol, preferably 10 to 500 mol per 1 mol of titanium atom.

In the present invention, the above two polymerization steps (a) and (b) are performed in any order. That is, after performing the polymerization step (a), the obtained ethylene copolymer [
The polymerization step (b) may be carried out in the presence of the ethylene polymer [II], or the polymerization step (b) may be carried out in the presence of the polymer [II].
), the obtained ethylene polymer [II]
The ethylene copolymer [I] may be formed by performing the polymerization step (a) in the presence of. In any case, both processes
Must be done sequentially. In other words, the polymerization steps carried out in the later stages must be carried out in the presence of the polymer formed in the earlier stages. Among these, in the present invention, it is preferable to perform the polymerization step (b) after the polymerization step (a).

In the polymerization step (a) and the polymerization step (b), the polymerization step (
The weight of the ethylene copolymer II obtained in a) was 10
When it is 0 parts by weight, the weight of the ethylene polymer [II1 obtained in the polymerization step (b) is preferably 10 to 1000 parts by weight, preferably 20 to 500 parts by weight.

In addition, the intrinsic viscosity [η] of all the polymers (ethylene polymer [I] and ethylene copolymer [II]) is 0.5 to 6 dl.
/g, preferably 0.7-4dN/g, and the density is preferably 0.87-0.94g/cm3, preferably 0.88-0
．． More preferably 0.89 to 0.92 g than 93 g/cm3
/cm3 is desirable.

Furthermore, a part of the melting curve measured by DSC is in the range of 110°C or higher, preferably 115 to 125°C, and the amount of n-decane soluble cotton (W w ) and density (D w
) is IogWw≦-50XDw+45.9,
Preferably, IogWw≦-50XDw+45.8, more preferably logWw≦-50XDw+45. 7
It is desirable that

In this specification, the density Dt of the ethylene polymer [I] or ethylene copolymer [II] obtained in the first stage polymerization step (a) is the density Dt obtained during MFR measurement at a load of 2.16 kg. The resulting strands were heat-treated at 120° C. for 1 hour, slowly cooled to room temperature over 1 hour, and then measured using a density gradient tube.

Further, the intrinsic viscosity [η] of the above polymer was measured at 135° C. in a decalin solvent. Furthermore, the amount of n-decane soluble fiber in the above polymer was measured as follows.

Accurately weigh 3 g of the copolymer, add to 450 ml of n-decane, dissolve at 145°C, and slowly cool to 23°C. Next, the amount of n-decane soluble cotton (% by weight based on the total copolymer) was determined by distilling off n-decane from the filtrate obtained by removing the n-decane insoluble portion by filtration.

This copolymer with a small amount of n-decane soluble cotton has excellent blocking resistance.

Further, in this specification, the density (D2), intrinsic viscosity [η], and amount of n-decane soluble cotton (W2) of the polymer obtained in the second stage polymerization step were calculated as follows.

[η ko w −f 1 [η ko 1 [η] 2- 2 In the formula, [η ko , [η], and [η] 2 are the intrinsic viscosity of the total polymer, respectively, and the intrinsic viscosity obtained in the first stage. The intrinsic viscosity of the polymer obtained in the second stage is the intrinsic viscosity of the polymer obtained in the second stage, and fl and f2 are the polymerization fractions (f + f2-1) in the first stage and second stage, respectively. .

( f2D, D.

D2′″ Dl-flD.

D, D, and D2 are the density of the total polymer, the density of the polymer obtained in the first stage, and the density of the polymer obtained in the second stage, respectively.

Ww-f, W.

2 - Ww, Wl, and W2 are the amount of n-decane soluble cotton in the entire polymer, the amount of n-decane soluble cotton in the polymer obtained in the first stage, and the amount of n-decane soluble cotton in the polymer obtained in the second stage, respectively. This is the amount of n-decane soluble cotton.

Moreover, the melting point of DSC was used as a measure of the heat resistance of the copolymer.

In addition, in the present invention, the olefin polymerization catalyst [I] or [
II] may contain other components useful for olefin polymerization in addition to the above-mentioned components.

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

Example 1 (Preparation of [C] titanium catalyst component) Under a nitrogen atmosphere, 1 mol of commercially available anhydrous magnesium chloride was suspended in hexane 2D, and 6 mol of ethanol was added dropwise over 1 hour with stirring, followed by 1 mol at room temperature. Time reacted. To this, 2.6 mol of diethylaluminum chloride was added dropwise at room temperature, and stirring was continued for 2 hours. Next, after adding 6 moles of titanium tetrachloride, the system was heated to 80° C. and the reaction was carried out with stirring for 3 hours. The solid after the reaction was separated and washed repeatedly with hexane. The solid component thus obtained (T: 3
．． 45.6 mmol of ethanol was added dropwise at room temperature to 200 ml of a decane suspension containing 5 mmol of Mg and 21 wt% of titanium atoms, followed by reaction at 90° C. for 1 hour. After cooling the system to room temperature, 15 mmol of triethylaluminum was added, and the reaction was allowed to proceed at room temperature for 1 hour to obtain titanium catalyst component [C].

([B] Preparation of organoaluminumoxy compound) Ag(So
) 7.1 g of 14H20B and 133 ml of toluene 3 were charged, and after cooling to -5°C, toluene 15
47.9 ml of trimethylaluminum diluted in 2 ml
1 was added dropwise over 1 hour. After that, after reacting at 0 to -5℃ for 1 hour, the temperature was raised to 40℃ over 3 hours, and 40℃
The reaction was continued for an additional 72 hours. After the reaction, solid separation was performed by filtration, and toluene was removed using the furnace solution to obtain a white solid benzene-soluble organoaluminumoxy compound.

58.4 ml of the benzene-soluble organoaluminumoxy compound obtained above was redissolved in toluene (All) -2,57 mol/1), and 90.5 ml of toluene.
and Teflon cylinder (1.2mmX2-■φ) 25g
was placed in a 400 ml flask.

After cooling the temperature in the system to -5°C, 1.08 ml of water was gradually added dropwise over 20 minutes. At that time, the temperature in the prefecture was set to O
It was kept at ~-5°C. After the dropwise addition was completed, the temperature was raised to 80°C over 30 minutes, and the reaction was carried out at 80°C for 3 hours. After that, the Teflon cylinder was removed using a 32-mesh sieve, and the solubility in benzene at 60°C was 0.4 wt%, and the D / D ratio measured by IR was 0.
．． A benzene-insoluble organoaluminumoxy compound having the following formula was obtained.

(Polymerization) 900 ml of 4-methyl-1-pentene was charged into a 2ρ stainless steel autoclave which had been sufficiently purged with nitrogen, and the temperature inside the system was raised to 75°C. Thereafter, 0.5 mmol of triisobutylaluminum and 0.5 mmol of benzene-insoluble organic aluminum oxy compound in terms of aluminum atoms.
．． Polymerization was initiated by injecting 1 milligram atom and 0.001 mmol of bis(methylcyclopentagenyl)zirconium dichloride with ethylene. Polymerization was carried out at 80° C. for 40 minutes while keeping the total pressure at 8 kg/cd-G while continuously supplying ethylene [Step (a)].

Immediately thereafter, 800 ml of cyclohexane was added. Hydrogen 0.5
180 ml of the above polymerization solution was pumped with ethylene into an autoclave separate from step (a) charged with Ng and 0.3 mmol of ethylaluminum sesquichloride and heated to 170°C, and then the Ti catalyst component prepared above was 0.003 milligrams of titanium atoms were injected with ethylene to start polymerization again. While continuously supplying ethylene, the total pressure was maintained at 25 kg/cd-G, and 170
Polymerization was carried out at ℃ for 15 minutes [step (b)]. Polymerization was stopped by adding a small amount of methanol to the polymerization system, and the resulting polymer solution was precipitated in a large amount of methanol, collected, and dried under reduced pressure at 80° C. overnight. As a result, [η] is 1.63dj2/g, and the density is 0.90
5g/cm3, n-decane soluble member is 2.7wt
%, and the melting point peak measured by DSC is 122.
25.3 g of ethylene/4-methylpentene copolymer appearing at 112.93°C was obtained.

In addition, by performing only the above step (a), polymer solution 1
As a result of recovering the polymer in 50ml, [η] was 1.8
0dN/g, density is 0.891g/cm3, n-decane soluble member is 4.3wt%, and melting point is 83
9.6 g of ethylene/4-methyl-1-pentene copolymer was obtained. Also, according to the result of this step (a),
Ethylene 4-methyl-1- obtained in step (b) above
[η] of the pentene copolymer is 1.53 dN/g,
It was calculated that the density was 0.914 g/cm3, the n-decane soluble member was 1.7 wt%, and the polymerization amount was 15.7 g.

Comparative Example 1 2, l! with sufficient nitrogen substitution! 900ml of 4-methyl-1-pentene was charged into a stainless steel autoclave.
The temperature in the prefecture has been raised to 90 degrees Celsius. Thereafter, 1.0 mmol of triisobutylaluminum, 0.2 mg atom of the benzene-insoluble organoaluminumoxy compound prepared in Example 1 in terms of aluminum atom, and bis(
cyclopentagenyl) zirconium dichloride 0.0
Polymerization was initiated by injecting 0.2 mmol of ethylene. Total pressure 20kg while continuously supplying ethylene
/cJ-G, polymerization was carried out at 100°C for 40 minutes [η
] is 1.56d, Q/g, and the density is 0.907g/g.
cm3, n-decane soluble member is 0.65 wt%, and melting point is 97°C. Ethylene 4-methyl-1-
Pentene copolymer 91. I got og.

Comparative Example 2 200 ml of 4-methyl-(-pentene, 800 ml of cyclohexane and 0.5 Nj! of hydrogen were charged into a 2Il stainless steel autoclave which had been sufficiently purged with nitrogen, and the temperature inside the system was raised to 160°C. Thereafter, 0.135 mmol of ethylaluminum sesquichloride and the Ti catalyst component prepared in Example 1 were converted into titanium atoms.
Polymerization was started by injecting 0.013 mg atoms with ethylene. Total pressure 25kg/c while continuously supplying ethylene
Polymerization was carried out at 170°C for 40 minutes while maintaining If-G [η]
is 1.40 dD/g and the density is 0.908 g/cm
3, the n-decane soluble member is 3.9 wt%,
115 g of ethylene/4-methyl-1-pentene copolymer having a melting point of 122.7.112.6.96°C was obtained.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the amount of titanium used in step (b) was changed to 0.005 milligram atoms [η was 1.55611/g and the density was 0.907
g/cm3, and the n-decane soluble member is 2.5wt%.
36.9 g of ethylene/4-methyl-1-pentene copolymer having a melting point of 122.114.94°C was obtained.

In addition, [η] of the ethylene/4-methyl-1-pentene copolymer obtained in step (b) above is 1.46 dll/g.
It was calculated that the density was 0.913 g/aa, the n-decane soluble member was 1.9 wt%, and the polymerization amount was 27.3 g.

[Brief explanation of drawings]

FIGS. 1(a) and (b) are explanatory views of the olefin polymerization catalyst according to the present invention, FIG. 2 is an IR spectrum of a benzene-insoluble aluminum oxy compound, and FIG. 3 is an IR spectrum of a benzene-insoluble aluminum oxy compound. It is an IR spectrum of an aluminum oxy compound.

Claims (1)

[Claims] (1) Polymerization step (a): Using an olefin polymerization catalyst [I] consisting of a transition metal compound [A] containing a ligand having a cycloalkadienyl skeleton and an organoaluminumoxy compound [B], ethylene and Copolymerize with other α-olefins to form an ethylene copolymer [I] with a density of 0.91 g/cm^3 or less and an intrinsic viscosity [η] of 0.5 to 6 dl/g. and polymerization step (b): a titanium catalyst component [C] containing titanium, magnesium and halogen as essential components, and an organoaluminum compound [D] and/or an organoaluminumoxy compound [E] for olefin polymerization. Catalyst [I
I] is used to polymerize or copolymerize ethylene or ethylene and other α-olefins to produce a polymer that has a higher density than the above-mentioned ethylene copolymer [I] and has an intrinsic viscosity of 0.5 to 6 dl/g. A multi-stage process consisting of a step of forming a certain ethylene-based polymer [II], after performing the polymerization step (a), the polymerization step (b) is performed in the presence of the obtained ethylene-based copolymer [I]. Alternatively, after performing the polymerization step (b), the polymerization step (a) is performed in the presence of the obtained ethylene-based polymer [II], and the amount of polymerization in both of the above steps is adjusted to the ethylene-based copolymer [I]. ] The density is 0.87 to 0.93, characterized in that the ratio of the ethylene polymer [II] to 100 parts by weight is 10 to 1000 parts by weight.
g/cm^3, and the intrinsic viscosity [η] is 0.5 to 6
dl/g.