JPH06206923A - Catalyst for olefin polymerization and plymerization of olefin - Google Patents

Abstract

PURPOSE:To provide a catalyst for olefin polymerization produced by prepolymerizing a specific solid catalyst component with an olefin compound and capable of producing a film excellent in transparency and mechanical strength and an olefin polymer excellent in moldability. CONSTITUTION:The catalyst is obtained by prepolymerizing an olefin compound with a solid catalyst consisting of (A) a carrier, (B) a transition metal compound of the formula ML<1>x [M is transition metal which belongs to group NB in the periodic table; L<1> is ligand of M and at least two of the ligands are such as (methyl)cyclopentadienyl and the rest of them are 1-12C hydrocarbon and alkoxy; x is valence of M] [preferably, e.g. bis(n-butylcyclopentadienyl)zirconium dichloride], (C) a transition metal compound of the formula ML<2>x (L<2> is a ligand of M and at least two of the ligands are substituted cylopentadienyls having 2-5 of CH3 and/or C2H5 and the rest of them are such as H and halogen) [preferably, e.g. bis(1,3-dimethylcyclopentadienyl)zirconium dichloride] and (D) an organoaluminiumoxy compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins, and more specifically, to an olefin polymer capable of producing a film excellent in transparency and mechanical strength and excellent in moldability. The present invention relates to such an olefin polymerization catalyst and an olefin polymerization method.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene copolymers are molded by various molding methods and used for various purposes.
The ethylene copolymer has different required properties depending on the molding method and the application. For example, when an inflation film is to be molded at a high speed, there is no fluctuation or breakage of bubbles, and in order to perform a stable high speed molding, the melt tension (melt tension) of the ethylene-based copolymer should be considered for its molecular weight. You have to choose the bigger one. Similar properties are needed to prevent sagging or tearing in blow molding or to minimize width reduction in T die molding.

By the way, a method of improving the moldability by improving the melt tension (melt tension) and expansion ratio (die swell ratio) of an ethylene polymer obtained by using a Ziegler type catalyst, particularly a titanium catalyst, is disclosed in 56-90810
Japanese Patent Laid-Open No. 60-106806 and the like. However, ethylene-based polymers generally obtained by using a titanium-based catalyst, especially low-density ethylene-based copolymers, have a wide composition distribution, and there is a problem that molded products such as films are sticky.

Further, among ethylene polymers produced by using Ziegler type catalysts, ethylene polymers obtained by using chromium catalysts have a relatively high melt tension but are inferior in thermal stability. There is. It is considered that this is because the chain end of the ethylene polymer produced using the chromium catalyst is likely to be an unsaturated bond.

Among the Ziegler-type catalyst systems, ethylene-based polymers obtained by using a metallocene catalyst system are known to have advantages such as a narrow composition distribution and a molded product such as a film having less stickiness. However, for example, in JP-A-60-35007, an ethylene-based polymer obtained by using a zirconocene compound containing a cyclopentadienyl derivative as a ligand as a catalyst has one terminal unsaturated bond per molecule. There is a description that it contains, like the ethylene-based polymer obtained using the chromium-based catalyst,
It is expected that the thermal stability will be poor.

For this reason, if the olefin polymer has a high melt tension, good thermal stability, excellent mechanical strength and a narrow composition distribution, it can be used for olefin polymerization, especially for producing an ethylene copolymer. With the advent of catalysts and olefin polymerization processes, their industrial value is enormous.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and can produce a film excellent in transparency and mechanical strength, and to produce an olefin polymer excellent in moldability. It is an object of the present invention to provide an olefin polymerization catalyst and an olefin polymerization method that can be obtained.

[0008]

The olefin polymerization catalyst according to the present invention comprises: (a) a carrier, (b-I) at least one selected from the transition metal compounds represented by the following general formula [I], and ML ¹ _X [I] (wherein M is a transition metal atom selected from Group IVB of the periodic table, L ¹ is a ligand that coordinates with the transition metal atom M, and at least two of them are coordinated. The ligand L ¹ is a cyclopentadienyl group, a methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) (B-II) at least one selected from transition metal compounds represented by the following general formula [II], and ML ² _X ... [II] (wherein M is a transition selected from Group IVB of the periodic table) A metal atom, L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among these are 2 to 2 ligands selected from a methyl group and an ethyl group. It is a substituted cyclopentadienyl group having five, and the ligand L ² other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) (C) An organoaluminum oxy compound and a solid catalyst component carried thereon are preliminarily polymerized with an olefin.

The solid catalyst component of the present invention comprises the above-mentioned (b-I) transition metal compound, (b-II) transition metal compound, (c) organoaluminum oxy compound, and (d) an organoaluminum compound (a). ) It may be supported on a carrier.

The olefin polymerization catalyst of the present invention may be formed from a prepolymerization catalyst component composed of the above olefin polymerization catalyst and (e) an organoaluminum compound.

The olefin polymerization method of the present invention is characterized by polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst. Such an olefin polymerization catalyst and an olefin polymerization method have excellent moldability,
In addition, an olefin polymer having excellent transparency and mechanical strength can be produced.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method according to the present invention will be specifically described below.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymerization. May be used to mean coalesce.

Each catalyst component used in the olefin polymerization catalyst of the present invention will be described below. The carrier (a) used in the present invention (hereinafter sometimes referred to as “component (a)”) is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to 200 μm. Shaped or particulate solids are used. Among them, the inorganic compound is preferably a porous oxide, and specifically, S
iO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , Ca
O, ZnO, BaO, ThO _2, etc. or mixtures thereof, such as SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ ,
_{SiO 2 -V 2 O 5, SiO} 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO
Etc. can be illustrated. Among these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

The above inorganic oxide contains a small amount of Na ₂ CO.
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 (N
It does not matter even if it contains a carbonate, a sulfate, a nitrate or an oxide component such as O ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a carrier (a) differ depending on the type and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. , The pore volume is 0.3-
It is preferably 2.5 cm ³ / g. The carrier is, if necessary, 100 to 1000 ° C, preferably 150 to 70 ° C.
It is used after firing at 0 ° C.

In such a carrier (a), it is desirable that the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl group is 1.0% by weight or more, preferably 1.0%. 5 to 4.0% by weight, particularly preferably 2.0 to 3.5
It is desirable that the content is wt%.

Here, the amount of water adsorbed on the carrier (a) (% by weight)
And the amount of surface hydroxyl groups (% by weight) is determined as follows. [Amount of adsorbed water] 4 at normal temperature and nitrogen flow at a temperature of 200 ° C
The weight loss when dried for an hour is defined as the amount of adsorbed water. [Amount of surface hydroxyl groups] X (g) is the weight of the carrier obtained by drying at a temperature of 200 ° C under normal pressure and nitrogen flow for 4 hours.
Furthermore, the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours in which the surface hydroxyl groups have disappeared is Y (g),
Calculate by the following formula.

Surface hydroxyl group amount (% by weight) = {(X−Y) / X} × 100 Further, the carrier (a) that can be used in the present invention is an organic compound having a particle size in the range of 10 to 300 μm. The granular or fine particle solids can be mentioned. Examples of these organic compounds include α-C 2 -C 14 such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene.
Examples thereof include (co) polymers containing olefin as a main component, and polymers or copolymers containing vinylcyclohexane and styrene as main components.

Next, the transition metal compound catalyst components (b-I) and (b-II) will be described. The transition metal compound catalyst component (b-I) used in the present invention is a transition metal compound represented by the following formula [I], and the transition metal compound catalyst component (b-II) is represented by the following formula [II]. Transition metal compound.

ML ¹ _X ... [I] (wherein M is a transition metal atom selected from Group IVB of the periodic table, L ¹ is a ligand coordinated to the transition metal atom M, and At least two of the ligands L ¹ are a cyclopentadienyl group, a methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ML ² _X ... [II] (wherein M is a transition metal atom selected from Group IVB of the Periodic Table, L ² is a ligand coordinated to the transition metal atom, and at least 2 of these are included). The individual ligand L ² is a substituted cyclopentadienyl group having only 2 to 5 substituents selected from a methyl group and an ethyl group, and the ligand L ² other than the substituted cyclopentadienyl group is 1 to 12 carbon atoms
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) Hereinafter, the transition metal compound represented by the general formula [I] or [II] will be described more specifically.

In the above formula [I], M is IV of the periodic table.
A transition metal atom selected from Group B, specifically zirconium, titanium or hafnium, preferably zirconium.

L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are
At least one selected from a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, or a hydrocarbon group having 3 to 10 carbon atoms.
It is a substituted cyclopentadienyl group having certain substituents. These ligands may be the same or different. The ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom.

The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. When the substituted cyclopentadienyl group has two or more substituents, at least one substituent may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituents include a methyl group and an ethyl group. Alternatively, it is a hydrocarbon group having 3 to 10 carbon atoms.

Specific examples of the hydrocarbon group having 3 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, etc. Examples thereof include an alkyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a neofil group.

Of these, alkyl groups are preferable, and n-propyl group and n-butyl group are particularly preferable. In the present invention, the (substituted) cyclopentadienyl group coordinated to the transition metal is preferably a substituted cyclopentadienyl group, more preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms, A substituted cyclopentadienyl group is more preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable.

In the above general formula [I], the ligand L ¹ other than the (substituted) cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, It is an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom.

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, and more specifically, a methyl group, an ethyl group and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, alkyl group such as decyl group; cyclopentyl group, cyclohexyl group, etc. A cycloalkyl group of phenyl group,
Examples thereof include aryl groups such as tolyl group; and aralkyl groups such as benzyl group and neophyll group.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group and octoxy group. Can be illustrated.

Examples of the aryloxy group include a phenoxy group and the like. Examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group.

Halogen atoms are fluorine, chlorine, bromine and iodine.

Examples of the transition metal compound represented by the general formula [I] include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, and bis (ethylcyclopentadienyl) zirconium. Dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopenta) Dienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxychloride, bis (N-butylcyclopentadienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium diethoxide,
Bis (n-butylcyclopentadienyl) zirconium methyl chloride, bis (n-butylcyclopentadienyl)
Zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) zirconium phenyl chloride, bis (n-butyl) Cyclopentadienyl)
Zirconium hydride chloride, and the like. In the above example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product is
Includes 1,2,3- and 1,2,4-substitutes. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula [I], bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1 -Methyl-3-n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride are particularly preferred.

In the above general formula [II], M is the periodic table
A transition metal atom selected from Group IVB, specifically,
Zirconium, titanium or hafnium, preferably zirconium.

L ² is a ligand coordinated to the transition metal atom M, and at least two ligands L ² among them have only 2 to 5 substituents selected from a methyl group and an ethyl group.
And substituted cyclopentadienyl groups, each of which may be the same or different. The substituted cyclopentadienyl group is a substituted cyclopentadienyl group having two or more substituents, preferably a substituted cyclopentadienyl group having two to three substituents, and a disubstituted cyclopentadienyl group. An enyl group is more preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable.
In addition, each substituent may be the same or different.

In the above formula [II], the ligand L ² other than the substituted cyclopentadienyl group coordinated to the transition metal atom M has the same carbon number of 1 as L ¹ in the above general formula [I]. ~ 1
2 is a hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom.

Examples of the transition metal compound represented by the general formula [II] include bis (dimethylcyclopentadienyl) zirconium dichloride, bis (diethylcyclopentadienyl) zirconium dichloride, and bis (methylethylcyclopentadienyl). ) Zirconium dichloride Bis (dimethylethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dibromide, bis (dimethylcyclopentadienyl) zirconium methoxychloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride , Bis (dimethylcyclopentadienyl) zirconium butoxycyclolide, bis (dimethylcyclopentadienyl) zirconium diethoxide, bis (dimethylcyclopentadiene Nil) zirconium methyl chloride, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium benzyl chloride, bis (dimethylcyclopentadienyl) zirconium dibenzyl, bis (dimethylcyclopentadienyl) zirconium Examples thereof include phenyl chloride and bis (dimethylcyclopentadienyl) zirconium hydride chloride. In the above example, the disubstituted cyclopentadienyl ring is
Includes 1,2- and 1,3-substitutions, tri-substitutions include 1,2,3- and
Includes 1,2,4-substitutes. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula [II], bis (1,3-dimethylcyclopentadienyl) zirconium dichloride and bis (1,3-diethylcyclopentadienyl) zirconium dichloride ,
Bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride is particularly preferred.

In the present invention, the transition metal compound (b) is selected from at least one selected from the transition metal compounds represented by the above general formula [I] and the transition metal compound represented by the above general formula [II]. It is preferable to use in combination with at least one of the above. Specifically, a combination of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-n-propyl) Combination of methylcyclopentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride and bis (1,3-dimethylcyclopentadiene) A combination with (enyl) zirconium dichloride is preferred.

At least one transition metal compound selected from the transition metal compounds (bI) represented by the general formula [I] and the transition metal compound (b-
The at least one transition metal compound selected from II) is 99/1 to 50/50, preferably 97/3 to 70/30, and more preferably 95 / in terms of molar ratio (bI / b-II).
5-75 / 25, most preferably 90 / 10-80 / 2
It is desirable to use it in such an amount that the range is 0.

At least one selected from the transition metal compounds (bI) represented by the above general formula [I] and at least one selected from the transition metal compounds (b-II) represented by the above general formula [II]. The transition metal compound catalyst component containing one kind may be referred to as “component (b)”.

The organoaluminum oxy compound (c) (hereinafter sometimes referred to as the "component (c)") used in the present invention may be a conventionally known benzene-soluble aluminoxane, and is also known in JP-A No. 2-2980. It may be a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-276807.

The aluminoxane as described above can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

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

Specific examples of the organoaluminum compound used for producing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and tri-n-.
Trialkyl aluminum such as butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricyclohexyl aluminum, tricyclooctyl aluminum, etc. Tricycloalkyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dimethyl aluminum methoxide, diethyl aluminum ethoxy Like dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide; dialkylaluminum alkoxides such as.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable. 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) Isoprenylaluminum may also be used.

The organoaluminum compound as described above is
Used alone or in combination. As the solvent used in the production of aluminoxane, benzene, toluene, xylene, cumene, aromatic hydrocarbons such as 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 hydrocarbon solvents such as halides of aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component dissolved in benzene at 60 ° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. , Insoluble or sparingly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is 10 times that of the organoaluminum oxy compound corresponding to 100 mg of Al.
After suspending in 0 ml of benzene and mixing under stirring at 60 ° C for 6 hours, the solid portion separated on the filter was subjected to filtration at 60 ° C using a jacketed G-5 glass filter while hot. Amount of Al atoms present in all the filtrates after washing 4 times with 50 ml of benzene at ℃ (x
It is determined by measuring (mmol) (x%).

The olefin polymerization catalyst according to the present invention comprises the above-mentioned (a) carrier, (b-I) transition metal compound, and (b).
It is formed from -II) transition metal compound and (c) organoaluminum oxy compound, but if necessary, the following (d) organoaluminum compound may be used.

Examples of the (d) organoaluminum compound (hereinafter sometimes referred to as “component (d)”) used in the present invention include organoaluminum represented by the following general formula [III]. A compound can be illustrated.

R ¹ _n AlX _3-n ... [III] (In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, and X 1
Is a halogen atom or a hydrogen atom, and n is 1 to 3. In the above general formula [III], R ¹ 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, n- Examples include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of the (d) organoaluminum compound include the following compounds. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

Further, (d) an organoaluminum compound
It is also possible to use a compound represented by the following general formula [IV]
it can. R¹ _nAlY_3-n ... [IV] (wherein R¹Is the same as above, and Y is -OR²Group,-
OSiR³ ₃Group, -OAlR ^Four ₂Group, -NR^Five ₂Group, -SiR⁶ ₃
Group or -N (R⁷) AlR⁸ ₂And n is 1-2.
R², R³, R^FourAnd R⁸Is a methyl group, an ethyl group,
Sopropyl group, isobutyl group, cyclohexyl group,
Such as a nyl group, R^FiveIs hydrogen atom, methyl group, ethyl
Group, isopropyl group, phenyl group, trimethylsilyl group
And so on, R⁶And R⁷Is a methyl group, ethyl group, etc.
Is. ) As such an organoaluminum compound,
The following compounds are used. (1) R¹ _nAl (OR²)_3-nA compound represented by
Methyl aluminum methoxide, diethyl aluminum
Ethoxide, diisobutylaluminum methoxide
(2) R¹ _nAl (OSiR³ ₃)_3-nA compound represented by
If Et₂Al (OSi Me₃), (Iso-Bu)₂Al (OSiMe₃),
(iso-Bu)₂Al (OSiEt₃) Etc .; (3) R¹ _nAl (OAlR^Four ₂)_3-nCompounds represented by
If Et₂AlOAlEt₂, (Iso-Bu)₂AlOAl (iso-Bu)
₂Etc. (4) R¹ _nAl (NR^Five ₂)_3-nA compound represented by, for example
Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt,
Et₂AlN (SiMe₃)₂, (Iso-Bu)₂AlN (SiMe₃)₂ Na
DO; (5) R¹ _nAl (SiR⁶ ₃)_3-nA compound represented by, for example
(iso-Bu)₂AlSiMe₃ Etc .; (6) R¹ _nAl (N (R⁷) AlR⁸ ₂)_3-nCompound represented by
Thing, eg Et₂AlN (Me) AlEt₂, (Iso-Bu)₂AlN
(Et) Al (iso-Bu)₂Such .

Among the organoaluminum compounds represented by the above general formulas [III] and [IV], the general formula R ¹ ₃ Al,
The compounds represented by R ¹ _n Al (OR ² ) _3-n and R ¹ _n Al (OA1R ⁴ ₂ ) _3-n are preferable, and the compound in which R is an isoalkyl group and n = 2 is particularly preferable.

In the olefin polymerization catalyst of the present invention, the olefin is added to the solid catalyst component in which the component (b) and the component (c) as described above, and optionally the component (d) are supported on the component (a). It is a prepolymerization catalyst obtained by prepolymerization, or a catalyst comprising the prepolymerization catalyst (component) and (e) an organoaluminum compound. FIG. 1 shows a process for preparing an olefin polymerization catalyst according to the present invention.

The method for preparing the olefin polymerization catalyst of the present invention will be specifically described below. The solid catalyst component used in the present invention can be prepared by mixing and contacting the component (a), the component (b) and the component (c), and optionally the component (d). The contacting order of the components (a) to (d) at the time of preparing the solid catalyst component is arbitrarily selected, but the components (a) and (c) are preferably mixed and contacted, and then the component (b) is mixed. Are mixed and brought into contact with each other, and if necessary, the component (d) is mixed and brought into contact therewith. Component (b)
It is preferable that two or more kinds of transition metal compounds forming the component (b) are mixed in advance and then mixed and contacted with other components.

The contact of the above components (a) to (d) can be carried out in an inert hydrocarbon solvent. Specific examples of the inert hydrocarbon solvent used for preparing the catalyst include propane, butane, Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ethylene chloride , Halogenated hydrocarbons such as chlorobenzene and dichloromethane, or a mixture thereof.

When the components (a), (b) and (c) and, if necessary, the component (d) are mixed and contacted, the component (b) is usually added in an amount of 5 × 10 5 per 1 g of the component (a).
^{-6 to} 5 × 10 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol, and the concentration of component (b) is about 10 ^-4 to 2
× 10 ^-2 mol / liter (solvent), preferably 2 × 10
It is in the range of ^-4 to 10 ^-2 mol / liter (solvent). The atomic ratio (Al / transition metal) of aluminum of the component (c) to the transition metal in the component (b) is usually 10 to 500, preferably 20 to 200. Atom ratio (Al-d / Al-c) of aluminum atom (Al-d) of component (d) and aluminum atom (Al-c) of component (c) that are used as necessary.
Is usually in the range of 0.02 to 3, preferably in the range of 0.05 to 1.5. Component (a), component (b) and component (c),
The mixing temperature at the time of mixing and contacting the component (d) as necessary is usually -50 to 150 ° C, preferably -20 to 120.
And the contact time is 1 minute to 50 hours, preferably 10
Minutes to 25 hours.

The solid catalyst component obtained as described above has 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom of transition metal atom derived from the component (b) per 1 g of the component (a), preferably 10 g. ^{-5 to} 2 × 10 ^-4 gram atom, and 10 ^{-3 to} 5 × 10 ^-2 gram atom of aluminum atom derived from component (c) and component (d) per 1 g of component (a),
It is preferable that the carrier is supported in an amount of 2 × 10 ^{−3 to} 2 × 10 ⁻² gram atom.

The olefin polymerization catalyst (preliminary polymerization catalyst component) used in the present invention is prepared by introducing olefin into an inert hydrocarbon solvent in the presence of the above components (a) to (c) to carry out preliminary polymerization. It can be prepared. The solid catalyst component is preferably formed from the components (a) to (c). In this case, in addition to the solid catalyst component, component (c) and / or component (d) may be added.

As the olefin used in the prepolymerization, ethylene and α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1 -Octene, 1-decene, 1
Examples include -dodecene and 1-tetradecene. Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

As the inert hydrocarbon solvent, specifically, the same inert hydrocarbon solvent as that used in the preparation of the above solid catalyst component can be used. In the prepolymerization, the above component (b) is usually 10 ⁻⁶ to 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁶ in terms of the transition metal derived from the component (b). It is used in an amount of ^-5 to 10 ^-2 mol / liter (solvent), and component (b) is 1 g of component (a).
As a transition metal, it is usually used in an amount of 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ mol. The atomic ratio (Al / transition metal) between the aluminum of the component (c) and the transition metal in the component (b) is usually 10 to 50.
It is 0, preferably 20 to 200. The atomic ratio of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-c) of the component (c) that are used as necessary (Al-d /
Al-c) is usually 0.02 to 3, preferably 0.05 to 1.
The range is 5. The prepolymerization temperature is −20 to 80 ° C., preferably 0 to 60 ° C., and the prepolymerization time is 0.5 to 0.5 ° C.
It is 100 hours, preferably about 1 to 50 hours.

The olefin polymerization catalyst of the present invention is specifically prepared, for example, as follows. That is,
The carrier (component (a)) is suspended in an inert hydrocarbon.
Next, an organoaluminum oxy compound (component (c)) is added to this suspension and reacted for a predetermined time. The supernatant is then removed and the solid component obtained is resuspended with an inert hydrocarbon. A transition metal compound (component (b)) is added to this system, and after reacting for a predetermined time, the supernatant liquid is removed to obtain a solid catalyst component. Subsequently, the solid catalyst component obtained above is added to an inert hydrocarbon containing an organoaluminum compound (component (d)), and an olefin is introduced therein to obtain a prepolymerization catalyst (component).

The amount of the olefin (co) polymer produced by the prepolymerization is 0.1 to 500 g, preferably 0.2 to 300 g, and more preferably 0.5 to 200 g, per 1 g of the carrier (a). desirable. Further, in the prepolymerization catalyst, the component (b) is about 5 as transition metal atoms per 1 g of the carrier (a).
× 10 ^{-6 to} 5 × 10 ^-4 gram atom, preferably 10 ^-5 to
Aluminum atoms (Al) derived from the component (c) and the component (d), which are supported in the amount of 2 × 10 ⁻⁴ gram atom, are
The molar ratio (Al / M) to the transition metal atom (M) derived from the component (b) is 5 to 200, preferably 10 to 15.
It is desirable that the amount is carried in the range of 0.

The prepolymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Producing a prepolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g, in the presence of hydrogen. Is desirable.

In the present invention, the olefin polymerization or copolymerization is carried out in the presence of the prepolymerization catalyst as described above, or in the presence of the prepolymerization catalyst (component) and (e) the organoaluminum compound as described above. It is carried out in the gas phase or in the liquid phase in the form of slurry. In the slurry polymerization, an inert hydrocarbon may be used as the solvent, or the olefin itself may be used as the solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane and methyl. Alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene;
Examples include petroleum fractions such as gasoline, kerosene, and light oil. Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferable.

When carrying out the slurry polymerization method or the gas phase polymerization method, the catalyst as described above is usually used as the concentration of the transition metal atom in the polymerization reaction system in the range of 10 ⁻⁸ to 10 ⁻³ gram atom /
It is desirable to use it in an amount of liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

At the time of polymerization, in addition to the organoaluminum oxy compound (component (c)) supported on the carrier, an unsupported organoaluminum oxy compound may be used. In this case, the atomic ratio (Al / M) between the aluminum atom (Al) derived from the unsupported organoaluminum oxy compound and the transition metal atom (M) derived from the transition metal compound (b) is 5 to 300. , Preferably 10 to 200, more preferably 15 to 150.

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, and when carrying out the gas phase polymerization method. The polymerization temperature is usually 0 to 120 ° C., preferably 20.
Is in the range of -100 ° C.

The polymerization pressure is usually atmospheric pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. In the present invention, the olefin polymerization catalyst can contain other components useful for olefin polymerization in addition to the above-mentioned components.

Examples of such olefins which can be polymerized by the olefin polymerization catalyst of the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene and 1-hexene. , 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, etc. Can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

The olefin polymerization catalyst and the olefin polymerization method of the present invention include, particularly, ethylene and 3 to 20 carbon atoms.
It is preferably used for copolymerization with α-olefin. In the ethylene / α-olefin copolymer obtained by the olefin polymerization catalyst and the olefin polymerization method of the present invention,
The structural unit derived from ethylene is 50 to 100% by weight, preferably 55 to 99% by weight, and more preferably 65.
~ 98 wt%, most preferably 70-96 wt%, with 0 to 50 wt%, preferably 1 to 45 wt%, more preferred constitutional units derived from an α-olefin having 3 to 20 carbon atoms. 2 to 35% by weight, most preferably 4
It is desirable to be present in an amount of ~ 30% by weight.

The composition of the ethylene / α-olefin copolymer is usually determined by measuring the ¹³ C-NMR spectrum of a sample prepared by uniformly dissolving about 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube at the measurement temperature. 120
℃, measurement frequency 25.05MHz, spectrum width 1500
Hz, pulse repetition time 4.2 sec., Pulse width 6 μsec.
It is determined by measuring under the measurement conditions of.

Such an ethylene / α-olefin copolymer usually has the following characteristics (i) to (ix). (I) Density (d) is 0.850 to 0.980 g / c
m ^3, preferably 0.880~0.960g / cm ^3, more preferably 0.890~0.935g / cm ^3, it is desirable and most preferably from 0.905~0.930g / cm ³ .

The density (d) is 2.90 at 190 ° C.
The strand obtained at the time of measuring the melt flow rate (MFR) under a load of 16 kg was heat treated at 120 ° C. for 1 hour, and
After slowly cooling to room temperature over time, measurement is performed with a density gradient tube.

(Ii) The melt flow rate (MFR) is
0.01 to 200 g / 10 minutes, preferably 0.05 to 50
g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.

The melt flow rate (MFR) is
Measured according to ASTM D1238-65T under conditions of 190 ° C. and 2.16 kg load. (Iii) Melt tension (MT (g)) and melt flow rate (MFR) are MT> 2.2 × MFR ^−0.84, preferably 8.0 × MFR ^−0.84 >MT> 2.3 × MFR ^{−0.84 Preferably} satisfies the relationship of 7.5 × MFR ^−0.84 >MT> 2.5 × MFR ^−0.84 .

Since such an ethylene / α-olefin copolymer has a high melt tension (MT), it has good moldability. In addition, melt tension (MT (g))
Is determined by measuring the stress when the molten polymer is stretched at a constant rate. That is, the produced polymer powder is melted by a usual method and then pelletized to obtain a measurement sample. Using an MT measuring device manufactured by Toyo Seiki Seisakusho, a resin temperature of 190 ° C., an extrusion speed of 15 mm / min, and a winding speed of 10 to 20 m / min. The nozzle diameter was 2.09 mm and the nozzle length was 8 mm. When pelletizing, ethylene
To the α-olefin copolymer, 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3- ( 0.1% by weight of 4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were added.

(Iv) Shear stress at 190 ° C. is 2.4
The fluidity index (FI (1 / sec)) and the melt flow rate (MFR) defined by the shear rate when reaching × 10 ⁶ dyne / cm ² are FI <150 × MFR, and preferably FI <140 × MFR. It is more desirable that the relationship represented by FI <130 × MFR is satisfied.

The flow index (FI) is determined by extruding the resin from the capillary while changing the shear rate and measuring the stress at that time. That is, using a sample similar to MT measurement, manufactured by Toyo Seiki Seisakusho,
It is measured with a capillary flow characteristic tester at a resin temperature of 190 ° C. and a shear stress range of about 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / cm ² .

The MFR of the resin to be measured (g / 10 minutes)
Change the nozzle diameter as follows and measure. 0.5 mm when MFR> 20 1.0 mm when 20 ≧ MFR> 3 2.0 mm when 3 ≧ MFR> 0.8 3.0 mm when 0.8 ≧ MFR (v) Molecular weight distribution measured by GPC ( Mw / Mn, where Mw: weight average molecular weight, Mn: number average molecular weight) is 1.
It is preferably in the range of 5 to 4.

The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore. The separation column is TSK GNH HT,
The column size is 72 mm in diameter and 600 mm in length,
The column temperature was 140 ° C, o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase, and BHT was used as the antioxidant.
(Takeda Pharmaceutical Co., Ltd.) Using 0.025% by weight, the sample was moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene has a molecular weight of Mw <100
0 and Mw> 4 × 10 ⁶ were manufactured by Tosoh Corporation, and 1000 <Mw <4 × 10 ⁶ were manufactured by Pressure Chemicals.

(Vi) MT / (Mw / Mn) and FI / MFR are MT / (Mw / Mn)> 0.03 × FI / MFR-3.0 (however, 0.03 × FI / MFR-3) The value of 0.0 is set to 0 when it is less than 0) preferably 0.03 × FI / MFR + 1.0> MT / (Mw / Mn)
> 0.03 × FI / MFR-2.8 (however, the value of 0.03 × FI / MFR-2.8 is 0 when it is less than 0) More preferably 0.03 × FI / MFR + 0.8 > MT / (Mw / Mn)
> 0.03 × FI / MFR-2.5 (where the value of 0.03 × FI / MFR-2.5 is 0 when it is less than 0) is preferably satisfied.

Since the MT value increases as the Mw / Mn value increases, the MT / (Mw / Mn) index was used to reduce the influence of the Mw / Mn value on the MT value. Similarly, since the FI value increases with an increase in the MFR value, the FI / MFR index was used to reduce the influence of the MFR value on the FI value.

(Vii) Temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
(° C.) and density (d) are represented by Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, and most preferably Tm <550 × d-391. It is desirable to meet the relationship.

The temperature at the maximum peak position of the endothermic curve (Tm (° C)) measured by a differential scanning calorimeter (DSC)
Packs about 5 mg of sample in an aluminum pan at 20 ° C / min.
Raise the temperature to 0 ° C and hold at 200 ° C for 5 minutes, then at 20 ° C
It can be obtained from the endothermic curve when the temperature is decreased to room temperature at the speed of 10 / min, and then the temperature is increased at 10 ° C./min. For the measurement, a Perkin Elmer DSC-7 type device is used.

(Viii) When the n-decane-soluble component amount fraction (W (wt%)) and the density (d) at 23 ° C. are MFR ≦ 10 g / 10 min, W <80 × exp (-100 ( d-0.88)) + 0.1, preferably W <60 * exp (-100 (d-0.8)
8)) + 0.1, more preferably W <40 × exp (−100 (d−0.8)
8)) + 0.1 When MFR> 10 g / 10 minutes W <80 × (MFR-9) ^0.26 × exp (−100 (d−
The relationship of 0.88)) + 0.1 is satisfied.

N of the ethylene / α-olefin copolymer
-The amount of soluble components in decane (the smaller the amount of soluble components, the narrower the composition distribution) is about 3 g of the copolymer n-decane 450.
In addition to ml, the solution was dissolved at 145 ° C., cooled to 23 ° C., the n-decane-insoluble part was removed by filtration, and the n-decane-soluble part was recovered from the filtrate.

Relationship between temperature (Tm) at maximum peak position of endothermic curve measured by differential scanning calorimeter (DSC) and density (d), and n-decane soluble component amount fraction (W)
It can be said that the ethylene / α-olefin copolymer having the above-described relationship between the density and the density (d) has a narrow composition distribution.

(Ix) The number of unsaturated bonds present in the molecule is preferably 0.5 or less per 1000 carbon atoms and less than 1 per molecule of the polymer. The unsaturated bond was quantified by ¹³ C-NMR using a signal other than the double bond, that is, a signal in the range of 10 to 50 ppm, and a signal belonging to the double bond, ie, 10.
The area intensity of the signal in the range of 5 to 150 ppm is obtained from the integral curve and is determined from the ratio.

The olefin polymerization catalyst of the present invention and the olefin polymer obtained by the olefin polymerization method are
A film can be obtained by processing by ordinary air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooled inflation molding and the like. The film formed in this manner has excellent transparency and mechanical strength, and has heat sealability, hot tackiness, heat resistance, good blocking properties, etc. which are features of ordinary LLDPE. Further, since the composition distribution of the olefin polymer is extremely narrow, the film surface is not sticky. Further, since the melt tension is high, the bubble stability during inflation molding is excellent.

The olefin polymerization catalyst of the present invention and the film obtained by molding the olefin polymer obtained by the olefin polymerization method can be used in various types such as standard bags, sugar bags, oil packaging bags, and water packaging bags. It is suitable for packaging films and agricultural materials. It can also be used as a multilayer film by laminating it with a base material such as nylon or polyester.

[0096]

The olefin polymerization catalyst and the olefin polymerization method of the present invention can produce an olefin polymer having a high melt tension and excellent moldability.
A film having excellent transparency and mechanical strength can be produced from such an olefin polymer.

[0097]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

In the present invention, the physical properties of the film were evaluated as follows. [Haze] Measured according to ASTM-D-1003-61. [Gloss] Measured according to JIS Z8741. [Film Impact] It was measured by a pendulum type film impact tester (film impact tester) manufactured by Toyo Seiki Seisakusho.

[0099]

Example 1 Production of ethylene / α-olefin copolymer [Preparation of catalyst component] 5.0 kg of silica dried at 250 ° C. for 10 hours was suspended in 80 liters of toluene, and then cooled to 0 ° C. . Then, a toluene solution of methylaluminoxane (Al; 1.33 mol / liter) 28.
7 liters were dropped in 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C for 30 minutes, then heated to 95 ° C over 1.5 hours, and reacted at that temperature for 20 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method.

The solid component thus obtained was washed twice with toluene and then resuspended in 80 liters of toluene. To this system, 7.4 liters of a solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in toluene (Zr; 34.0 millimils / liter) and bis (1.3-dimethylcyclopentadienyl) zirconium 1.0 liter of a toluene solution of dichloride (Zr; 28.1 mmol / liter) was added dropwise at 80 ° C. over 30 minutes, and the mixture was further reacted at 80 ° C. for 2 hours. afterwards,
By removing the supernatant and washing twice with hexane,
A solid catalyst was obtained containing 3.6 mg of zirconium per gram.

[Preparation of Prepolymerized Catalyst] In 85 liters of hexane containing 1.7 mol of triisobutylaluminum, 0.85 kg of the solid catalyst obtained above and 1-
Hexene (255 g) was added, and ethylene was prepolymerized at 35 ° C for 12 hours to obtain 3.3 m / g of the solid catalyst.
A prepolymerized catalyst containing g of zirconium and prepolymerized with 10 g of polyethylene was obtained. The [η] of this ethylene polymer was 1.74 dl / g.

[Polymerization] 150 g of sodium chloride (Wako Pure Chemical Industries, Ltd.) was charged into a stainless steel autoclave having an internal volume of 2 liters, which was sufficiently replaced with nitrogen, and dried under reduced pressure at 90 ° C. for 1 hour. Then, a mixed gas of ethylene, 1-butene, and hydrogen (1-butene content; 2.6 mol%, hydrogen content; 0.01
(2 mol%), the pressure was returned to normal pressure, and the inside of the system was heated to 70 ° C.

Then, 0.007 mg of zirconium atom and triisobutylaluminum of the prepolymerized catalyst prepared as described above were added to a 0.7 mmol autoclave.

Then, a mixed gas of ethylene, 1-butene and hydrogen having the same composition as described above was introduced, and the total pressure was 8 kg /
The polymerization was started at cm ² -G. Immediately 80 ℃ in the system
Rose to.

Then, only the mixed gas is replenished and the total pressure is adjusted to 8
Polymerization was carried out at 80 ° C. for 1.5 hours while maintaining the pressure at 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 was dried under reduced pressure at 0 ° C overnight. As a result, 190 ℃, 2.16
MFR measured under kg load is 2.0 g / 10 min, density is 0.922 g / cm ³ , and decane-soluble part at 23 ° C. is 0.20 wt% ethylene / 1-butene co-weight 290 g of a combined product was obtained. Table 1 shows the melt properties and the like of the obtained copolymer.

[0107]

Example 2 Production of ethylene / α-olefin copolymer [Preparation of catalyst component] A solid catalyst component was prepared in the same manner as in Example 1 except that the amount of the transition metal compound used was changed as follows. Toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter); 6.6 liters Toluene of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride Solution (Zr; 28.1 mmol / liter); 2.0 liters [Preparation of preliminarily polymerized catalyst] Preliminary preparation was conducted in the same manner as in Example 1 except that the solid catalyst component obtained in [Preparation of catalyst component] was used. A polymerization catalyst was obtained.

[Polymerization] An ethylene / 1-butene copolymer having a different density from MFR was obtained in the same manner as in Example 1 except that the prepolymerized catalyst obtained in the above [Preparation of prepolymerized catalyst] was used. . Table 1 shows the melt properties and the like of the obtained copolymer.

[0109]

Example 3 Production of ethylene / α-olefin copolymer [Preparation of catalyst component] A solid catalyst component was prepared in the same manner as in Example 1 except that the amount of the transition metal compound used was changed as follows. Toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr; 34.0 mmol / liter); 5.6 liters Toluene of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride Solution (Zr; 28.1 mmol / liter); 2.9 liters [Preparation of preliminarily polymerized catalyst] Preliminary preparation was conducted in the same manner as in Example 1 except that the solid catalyst component obtained in [Preparation of catalyst component] was used. A polymerization catalyst was obtained.

[Polymerization] An ethylene / 1-butene copolymer having a density different from that of MFR was obtained in the same manner as in Example 1 except that the prepolymerized catalyst obtained in the above [Preparation of prepolymerized catalyst] was used. It was Table 1 shows the melt properties and the like of the obtained copolymer.

[0111]

[Comparative Example 1] Bis (1,3-
n-Butylmethylcyclopentadienyl) zirconium dichloride was used in the same manner as in Example 1 except that only
An ethylene / 1-butene copolymer was produced. Table 1 shows the melt properties and the like of the obtained copolymer.

[0112]

Comparative Example 2 Bis (1,3-
An ethylene / 1-butene copolymer was produced in the same manner as in Example 1 except that only dimethylcyclopentadienyl) zirconium dichloride was used. Table 1 shows the melt properties and the like of the obtained copolymer.

[0113]

[Comparative Example 3] Bis (1,3-
An ethylene / 1-butene copolymer was produced in the same manner as in Example 1 except that only dimethylcyclopentadienyl) zirconium dichloride was used. Table 1 shows the melt properties and the like of the obtained copolymer.

[0114]

[Production Examples 1 to 3] Using the ethylene / 1-butene copolymers obtained in Examples 1 to 3, 20 mmφ · L / D = 26
25 mmφ die, lip width 0.7 mm, single slit air ring, air flow rate = 90 liter / min, extrusion rate = 9 g / min, blow ratio =
1.8, take-up speed = 2.4 m / min, processing temperature = 200
A film having a thickness of 30 μm was inflation-molded under the condition of ° C. Table 1 shows the physical properties of the obtained film. An inflation film having excellent moldability, optical properties and strength was obtained.

[0115]

Production Example 4 Using the ethylene / 1-butene copolymer obtained in Comparative Example 1 above, a film having a thickness of 30 μm was formed by inflation molding in the same manner as in Production Examples 1 to 3. The physical properties of the film are shown in Table 1. Table 1 shows the physical properties of the obtained film.

[0116]

[Production Examples 5 to 6] Using the ethylene / 1-butene copolymers obtained in Comparative Examples 2 and 3, a film having a thickness of 30 µm was formed by inflation molding in the same manner as in Production Examples 1 to 3. Table 1 shows the physical properties of the obtained film.

Comparing the MT of the copolymer obtained in Example 1 with the MT of the copolymer obtained in Comparative Example 1, Example 1
Is superior in moldability despite having a higher MFR. In addition, the copolymer obtained in Example 2 and MT of the copolymer obtained in Comparative Example 2 and the MT of the copolymer obtained in Example 3 and the copolymer obtained in Comparative Example 3 having the same MFR were obtained. Comparing the MTs of the obtained copolymers, the moldability (MT) of Examples 2 and 3 is better.
Excellent in.

The relationship between MFR and MT of the ethylene / α-olefin copolymer of the present invention and the conventional ethylene / α
The relationship between MFR and MT of the -olefin copolymer is shown in FIG.

Further, the haze of the film formed from the copolymer obtained in Example 2 and the haze of the film formed from the copolymers obtained in Comparative Examples 1, 2 and 3 having the same MFR and density. In comparison, the film formed from the copolymer obtained in Example 2 is superior in transparency of the film.

The catalysts used in Examples 1 to 3 were both the transition metal compound catalyst component in the catalyst component used in Comparative Example 1 and the transition metal compound catalyst component in the catalyst component used in Comparative Examples 2 and 3. Contains. As a result, the ethylene / α-olefin copolymerization that improves the MT (moldability) and improves the transparency of the inflation film, compared with the copolymer obtained by polymerizing each transition metal compound catalyst component alone. A coalescence was obtained.

[0121]

[Table 1]

[0122]

[Table 2]

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

FIG. 2 shows the relationship between MFR and MT of the ethylene / α-olefin copolymer obtained by the method of the present invention, and the MFR and MT of the ethylene / α-olefin copolymer obtained by the conventional method. It is a figure which shows a relationship.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Todo 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (8)

[Claims] 1. A carrier (a), (b-I) at least one selected from transition metal compounds represented by the following general formula [I], and ML ¹ _X ... [I] (wherein M is It is a transition metal atom selected from Group IVB of the Periodic Table, L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are cyclopentadienyl. Group, methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) (B-II) at least one selected from transition metal compounds represented by the following general formula [II], and ML ² _X ... [II] (wherein M is a transition selected from Group IVB of the periodic table) A metal atom, L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among these are 2 to 2 ligands selected from a methyl group and an ethyl group. It is a substituted cyclopentadienyl group having five, and the ligand L ² other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. (C) An olefin polymerization catalyst, characterized in that an olefin is prepolymerized on a solid catalyst component carrying an organoaluminum oxy compound. 2. A carrier (a), (b-I) at least one selected from the transition metal compounds represented by the following general formula [I], and ML ¹ _X ... [I] (wherein M is It is a transition metal atom selected from Group IVB of the Periodic Table, L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are cyclopentadienyl. Group, methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) (B-II) at least one selected from transition metal compounds represented by the following general formula [II], and ML ² _X ... [II] (wherein M is a transition selected from Group IVB of the periodic table) A metal atom, L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among these are 2 to 2 ligands selected from a methyl group and an ethyl group. It is a substituted cyclopentadienyl group having five, and the ligand L ² other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) (C) An organoaluminum oxy compound is supported on a solid catalyst component, and a prepolymerization catalyst component obtained by prepolymerizing an olefin, and (e) an organoaluminum compound are used for olefin polymerization. catalyst. 3. A carrier (a), (b-I) at least one selected from the transition metal compounds represented by the following general formula [I], ML ¹ _X ... [I] (wherein M is It is a transition metal atom selected from Group IVB of the Periodic Table, L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are cyclopentadienyl. Group, methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) (B-II) at least one selected from transition metal compounds represented by the following general formula [II], and ML ² _X ... [II] (wherein M is a transition selected from Group IVB of the periodic table) A metal atom, L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among these are 2 to 2 ligands selected from a methyl group and an ethyl group. It is a substituted cyclopentadienyl group having five, and the ligand L ² other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) A catalyst for olefin polymerization, characterized in that a solid catalyst component carrying (c) an organoaluminum oxy compound and (d) an organoaluminum compound is preliminarily polymerized with an olefin. 4. A carrier (a), (b-I) at least one selected from transition metal compounds represented by the following general formula [I], and ML ¹ _X ... [I] (wherein M is It is a transition metal atom selected from Group IVB of the Periodic Table, L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are cyclopentadienyl. Group, methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) (B-II) at least one selected from transition metal compounds represented by the following general formula [II], and ML ² _X ... [II] (wherein M is a transition selected from Group IVB of the periodic table) A metal atom, L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among these are 2 to 2 ligands selected from a methyl group and an ethyl group. It is a substituted cyclopentadienyl group having five, and the ligand L ² other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) (C) Organoaluminum oxy compound, (d) Organoaluminum compound supported on a solid catalyst component, a prepolymerized catalyst component obtained by prepolymerizing olefin, and (e) organoaluminum compound An olefin polymerization catalyst characterized by the above. 5. A carrier (a), (b-I) at least one selected from transition metal compounds represented by the following general formula [I], ML ¹ _X ... [I] (wherein M is It is a transition metal atom selected from Group IVB of the periodic table, L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are cyclopentadienyl. Group, methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) (B-II) at least one selected from transition metal compounds represented by the following general formula [II], and ML ² _X ... [II] (wherein M is a transition selected from Group IVB of the periodic table) A metal atom, L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among these are 2 to 2 ligands selected from a methyl group and an ethyl group. It is a substituted cyclopentadienyl group having five, and the ligand L ² other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. (C) An olefin polymerization method characterized by polymerizing an olefin in the presence of an olefin polymerization catalyst obtained by prepolymerizing an olefin on a solid catalyst component carrying an organoaluminum oxy compound. 6. A carrier (a), (b-I) at least one selected from the transition metal compounds represented by the following general formula [I], ML ¹ _X ... [I] (wherein M is It is a transition metal atom selected from Group IVB of the Periodic Table, L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are cyclopentadienyl. Group, methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) (B-II) at least one selected from transition metal compounds represented by the following general formula [II], and ML ² _X ... [II] (wherein M is a transition selected from Group IVB of the periodic table) A metal atom, L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among these are 2 to 2 ligands selected from a methyl group and an ethyl group. It is a substituted cyclopentadienyl group having five, and the ligand L ² other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) (C) An organoaluminum oxy compound is supported on a solid catalyst component, and a olefin is polymerized in the presence of a prepolymerization catalyst component obtained by prepolymerizing an olefin, and (e) an organoaluminum compound. And a method for polymerizing olefins. 7. A carrier (a), (b-I) at least one selected from transition metal compounds represented by the following general formula [I], ML ¹ _X ... [I] (wherein M is It is a transition metal atom selected from Group IVB of the periodic table, L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are cyclopentadienyl. Group, methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) (B-II) at least one selected from transition metal compounds represented by the following general formula [II], and ML ² _X ... [II] (wherein M is a transition selected from Group IVB of the periodic table) A metal atom, L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among these are 2 to 2 ligands selected from a methyl group and an ethyl group. It is a substituted cyclopentadienyl group having five, and the ligand L ² other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) (C) Organoaluminum oxy compound and (d) organoaluminum compound are supported on a solid catalyst component, and olefin is polymerized in the presence of an olefin polymerization catalyst formed by prepolymerizing olefin. A method for polymerizing an olefin. 8. A carrier (a), (b-I) at least one selected from the transition metal compounds represented by the following general formula [I], ML ¹ _X ... [I] (wherein M is It is a transition metal atom selected from Group IVB of the Periodic Table, L ¹ is a ligand that coordinates to the transition metal atom M, and at least two of these ligands L ¹ are cyclopentadienyl. Group, methylcyclopentadienyl group,
Ethylcyclopentadienyl group, or C3-10
Is a substituted cyclopentadienyl group having at least one group selected from the hydrocarbon groups, and the ligand L ¹ other than the (substituted) cyclopentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, An alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom, X
Is the valence of the transition metal M. ) (B-II) at least one selected from transition metal compounds represented by the following general formula [II], and ML ² _X ... [II] (wherein M is a transition selected from Group IVB of the periodic table) A metal atom, L ² is a ligand that coordinates to a transition metal atom, and at least two ligands L ² among these are 2 to 2 ligands selected from a methyl group and an ethyl group. It is a substituted cyclopentadienyl group having five, and the ligand L ² other than the substituted cyclopentadienyl group has 1 to 12 carbon atoms.
A hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a halogen atom or a hydrogen atom,
X is the valence of the transition metal atom M. ) In the presence of (e) an organoaluminum compound, and (e) a prepolymerization catalyst component obtained by prepolymerizing a solid catalyst component carrying an organoaluminum oxy compound and (d) an organoaluminum compound. A method for polymerizing an olefin, characterized in that an olefin is polymerized.