JP3431966B2 - Multi-stage polymerization of olefin - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a multi-stage polymerization method for olefins, and more specifically, it has excellent thermal stability and moldability as compared with conventionally known ethylene copolymers or ethylene copolymer compositions, The present invention also relates to a multi-stage polymerization method of an ethylene-based copolymer composition capable of forming a film having excellent transparency and mechanical strength.

[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 required to prevent sagging or tearing in blow molding or to minimize width reduction in T die molding. In addition, in such extrusion molding, it is necessary that the stress of the ethylene-based copolymer under extrusion under high shear is small from the economical viewpoint such as quality improvement of the molded article and reduction of power consumption during molding.

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

Among ethylene polymers produced by using Ziegler type catalysts, ethylene polymers obtained by using chromium catalysts are relatively excellent in melt tension but poor in thermal stability. There are disadvantages. 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, it is known that the ethylene-based polymer obtained by using the metallocene catalyst system has an advantage that the composition distribution is narrow and a molded product such as a film is less sticky. However, for example, JP-A-60-35007 describes that an ethylene-based polymer obtained by using a zirconocene compound composed of a cyclopentadienyl derivative as a catalyst contains one terminal unsaturated bond per molecule. However, like the ethylene-based polymer obtained using the above chromium-based catalyst, it is expected that the thermal stability is poor. Further, since the molecular weight distribution is narrow, there is concern that the fluidity during extrusion molding may be poor.

Therefore, a method for producing an ethylene-based polymer composition having a high melt tension, a small stress in a high shear region, a good thermal stability, an excellent mechanical strength, and a narrow composition distribution appears. If so, its industrial value is extremely high.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is an ethylene-based copolymer composition capable of producing a film having excellent moldability, transparency and mechanical strength. It is intended to provide a manufacturing method.

[0008]

SUMMARY OF THE INVENTION An olefin multistage polymerization method according to the present invention is selected from [I] (a) an organoaluminum oxy compound and (b-I) a transition metal compound represented by the following general formula [b-I]. At least one of ML ¹ _X ... [b-I] (wherein M is a transition metal atom selected from Group IVB of the periodic table, and L ¹ is a ligand coordinated to the transition metal atom M). And at least two of these 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. ) (B-II) At least one selected from the transition metal compounds represented by the following general formula [b-II], ML ² _X ... [b-II] (M in the formula is IVB of the periodic table) Is a transition metal atom selected from the group, L ² is a ligand that coordinates to the transition metal atom, and at least two ligands L ² among these are coordinations selected from a methyl group and an ethyl group. A substituted cyclopentadienyl group having only 2 to 5 children, 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 an olefin polymerization catalyst (C1) containing 3 to 2 carbon atoms.
A step of producing an ethylene / α-olefin copolymer [A] by copolymerizing 0-α-olefin, and [II] a polymerization vessel different from the polymerization vessel in which the copolymerization reaction is carried out. Ethylene in the presence of an olefin polymerization catalyst (C2) containing an organoaluminum oxy compound and a transition metal compound of Group IV of the periodic table containing a ligand having a (b-III) cyclopentadienyl skeleton Carbon number 3
Copolymerize with ~ 20 α-olefins to produce ethylene / α-
Producing an olefin copolymer [B] ,
The density of the ethylene / α-olefin copolymer [A],
The density of the ethylene / α-olefin copolymer [B]
Ratio ([A] / [B]) is 0.930 to 0.999.
It is characterized by that.

In the present invention, the olefin polymerization catalyst (C1) used in the copolymerization step [I] is the above-mentioned (a).
A catalyst containing (d) an organoaluminum compound in addition to the organoaluminum oxy compound, the (b-I) transition metal compound and the (b-II) transition metal compound may be used,
(C) A solid catalyst in which the (a) organoaluminum oxy compound, the (b-I) transition metal compound, and the (b-II) transition metal compound are supported on a carrier,
(C) Prepolymerization in which an olefin is prepolymerized on a solid catalyst component in which the (a) organoaluminum oxy compound, the (b-I) transition metal compound, and the (b-II) transition metal compound are supported on a carrier. It may be a catalyst. Further, it may be a catalyst composed of the solid catalyst (solid catalyst component) and (d) organoaluminum compound, or a catalyst composed of the prepolymerization catalyst (preliminary polymerization catalyst component) and (d) organoaluminum compound.

In the present invention, the olefin polymerization catalyst (C2) used in the copolymerization step [II] is the above-mentioned (a) organoaluminum oxy compound and (b-III).
It may be a catalyst containing (d) an organoaluminum compound in addition to the transition metal compound, and (c) a solid catalyst comprising the (a) organoaluminum oxy compound and the (b-III) transition metal compound supported on a carrier. May be, (c)
It may be a prepolymerization catalyst prepared by prepolymerizing an olefin on a solid catalyst component in which the (a) organoaluminum oxy compound and the (b-III) transition metal compound are supported on a carrier. Further, the solid catalyst (solid catalyst component) and (d)
It may be a catalyst composed of an organoaluminum compound, or a catalyst composed of the prepolymerization catalyst (preliminary polymerization catalyst component) and (d) an organoaluminum compound.

According to such a multi-stage polymerization method of olefins, it is possible to obtain an ethylene copolymer composition capable of producing a film which is excellent in thermal stability and moldability, and is excellent in transparency and mechanical strength.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The multi-stage olefin polymerization method according to the present invention will be specifically described below. First, (a) an organoaluminum oxy compound, which is a catalyst component forming the olefin polymerization catalyst (C1) used in the present invention, (b)
-I) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (b-II) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton A transition metal compound, (c) a carrier, (d) an organoaluminum compound, and (a) an organoaluminumoxy compound which is a catalyst component for forming an olefin polymerization catalyst (C2), and (b-III) a cyclopentadienyl skeleton. The transition metal compound of Group IV of the Periodic Table, the (c) carrier, and the (d) organoaluminum compound containing the ligand will be specifically described.

The (a) organoaluminumoxy compound (hereinafter sometimes referred to as "component (a)") forming the olefin polymerization catalysts (C1) and (C2) used in the present invention is conventionally known. It may be a benzene-soluble aluminoxane or a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-276807.

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 steam is directly applied to 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 organometallic 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, octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light 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 mg 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%).

Next, the (b-I) transition metal compound and the (b-II) transition metal compound forming the olefin polymerization catalyst (C1) used in the present invention will be described. The (b-I) transition metal compound used in the present invention is represented by the following general formula [b-I], and the (b-II) transition metal compound is represented by the following general formula [b-II].

ML ¹ _X ... [b-I] (where 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, At least two of these 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 ... [b-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 among these, The at least two ligands L ² are a substituted cyclopentadienyl group having only 2 to 5 substituents selected from a methyl group and an ethyl group, and a 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. ) Hereinafter, the transition metal compound represented by the general formula [b-I] or [b-II] will be described more specifically.

In the above formula [b-I], M is the periodic table
A transition metal atom selected from Group IVB, 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, an alkyl group is preferable, and an n-propyl group and an 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 [b-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. A group, aryloxy group, trialkylsilyl group, halogen atom or 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, octoxy group and the like. 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 [b-I] include bis (cyclopentadienyl)
Zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, 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-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n- Butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxychloride, bis (n-butylsik) Pentadienyl) 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) Examples thereof include zirconium phenyl chloride, bis (n-butylcyclopentadienyl) zirconium hydride chloride, and the like. In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound includes 1,2,3- and 1,2,4-substituted compounds. Including. In the present invention,
In the zirconium compound as described above, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.

Among these transition metal compounds represented by the general formula [b-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 [b-II], M is a transition metal atom selected from Group IVB of the periodic table, 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 [b-II], the ligand L ² other than the substituted cyclopentadienyl group coordinated to the transition metal atom M is the same as L ¹ in the above general formula [b-I]. 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.

Examples of the transition metal compound represented by the general formula [b-II] include bis (dimethylcyclopentadienyl) zirconium dichloride, bis (diethylcyclopentadienyl) zirconium dichloride and bis (methylethylcyclopenta). Dienyl) 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 (dimethylcyclopentadienyl) zirconium methyl chloride, bis (Dimethylcyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium benzyl chloride, bis (dimethylcyclopentadienyl) zirconium dibenzyl, bis (dimethylcyclopentadienyl) zirconium phenyl chloride, bis (dimethylcyclo Pentadienyl) 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 1,2,
Includes 3- and 1,2,4-substitutes. In the present invention, in the zirconium compound as described above, zirconium metal,
A transition metal compound substituted with titanium metal or hafnium metal can be used.

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

In the present invention, at least one selected from the transition metal compounds represented by the above general formula [b-I] as the transition metal compound catalyst component and the transition metal represented by the above general formula [b-II]. It is preferable to use in combination with at least one selected from the compounds. 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 above general formula [b-I] and the transition metal compound (b represented by the above general formula [b-II] -II) and at least one transition metal compound are 99/1 to 50/5 in molar ratio (bI / b-II).
0, preferably 97/3 to 70/30, more preferably 95/5 to 75/25, most preferably 90/10 to 8
It is preferably used in an amount such that the range is 0/20.

Hereinafter, the term "component (b)" means at least one selected from the transition metal compounds (bI) represented by the above general formula [b-I] and the above general formula [b-II]. In some cases, it means a transition metal compound catalyst component containing at least one selected from the transition metal compounds (b-II).

A transition metal compound of Group IV of the periodic table containing a ligand having a (b-III) cyclopentadienyl skeleton which forms the catalyst (C2) for olefin polymerization used in the present invention (hereinafter referred to as "component ( b-III) ".)
Is not particularly limited as long as it is a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, but it is a transition metal compound represented by the following general formula [b-III]. preferable.

ML _x [b-III] [wherein M is a transition metal atom selected from Group IVB of the periodic table, L is a ligand which coordinates with the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group. , SO ₃ R
A group (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom or a hydrogen atom, and x is a valence of the transition metal. The transition metal compound represented by the above general formula [b-III] is a transition metal compound (bI) represented by the above general formula [b-I] and a transition metal compound represented by the above general formula [b-II]. Metal compound (bI
I) is included.

In the above general formula [b-III], M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium,
Preferred is zirconium.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a trialkylsilyl group or a halogen atom.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula [b-III] contains two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons among them are Alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene groups,
It may be bonded via a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. 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. More specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, etc., cycloalkyl group, cyclopentyl group, cyclohexyl group, etc., aryl group, phenyl group, tolyl group, etc., aralkyl group, benzyl group, neophyll group, etc. Are exemplified.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. A transition metal compound containing a ligand having such a cyclopentadienyl skeleton has, for example, when the valence of the transition metal is 4,
More specifically, it is represented by the following general formula [b-III ′].

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ... [b-III '] (In the formula, M is the above transition metal atom, and R ² is a group having a cyclopentadienyl skeleton (coordination). Child) and R ³ ,
R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton,
Alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, trialkylsilyl group, SO ₃ R group, halogen atom or hydrogen atom, k is an integer of 1 or more, and k + l + m + n = 4 is there. ) In the present invention, in the above general formula, R ² , R ³ , R ⁴
A metallocene compound in which two of R ⁵ and R ⁵ (for example, R ² and R ³ ) are groups (ligands) having a cyclopentadienyl skeleton is preferably used. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene, and methylphenylsilylene groups. It may be connected via. Further, in this case, the other ligands (for example, R ⁴ and R ⁵ ) are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group. , SO ₃ R, a halogen atom or a hydrogen atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (Indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5, 6,7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) Zirconium dichloride, dimethyl silylene bis (methylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (dimethyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (trimethylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride , Dimethyl silylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), dimethyl silane Renbis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (Cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl)
Methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, Bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

In the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can be used. The olefin polymerization catalyst (C1) used in the present invention has the above-mentioned (a).
The catalyst may be composed of an organoaluminum oxy compound, a (b-I) transition metal compound, and a (b-II) transition metal compound. The solid catalyst on which the (b-I) transition metal compound or the (b-II) transition metal compound is supported may be used. Further, the olefin polymerization catalyst (C2) used in the present invention may be a catalyst comprising the above-mentioned (a) organoaluminum oxy compound and (b-III) transition metal compound. c) on the carrier,
The above (a) organoaluminum oxy compound, the above (b-I
II) A solid catalyst on which a transition metal compound is supported may be used.

The carrier (c) forming the olefin polymerization catalysts (C1) and (C2) used in the present invention (hereinafter sometimes referred to as "component (c)") is an inorganic or organic compound. The particle size is 10 to 300 μm,
Preferably, a granular or particulate solid having a particle size of 20 to 200 μm is used. Among these, porous oxides are preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , M
gO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, B
aO, ThO _2, etc. or a mixture 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. Of 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 inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
Carbonate such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O,
It does not matter if it contains sulfates, nitrates or oxides.

The carrier (c) has different properties depending on its 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 ² / 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 carrier (c), 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% by weight. 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 (c) (% 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 (c) that can be used in the present invention is a granule of an organic compound having a particle size of 10 to 300 μm. Examples thereof include solid or fine particle solids. These organic compounds include ethylene, propylene, 1-butene,
Examples of (co) polymers formed mainly from α-olefins having 2 to 14 carbon atoms such as 4-methyl-1-pentene, or polymers or copolymers formed mainly from vinylcyclohexane or styrene can do.

Further, as a catalyst component forming the olefin polymerization catalyst (C1) and the olefin polymerization catalyst (C2) used in the present invention, the following (d) organoaluminum compound can be used, if necessary. .

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

R ¹ _n AlX _3-n ... [IV] (In the formula [IV], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1
It is 3. ) In the above general formula [IV], 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.

Such an organoaluminum compound (d)
Specifically, the following compounds may be mentioned. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum 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.

As the organoaluminum compound (d), a compound represented by the following general formula [V] can be used. R ¹ _n AlY _3-n ... [V] (In the formula [V], R ¹ is the same as above, and Y is —OR ²
Group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -
SiR ⁶ ₃ group or —N (R ⁷ ) AlR ⁸ ₂ group, n is 1 to
2, R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (1) A compound represented by R ¹ _n Al (OR ² ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc. (2) R ¹ _n Al (OSiR ³ ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc .; (3) Compounds represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , for example, Et ₂ AlOAiLet ₂ , (iso-Bu) ₂ AlOAl (iso-B
u) _{2 and the} like; (4) compounds represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt,
_{Et 2 AlN (SiMe 3) 2} , (iso-Bu) 2 AlN (SiMe 3) 2
(5) A compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , such as (iso-Bu) ₂ AlSi Me ₃ ; (6) R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN
(Et) Al (iso-Bu) ₂ etc.

Among the organoaluminum compounds represented by the above general formulas [IV] and [V], the general formulas R ¹ ₃ Al and R ¹
_The compounds represented by _n Al (OR ² ) _3-n and R ¹ _n Al (OAlR ⁴ ₂ ) _3-n are preferable, and R is an isoalkyl group.
Compounds with n = 2 are preferred.

The olefin polymerization catalyst (C1) used in the present invention is a catalyst (C1-i) composed of the above-mentioned component (a), component (b-I) and component (b-II), and component (C1-i). Solid catalyst (C1-ii) in which component (a), component (b-I) and component (b-II) are supported on c), and olefin is preliminarily stored on the solid catalyst (C1-ii) (solid catalyst component). A prepolymerized catalyst (C1-iii) obtained by polymerization, or a catalyst comprising the catalyst (C1-i) (catalyst component) and the component (d), the solid catalyst (C1-ii) (solid catalyst component) and the component ( and a catalyst comprising the prepolymerization catalyst (C1-iii) (preliminary polymerization catalyst component) and the component (d).

The olefin polymerization catalyst (C2) used in the present invention comprises the above-mentioned component (a) and component (b-I).
II) a catalyst (C2-i), a solid catalyst (C2-ii) in which the component (a) and the component (b-III) are supported on the component (c), the solid catalyst (C2-ii) (solid catalyst) Component)) a prepolymerization catalyst (C2-iii) obtained by prepolymerizing olefin, or a catalyst comprising the catalyst (C2-i) and the component (d), the solid catalyst (C2-ii) (solid catalyst component), A catalyst comprising the component (d), the prepolymerization catalyst (C2-iii) (preliminary polymerization catalyst component)
And a component (d).

FIG. 1 shows the steps for preparing the olefin polymerization catalyst used in the present invention. Catalyst (C1-i) and catalyst (C2
In -i), the catalyst components can be prepared by mixing and contacting each catalyst component inside or outside the polymerization vessel. However, after the component (a) is made into a solid component, the component (b) (or the component (b- III)) is mixed and contacted to form a solid catalyst, or component (a) and component (b) (or component (b-III)) are mixed and contacted in advance to form a solid catalyst, It is also possible to add a solid catalyst to the polymerization system.

The catalyst (C1-i) is a component (a) and a component (b) in an inert hydrocarbon solvent, and optionally a component (d).
Can be formed by mixing and contacting. The order of contacting each component is arbitrarily selected, but when the components (a) and (b) are mixed and contacted, it is preferable to add the component (b) to the suspension of the component (a). The component (b) is preferably prepared by mixing in advance two or more transition metal compounds forming the component (b) and then mixing and contacting with other components.

Specific examples of the inert hydrocarbon solvent used for preparing the catalyst (C1-i) include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbons such as pentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or a mixture thereof. .

When the components (a) and (b) and, if necessary, the component (d) are mixed and contacted, the concentration of aluminum in the component (a) is about 0.1 to 5 mol / liter (solvent), It is preferably in the range of 0.3 to 3 mol / liter (solvent). The atomic ratio (Al / transition metal) of aluminum of the component (a) to the transition metal in the component (b) is
It is usually 10 to 500, preferably 20 to 200. The atomic ratio (Al-d / Al-a) of the aluminum atom (Al-d) of the component (d) and the aluminum atom (Al-a) of the component (a), which are used as necessary, is usually 0.02 to 3, preferably in the range of 0.05 to 1.5. The mixing temperature for mixing and contacting the component (a) and the component (b), and optionally the component (d), is usually -50 to 150 ° C, preferably -20.
The contact time is 1 minute to 50 hours, preferably 10 minutes to 25 hours.

The catalyst (C2-i) used in the present invention is the same as the above-mentioned catalyst (C1-i) by using the component (a) and the component (b-III) and, if necessary, the component (d). Can be prepared.

Catalyst (C1-i) prepared as described above
And the catalyst (C2-i) has 5 × 1 transition metal atoms derived from the component (b) (or the component (b-III)) per 1 g of the catalyst.
0 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2 ×
Aluminum atoms contained in an amount of 10 ⁻⁴ gram atom and derived from component (a) and component (d) are from 10 ⁻² to
2.5 × 10 ^-2 gram atom, preferably 1.5 × 10 ^-2
It is preferably contained in an amount of 2 × 10 ^-2 gram atom.

Solid catalyst used in the present invention (C1-ii)
Can be prepared by making the component (c) support the component (a) and the component (b) as described above, and optionally the component (d). The solid catalyst (C2-ii) used in the present invention is prepared by supporting the above-mentioned component (a) and component (b-III) and, if necessary, component (d) on component (c). It can be prepared.

The order of contacting the components (a) to (d) when preparing the solid catalyst (C1-ii) of the present invention is arbitrarily selected, but the components (a) and (c) are preferred. Are mixed and contacted, then component (b) is mixed and contacted, and further component (d) is mixed and contacted, if necessary. Component (b)
Is preferably 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. Specifically, as the inert hydrocarbon solvent used for preparing the catalyst, specifically, the above catalyst ( Mention may be made of the inert hydrocarbon solvent used in the preparation of C1-i).

When the component (a), the component (b), the component (c) and, if necessary, the component (d) are mixed and contacted, the component (b) is usually 5 × 10 5 g per 1 g of the component (c).
^{-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 (a) to the transition metal in the component (b) is usually 10 to 500, preferably 20 to 200. Atom ratio (Al-d / Al-a) of aluminum atom (Al-d) of component (d) and aluminum atom (Al-a) of component (a) 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.

Solid catalyst used in the present invention (C2-ii)
Is a solid catalyst (C1-i) obtained by using the component (a), the component (b-III) and the component (c), and optionally the component (d).
It can be prepared in the same manner as i).

The solid catalyst (C1
-ii) and solid catalyst (C2-ii) per 1 g of component (c)
Transition gold derived from component (b) (or component (b-III))
5 x 10 genus atoms^-6~ 5 x 10^-FourGram atom, preferably
Is 10^-Five~ 2 x 10^-FourIt is carried in the amount of gram atom, and also
Originated from component (a) and component (d) per 1 g of component (c)
10 aluminum atoms^-3~ 5 x 10^-2Gram Hara
Child, preferably 2 × 10 ^-3~ 2 x 10^-2Amount of gram atom
It is desirable to be supported by.

The prepolymerization catalyst (C1-ii used in the present invention
i) can be prepared by introducing an olefin into an inert hydrocarbon solvent and performing prepolymerization in the presence of the above components (a) to (c). In addition, the above component (a)
The solid catalyst component (C1-ii) is preferably formed from the component (c). In this case, in addition to the component (C1-ii), the component (a) and / or the component (d) may be added.

Further, the prepolymerization catalyst (C2 used in the present invention
-iii) can be prepared by introducing an olefin into an inert hydrocarbon solvent and carrying out prepolymerization in the presence of the above component (a), component (b-III) and component (c). The solid catalyst component (C2-ii) is preferably formed from the above component (a), component (b-III) and component (c). In this case, in addition to the component (C2-ii), the component (a) and / or the component (d) may be added.

As the prepolymerization catalyst (C1-iii), an olefin may be introduced into a suspension in which the above-mentioned solid catalyst (C1-ii) (solid catalyst component) is prepared, or the solid catalyst (C1-ii) After preparing (solid catalyst component), the produced solid catalyst (C1-i
The i) (solid catalyst component) may be separated from the suspension, and then the solid catalyst (C1-ii) (solid catalyst component) may be suspended again with an inert hydrocarbon, and the olefin may be introduced therein.

In the prepolymerization, the above component (b) is
It is usually 10 ⁻⁶ to when converted to the transition metal atom in the component (b).
2 × 10 ^-2 mol / liter (solvent), preferably 5 × 1
Used in an amount of 0 ^-5 to 10 ^-2 mol / liter (solvent),
The component (b) is usually 5 × 10 ^{−6 to} 5 per 1 g of the component (c).
It is used in an amount of × 10 ^-4 mol, preferably 10 ^-5 to 2 × 10 ^-4 mol. Aluminum as component (a) and component (b)
The atomic ratio with the transition metal (Al / transition metal) is usually 1
It is 0 to 500, preferably 20 to 200. The aluminum atom (Al-
The atomic ratio (Al-d / Al-a) between the d) and the aluminum atom (Al-a) of the component (a) is usually 0.02 to 3, preferably 0.02.
It is in the range of 05 to 1.5.

The solid catalyst component is usually 10 ⁻⁶ to 2 × as a transition metal derived from the transition metal compound in the solid catalyst component.
10 ^-2 mol / liter (solvent), preferably 5 x 10 ^-5
Used in an amount of -10 ^-2 mol / liter (solvent).

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 10 ° C.
It is 0 hours, preferably about 1 to 50 hours.

As the olefin used in the prepolymerization, ethylene and α-olefin having 3 to 20 carbon atoms, such as 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.

The prepolymerization catalyst (C1-iii) is prepared, for example, as follows. That is, the carrier (component (c))
Are suspended in an inert hydrocarbon. Next, an organoaluminum oxy compound (component (a)) is added to this suspension, and the mixture is reacted for a predetermined time. The supernatant is then removed and the solid component obtained is resuspended with an inert hydrocarbon. Transition metal compounds (component (b) or component (b-II
After adding I)) and 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. Used in the present invention. The prepolymerization catalyst (C2-iii) can be prepared in the same manner as the above-mentioned prepolymerization catalyst (C1-iii) in the presence of the above solid catalyst (C2-ii) (solid catalyst component). .

In the prepolymerization, the olefin polymer produced 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 (c).
Is desirable. In addition, the prepolymerization catalyst (C1-i
ii) and the prepolymerization catalyst (C2-iii), the carrier (c) 1
The amount of component (b) (or component (b-III)) per g is about 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ gram atom as a transition metal atom. Carried by
The aluminum atom (Al) derived from the component (a) and the component (d) has a molar ratio (Al / M) to the transition metal atom (M) derived from the component (b) of 5 to 200, preferably 10. It is desirable that the amount is carried in the range of 150.

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,
Intrinsic viscosity [η] measured in decalin of at least 135 ° C. in the presence of hydrogen in the range of 0.2 to 7 dl / g,
It is desirable to produce a prepolymer such that it is preferably 0.5-5 dl / g.

The olefin multistage polymerization method according to the present invention comprises:
A step of producing an ethylene / α-olefin copolymer [A] by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of the above-mentioned olefin polymerization catalyst (C1) [I] ], And ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized in the presence of the above-mentioned olefin polymerization catalyst (C2) to produce an ethylene / α-olefin copolymer [B]. The process [II] is included.

The α having 3 to 20 carbon atoms used in the present invention
-Specifically as olefin, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Hexadecene, 1-octadecene, 1-eicosene and the like.

In the present invention, the copolymerization of ethylene and α-olefin is carried out in the gas phase or in the slurry liquid phase. 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 above olefin polymerization catalysts (C1 and C2) usually have a concentration of the transition metal atom in the polymerization reaction system of 10 ^-8 to It is desirable to use an amount of 10 ⁻³ gram atom / liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

Further, in the polymerization, in addition to the organoaluminum oxy compound (component (a)) supported on the carrier, an unsupported organoaluminum oxy compound may be used. In this case, an atom of an aluminum atom (Al) derived from the unsupported organoaluminum oxy compound and a transition metal atom (M) derived from the transition metal compound (b) (or transition metal compound (b-III)) The ratio (Al / M) is 5 to 300, preferably 10 to 2
00, 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 carried out under a pressurized condition of cm ² , preferably ² to 50 kg / cm ² . In the olefin multistage polymerization method of the present invention, an ethylene / α-olefin copolymer [A] is first produced in the presence of an olefin polymerization catalyst (C1) using a plurality of polymerization vessels connected in series, and then The ethylene / α-olefin copolymer [B] is copolymerized in the presence of the olefin polymerization catalyst (C2) in a polymerization reactor different from the polymerization reactor in which the copolymerization reaction is performed, or first, the olefin polymerization catalyst is used. The ethylene / α-olefin copolymer [B] is produced in the presence of (C2), and then in the presence of the olefin polymerization catalyst (C1) in a polymerization vessel different from the polymerization vessel in which the copolymerization reaction is performed. It can be produced by copolymerizing an ethylene / α-olefin copolymer [A]. In addition, a plurality of polymerization vessels are connected in parallel, the ethylene / α-olefin copolymer [A] and the ethylene / α-olefin copolymer [B] are copolymerized in each polymerization vessel, and then the ethylene / α-olefin copolymer is copolymerized. The polymer [A] and the ethylene / α-olefin copolymer [B] may be blended.

In the multi-stage olefin polymerization method of the present invention, when the ethylene / α-olefin copolymer [A] is produced by the slurry polymerization method, the polymerization temperature is usually -5.
In the range of 0 to 90 ° C., preferably 0 to 85 ° C., when producing by a gas phase polymerization method, the polymerization temperature is usually 0 to 100.
It can be obtained by copolymerization under the condition that the temperature is in the range of 20 ° C, preferably 20 to 90 ° C. When the ethylene / α-olefin copolymer [B] is produced by the slurry polymerization method, the polymerization temperature is usually −30 to 100 ° C., preferably 2
In the case of producing by a gas phase polymerization method in the range of 0 to 90 ° C., the polymerization temperature is usually 20 to 120 ° C., preferably 30 to 120 ° C.
It can be obtained by copolymerization under the conditions of 100 ° C.

[Ethylene / α-olefin copolymer [A]] In the multi-stage olefin polymerization method of the present invention, the ethylene / α-olefin copolymer [A] produced in the step [I] is composed of ethylene and carbon. It is a random copolymer with an α-olefin of several 3 to 20.

Ethylene / α-olefin copolymer [A]
Then, the structural unit derived from ethylene is 50 to 100.
%, Preferably 55-99% by weight, more preferably 65-98% by weight, most preferably 70-96% by weight, with 0 to 3 constituent units derived from the α-olefin having 3 to 20 carbon atoms. It is desirable to be present in an amount of -50 wt%, preferably 1-45 wt%, more preferably 2-35 wt%, most preferably 4-30 wt%.

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 ethylene / α-olefin copolymer [A] preferably has the following characteristics (A-i) to (A-vi). ) ~ (A-vi
It is more preferable to have the characteristics shown in ii).

(A-i) The density (d) is 0.850 to 0.9.
80 g / cm ³ , preferably 0.880 to 0.940 g /
cm ³ , more preferably 0.890 to 0.935 g / c
m ³ , most preferably in the range of 0.900 to 0.930 g / 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.

(A-ii) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.4 to 8 dl / g, preferably 1.25.
It is desirable to be in the range of ˜8 dl / g, more preferably 1.27 to 6 dl / g.

(A-iii) Melt tension (MT (g)) and melt flow rate (MFR) at 190 ° C. are MT> 2.2 × MFR ^−0.84, preferably 8.0 × MFR ^−0.84 >MT> 2 it is desirable to preferably from .3 × MFR ^-0.84 satisfy the relationship represented by ^{7.5 × MFR -0.84>MT> 2.5} × MFR -0.84.

Such an ethylene / α-olefin copolymer [A] has a large melt tension (MT) and good moldability. The melt tension (MT (g)) is determined by measuring the stress when the melted 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, and the resin temperature is set to 190 by using an MT measuring machine manufactured by Toyo Seiki Seisakusho.
C, extrusion speed 15 mm / min, winding speed 10-20
m / min, nozzle diameter 2.09 mmφ, nozzle length 8 mm. When pelletizing, 0.05% by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant was added to the ethylene / α-olefin copolymer [A] beforehand, and it was heat resistant and stable. N-octadecyl-as an agent
0.1% by weight of 3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate and 0.05% by weight of calcium stearate as a hydrochloric acid absorbent were added.

The melt flow rate (MFR) is AST
Measured under the conditions of 190 ° C. and 2.16 kg load according to M D1238-65T. (A-iv) The flow index (FI (1 / sec)) defined by the shear rate when the stress at 190 ° C. reaches 2.4 × 10 ⁶ dyne / cm ² and the melt flow rate (MFR) FI <150 × MFR, preferably FI <140 × MFR, and more preferably FI <130 × MFR.

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 preferably in the range of 1.5 to 4. The molecular weight distribution (Mw / Mn) is GPC manufactured by Millipore.
It measured using -150C as follows.

The separation column was TSK GNH HT, the column size was 72 mm in diameter and 600 mm in length, the column temperature was 140 ° C., the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
T (Takeda Yakuhin) 0.025% by weight was used, 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 <10
00 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 / MF
R and MT / (Mw / Mn)> 0.03 × FI / MFR-3.0 (provided that the value of 0.03 × FI / MFR-3.0 is 0 when it is less than 0). 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 effect 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.

(A-vii) Temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
(° C.)) and the density (d) are represented by Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, particularly 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 DSC-7 type device manufactured by Perkin Elmer was used.

(A-viii) When the n-decane soluble component amount fraction (W (wt%)) and the density (d) at room temperature 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 MFR> 10 g / 10 min W <80 × (MFR-9) ^0.26 × exp (−100 (d−
The relationship of 0.88)) + 0.1 is satisfied.

The amount of soluble component of n-decane (the smaller the soluble component, the narrower the composition distribution) was about 3% of the copolymer.
g to 450 ml of n-decane, dissolved at 145 ° C., cooled to room temperature, the n-decane-insoluble part is removed by filtration, and the n-decane-soluble part is recovered from the filtrate.

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

[Ethylene / α-olefin copolymer [B]] In the multi-stage polymerization method of olefin of the present invention, the ethylene / α-olefin copolymer [B] produced in the step [II] is composed of ethylene and carbon. It is a random copolymer with an α-olefin of several 3 to 20.

Ethylene / α-olefin copolymer [B]
Then, the structural unit derived from ethylene is 50 to 100.
%, Preferably 55-99% by weight, more preferably 65-98% by weight, most preferably 70-96% by weight, with 0 to 3 constituent units derived from the α-olefin having 3 to 20 carbon atoms. It is desirable to be present in an amount of -50 wt%, preferably 1-45 wt%, more preferably 2-35 wt%, most preferably 4-30 wt%.

The ethylene / α-olefin copolymer [B] has the following characteristics (B-i) to (B-iv). (B-i) Density (d) is 0.850 to 0.980 g / cm
³ , preferably 0.910 to 0.960 g / cm ³ , more preferably 0.915 to 0.955 g / cm ³ , and most preferably 0.920 to 0.950 g / cm ³ .

(B-ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.4-8 dl / g, preferably 0.4-
1.25 dl / g, more preferably 0.5-1.23 dl / g
It is desirable to be in the range of.

(B-iii) The temperature (Tm (° C.)) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC) and the density (d) are Tm <400 × d-250, preferably Tm. <450 × d-297 More preferably, Tm <500 × d-344, particularly preferably Tm <550 × d-391.

(B-iv) When the n-decane-soluble component amount fraction (W (% by weight)) and the density (d) at room temperature 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 MFR> 10 g / 10 min W <80 × (MFR-9) ^0.26 × exp (−100 (d−
The relationship of 0.88)) + 0.1 is satisfied.

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

[Ethylene Copolymer Composition] The ethylene copolymer composition produced by the multi-stage olefin polymerization method of the present invention comprises the ethylene / α-olefin copolymer [A] and ethylene / α. -Olefin copolymer [B], the ethylene / α-olefin copolymer [A] is contained in an amount of 20 to 90% by weight, preferably 40 to 75% by weight. Coalescence [B] is 1
It is desirable that it is contained in an amount of 0 to 80% by weight, preferably 25 to 60% by weight. (However, ethylene / α-olefin copolymer [A] and ethylene / α-olefin copolymer [B] are not the same)

Ethylene / α-olefin copolymer [A]
And [B] have a ratio ([A] / [B]) of the density of the ethylene / α-olefin copolymer [A] to the density of the ethylene / α-olefin copolymer [B] is preferably 1
Less, more preferably 0.930 to 0.999.

Such an ethylene copolymer composition is
It is preferable to have the following characteristics (i) to (vi). (I) density 0.850~0.980g / cm ^3, preferably 0.890~0.955g / cm ^3, more preferably it is preferably in the range of 0.900~0.950g / cm ^3.

(Ii) The melt flow rate (MFR) of the composition at 190 ° C. under a load of 2.16 kg is 0.1 to
It is desirable to be in the range of 100 g / 10 minutes, preferably 0.2 to 50 g / 10 minutes.

(Iii) It is desirable that the melt tension (MT (g)) and the melt flow rate (MFR) at 190 ° C. satisfy the relationship of MT ≧ 2.2 × MFR ^−0.84 .

(Iv) The stress at 190 ° C. is 2.4 × 1
The flow index (FI (1 / sec)) and the melt flow rate (MFR) defined by the shear rate when reaching 0 ⁶ dyne / cm ² are FI> 100 × MFR, and more preferably FI> 130 × MFR. Preferably satisfies the relationship represented by FI> 150 × MFR.

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

(Vi) When the n-decane-soluble component amount fraction (W (% by weight)) and the density (d) at room temperature 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 MFR> 10 g / 10 min W <80 × (MFR-9) ^0.26 × exp (−100 (d−
It is desirable that the relationship shown in 0.88)) + 0.1 is satisfied.

The ethylene copolymer composition obtained by the multi-stage olefin polymerization method according to the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, and an antifogging agent. Additives such as a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an antiaging agent, a hydrochloric acid absorbent, and an antioxidant may be added if necessary.

The ethylene-based copolymer composition obtained by the multi-stage olefin polymerization method according to the present invention is a conventional air-cooled inflation molding, air-cooled two-stage cooling inflation molding, high-speed inflation molding, T-die film molding, water-cooled inflation molding. A film can be obtained by processing such as molding. The film thus formed is excellent in transparency, mechanical strength and blocking resistance, and has the heat sealability, hot tack property, heat resistance and the like which are the features of ordinary LLDPE. Also,
Ethylene / α-olefin copolymers [A] and [B]
Since the composition distribution of is extremely narrow, there is no stickiness on the film surface. Further, since the melt tension is high, the bubble stability during inflation molding is excellent, the stress in the high shear region is low, and high-speed extrusion is possible, and the power consumption is low, which is economically advantageous.

The film obtained by processing the ethylene copolymer composition obtained by the multi-stage olefin polymerization method according to the present invention is a standard bag, a sugar bag, an oil packaging bag, an aquatic packaging bag, or the like. It is suitable for various 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.

[0141]

The ethylene-based copolymer composition obtained by the multi-stage olefin polymerization method according to the present invention comprises an ethylene / α-olefin copolymer [A] having specific physical properties,
Since it is formed from the ethylene / α-olefin copolymer [B], it is possible to produce a film having excellent heat stability and moldability, transparency, mechanical strength, and blocking resistance.

[0142]

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.

[0145]

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. did. 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 was added bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in toluene (Zr; 34.0 mmol / liter) in 7.4 liters and bis (1,3-dimethylcyclopentadienyl). ) 1.0 L of a zirconium dichloride toluene solution (Zr; 28.1 mmol / L) 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] 0.85 kg of the solid catalyst obtained above and 1-85 g of hexane containing 1.7 mol of triisobutylaluminum were added.
Hexene (255 g) was added and ethylene was prepolymerized at 35 ° C. for 12 hours to obtain a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst. The [η] of this ethylene polymer was 1.74 dl / g.

[Polymerization] Copolymerization of ethylene and 1-hexene was carried out using two continuous fluidized bed gas phase polymerization apparatuses connected in series. At the first stage, total pressure 18kg / cm ² −
G, under the conditions of a polymerization temperature of 75 ° C., the prepolymerized catalyst prepared above was converted into zirconium atom at 1.5 mmol / h,
Triisobutylaluminum was continuously supplied at a rate of 30 mmol / h, and ethylene, 1-hexene, hydrogen, and nitrogen were continuously supplied to maintain a constant gas composition during the polymerization (gas composition; 1- Hexene / Ethylene = 0.04
0, hydrogen / ethylene = 4.0 × 10 ⁻⁴ , ethylene concentration =
25%).

At the second stage, the total pressure is 16 kg / cm ²
Ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied under the conditions of -G and polymerization temperature of 75 ° C (gas composition; 1-hexene / ethylene = 0.020, hydrogen / ethylene = 16x).
10 ^-4 , ethylene concentration = 34%).

The residence time in the first stage is 3 hours,
The production rate of the copolymer was 60 kg / h. The copolymer thus obtained had an MFR of 0.5 g / 10 min, a density of 0.912 g / cm ³ and a decane-soluble portion at 23 ° C. of 0.55 wt%. On the other hand, the residence time in the second stage was 1.5 hours, and the production rate of the copolymer in the second stage polymerization vessel was 33 kg / h. The MFR of the obtained copolymer was 1.5 g / 10 minutes, the density was 0.922 g / cm ³ , and the decane-soluble portion at 23 ° C. was 0.51 wt%.

[Film Processing] Using the obtained ethylene / 1-hexene copolymer, a 25 mmφ die and a lip width of 0.7 m were obtained using a single screw extruder of 20 mmφ · L / D = 26.
m, using a single slit air ring, air flow rate = 90 liters / min., extrusion rate = 9 g / min., blow ratio =
1.8, take-up speed = 2.4 m / min., Processing temperature =
A film having a thickness of 30 μm was inflation-molded at 200 ° C.

Table 1 shows the melt properties and film properties. An inflation film having excellent moldability, optical properties and mechanical strength was obtained.

[0153]

[Comparative Example 1] Using one continuous fluidized bed gas phase polymerization apparatus,
Copolymerization of ethylene and 1-hexene was performed. The catalyst used was the same as that used in Example 1.

The MFR of the obtained copolymer was 1.5 g / 1.
It was 0 minutes and the density was 0.922 g / cm ³ . Example 1 using the obtained ethylene / 1-hexene copolymer
Inflation molding in the same manner as above, but with a thickness of 30 μm
Was formed into a film. Table 1 shows the melt properties and film properties.

As is clear from Table 1, the ethylene / 1-hexene copolymers obtained in Example 1 and Comparative Example 1 were
Despite the comparable MFR and density, the copolymer obtained according to Example 1 had a fluidity (F) in the high shear region.
In addition, the blown film has excellent film impact.

[0156]

Example 2 [Production of ethylene / α-olefin copolymer] [Preparation of catalyst component] The same procedure as in Example 1 was carried out except that the amount of zirconium compound used was changed to the following amount.

A solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in toluene (Z
r; 34.0 mmol / liter) 6.6 liters Toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr; 28.1 mmol / liter) 2.0 liters [Preparation of prepolymerization catalyst] A prepolymerized catalyst was obtained in the same manner as in Example 1 except that the catalyst component obtained in the above [Preparation of catalyst component] was used.

[Polymerization] An ethylene / 1-hexene 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 [Preparation of prepolymerized catalyst] was used. . The copolymer obtained had an MFR of 2.2 g / 10 min, a density of 0.923 g / cm ³ , and a decane-soluble portion at 23 ° C. of 0.46 wt%.

Using the obtained ethylene / 1-hexene copolymer, a film having a thickness of 30 μm was formed by inflation molding in the same manner as in Example 1. Table 1 shows the melt properties and film properties.

An inflation film having excellent moldability, optical properties and mechanical strength was obtained.

[0161]

Comparative Example 2 Using one continuous fluidized bed gas phase polymerization apparatus,
Copolymerization of ethylene and 1-hexene was performed. The same catalyst as that used in Example 2 was used.

The MFR of the obtained copolymer was 2.1 g / 1.
It was 0 minutes and the density was 0.923 g / cm ³ . A film having a thickness of 30 μm was formed by inflation molding using the obtained ethylene / 1-hexene copolymer in the same manner as in Example 1. Table 1 shows the melt properties and film properties.

As is clear from Table 1, the ethylene / 1-hexene copolymers obtained in Example 2 and Comparative Example 2 were
Despite the comparable MFR and density, the copolymer obtained according to Example 2 had a fluidity (F) in the high shear region.
In addition, the blown film has excellent film impact.

[0164]

Example 3 [Production of ethylene / α-olefin copolymer] [Preparation of catalyst component] The same procedure as in Example 1 was carried out except that the amount of the zirconium compound used was changed to the following amount.

A solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in toluene (Z
r; 34.0 mmol / liter) 5.6 liters Toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr; 28.1 mmol / liter) 2.9 liters [Preparation of prepolymerization catalyst] A prepolymerized catalyst was obtained in the same manner as in Example 1 except that the catalyst component obtained in the above [Preparation of catalyst component] was used.

[Polymerization] An ethylene / 1-hexene 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. . The copolymer obtained had an MFR of 1.2 g / 10 min, a density of 0.920 g / cm ³ , and a decane-soluble portion at 23 ° C. of 0.52 wt%.

Using the obtained ethylene / 1-hexene copolymer, a film having a thickness of 30 μm was formed by inflation molding in the same manner as in Example 1. Table 1 shows the melt properties and film properties.

An inflation film excellent in moldability, optical properties and mechanical strength was obtained.

[0169]

[Comparative Example 3] Using one continuous fluidized bed gas phase polymerization apparatus,
Copolymerization of ethylene and 1-hexene was performed. The same catalyst as that used in Example 3 was used. The MFR of the obtained copolymer was 1.2 g / 10 minutes and the density was 0.919 g / cm ³ . A film having a thickness of 30 μm was formed by inflation molding using the obtained ethylene / 1-hexene copolymer in the same manner as in Example 1. Table 1 shows the melt properties and film properties.

As is apparent from Table 1, the ethylene / 1-hexene copolymers obtained in Example 3 and Comparative Example 3 were
Despite the comparable MFR and density, the copolymer obtained according to Example 3 had a fluidity (F) in the high shear region.
In addition, the blown film has excellent film impact.

[0171]

[Table 1]

[0172]

[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.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Tohdo 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd. (56) Reference JP-A-60-35006 (JP, A) JP-A-3-234717 (JP, A) JP-A-6-207057 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (11)

(57) [Claims] 1. [I] (a) an organoaluminum oxy compound, (b-I) at least one selected from transition metal compounds represented by the following general formula [b-I], and ML ¹ _X ... [ b-I] (In the formula, 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 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 the transition metal compounds represented by the following general formula [b-II], ML ² _X ... [b-II] (M in the formula is IVB of the periodic table) Is a transition metal atom selected from the group, L ² is a ligand that coordinates to the transition metal atom, and at least two ligands L ² among these are coordinations selected from a methyl group and an ethyl group. A substituted cyclopentadienyl group having only 2 to 5 children, 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 an olefin polymerization catalyst (C1) containing 3 to 2 carbon atoms.
A step of producing an ethylene / α-olefin copolymer [A] by copolymerizing 0-α-olefin, and [II] a polymerization vessel different from the polymerization vessel in which the copolymerization reaction is carried out. Ethylene in the presence of an olefin polymerization catalyst (C2) containing an organoaluminum oxy compound and a transition metal compound of Group IV of the periodic table containing a ligand having a (b-III) cyclopentadienyl skeleton density of copolymerizing the alpha-olefin having 3 to 20 carbon atoms, and a step of producing ethylene · alpha-olefin copolymer [B], the ethylene · alpha-olefin copolymer [a]
And the ethylene / α-olefin copolymer [B]
Ratio with degree ([A] / [B]) is 0.930 to 0.999
Multistage polymerization of olefins, characterized in that it. 2. The olefin polymerization catalyst (C1) comprises the (a) organoaluminum oxy compound and the (b-
The multistage polymerization method of an olefin according to claim 1, which is a catalyst containing I) a transition metal compound and (d) an organoaluminum compound in addition to the (b-II) transition metal compound. 3. The olefin polymerization catalyst (C1),
(C) a carrier, the (a) organoaluminum oxy compound, the (b-I) transition metal compound, and the (b-II)
The multi-stage olefin polymerization method according to claim 1, wherein the transition metal compound is a supported solid catalyst. 4. The olefin polymerization catalyst (C1) comprises:
(C) a carrier, the (a) organoaluminum oxy compound, the (b-I) transition metal compound, and the (b-II)
A transition metal compound, a solid catalyst component supported,
The multi-stage olefin polymerization method according to claim 1, which is a catalyst comprising (d) an organoaluminum compound. 5. The olefin polymerization catalyst (C1) comprises:
(C) a carrier, the (a) organoaluminum oxy compound, the (b-I) transition metal compound, and the (b-II)
The multi-stage olefin polymerization method according to claim 1, wherein the transition metal compound is a prepolymerization catalyst in which an olefin is prepolymerized on a supported solid catalyst component. 6. The olefin polymerization catalyst (C1) comprises:
(C) a carrier, the (a) organoaluminum oxy compound, the (b-I) transition metal compound, and the (b-II)
A transition metal compound, a solid catalyst component supported, a prepolymerized catalyst component obtained by prepolymerizing an olefin,
The multi-stage olefin polymerization method according to claim 1, which is a catalyst comprising (d) an organoaluminum compound. 7. The olefin polymerization catalyst (C2) comprises the organoaluminum oxy compound (a) and the (b) organoaluminum oxy compound.
The multi-stage polymerization method for olefins according to claim 1, which is a catalyst containing (d) an organoaluminum compound in addition to -III) a transition metal compound. 8. The olefin polymerization catalyst (C2) comprises:
The multistage polymerization method of olefins according to any one of claims 1 to 6, wherein the (c) carrier is a solid catalyst in which the (a) organoaluminum oxy compound and the (b-III) transition metal compound are supported. 9. The olefin polymerization catalyst (C2) comprises:
A catalyst comprising (a) a solid catalyst component in which (a) an organoaluminum oxy compound and (b-III) a transition metal compound are supported on a carrier, and (d) an organoaluminum compound. Item 7. A multistage olefin polymerization method according to any one of items 1 to 6. 10. The olefin polymerization catalyst (C2) is
A prepolymerization catalyst obtained by prepolymerizing an olefin on a solid catalyst component in which the (a) organoaluminum oxy compound and the (b-III) transition metal compound are supported on a (c) carrier. The multistage polymerization method of the olefin as described in 1-6. 11. The olefin polymerization catalyst (C2) comprises:
A prepolymerization catalyst component obtained by prepolymerizing an olefin on a solid catalyst component in which the (a) organoaluminum oxy compound and the (b-III) transition metal compound are supported on a carrier (c), The multi-stage olefin polymerization method according to claim 1, which is a catalyst comprising d) an organoaluminum compound.