JPH06172434A - Catalyst for olefin polymerization and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst consisting of a specific transition metal compound, an organoaluminum compound and a contact product of a Mg compound and an electron donative substance, excellent in both of olefin polymerization activityt and economical efficiency and capable of producting an olefin polymer in high yield. CONSTITUTION:The objective catalyst consists of (A) a transition metal compound of the group IVB of the periodic table including a ligand having cyclopentadienyl skeleton [preferably bis(methylcyclopentadienyl)zirconium dichloride, etc.], (B) an organoaluminum compound (preferably >=4C trialkylaluminum, etc.) and (C) a contact product of a Mg compound and an electron donative substance (preferably magnesium chloride.2-ethylhexyl alcohol complex, etc.). Furthermore, the catalyst is preferably prepared by a method comprising bringing the component A into contact with the component B and then bringing the product into contact with the component C or bringing the component B into contact with C and then bringing the product into contact with the component A. The contact temperature is preferably 10-150 deg.C and the contact time is preferably 1sec to 1hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and an olefin polymerization method, and more particularly to a Ziegler type olefin polymerization catalyst containing no organoaluminumoxy compound and an olefin polymerization method using this catalyst. Is.

[0002]

BACKGROUND OF THE INVENTION A Ziegler type catalyst composed of a transition metal compound such as a zirconium compound and an organoaluminumoxy compound (aluminoxane) has been used as a catalyst for producing an olefin (co) polymer with high polymerization activity. Olefin polymerization catalysts are known, and a method for producing an ethylene / α-olefin copolymer using such a catalyst is disclosed, for example, in JP-A-58-19309.
JP-A-60-35005 and JP-A-60-35006
Japanese Patent Laid-Open No. 60-35007, Japanese Patent Laid-Open No. 60-3
It is proposed in Japanese Patent Publication No. 5008. In addition, JP-A-60
-260602 and JP-A-60-130604 disclose a method of polymerizing an olefin using a catalyst formed of a transition metal compound and a mixed organoaluminum compound of an aluminoxane and an organoaluminum compound. Proposed.

A catalyst comprising such a transition metal compound and an organoaluminum oxy compound can polymerize an olefin with high polymerization activity, but the organoaluminum oxy compound used here has a problem that it is expensive. Further, the organoaluminum oxy compound is usually produced by reacting an organoaluminum compound with water, but there is a problem that the production process is complicated.

For this reason, the advent of an olefin polymerization catalyst comprising a transition metal compound and an organometallic compound other than aluminoxane, which is excellent in olefin polymerization activity and is also economical, and an olefin polymerization method using this catalyst. Is desired.

As such an olefin polymerization catalyst, a catalyst composed of a transition metal compound, a Lewis acid, and an organic aluminum compound has been proposed in JP-A-3-179005.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is an olefin polymerization catalyst excellent in olefin polymerization activity and economically excellent, and an olefin polymerization method using this catalyst. Is intended to provide.

[0007]

SUMMARY OF THE INVENTION A first olefin polymerization catalyst according to the present invention is [A] a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton, and [B] an organoaluminum compound. , And [C] (C-1) magnesium compound, and (C-2) a contact product of an electron donor.

The second catalyst for olefin polymerization according to the present invention is [A] a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton, [B] an organoaluminum compound, and , [C ′] (C-1) magnesium compound, (C-2) electron donor, and (C-3) organometallic compound in contact with each other.

The olefin polymerization method according to the present invention is characterized by polymerizing an olefin in the presence of the above-mentioned first olefin polymerization catalyst or second olefin polymerization catalyst.

Such an olefin polymerization catalyst and an olefin polymerization method are excellent in olefin polymerization activity and economical.

[0011]

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 specification, 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.

First, each catalyst component used in the present invention will be specifically described. A transition metal compound of Group IVB of the periodic table containing a ligand having an [A] cyclopentadienyl skeleton used in the first and second olefin polymerization catalysts according to the present invention (hereinafter referred to as "component [A]"). Is a transition metal compound represented by the following formula [I].

ML _x [I] [wherein M is a transition metal selected from Group IVB of the periodic table, L is a ligand that coordinates to the transition metal, and at least one L is cyclo). L is a ligand having a pentadienyl 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, an SO ₃ R 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 transition It is the valence of the metal. In the above general formula [I], M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, and preferably zirconium.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group and 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 halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula [I] contains two or more groups having a cyclopentadienyl skeleton, the groups having two cyclopentadienyl skeletons are alkylene such as ethylene and propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group, and the like.

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. The metallocene compound containing a ligand having such a cyclopentadienyl skeleton is more specifically represented by the following general formula [I ′] when the valence of the transition metal is 4, for example.

R ¹ _k R ² _l R ³ _m R ⁴ _n M ... [I '] (In the formula, M is a transition metal similar to the above general formula [I], and R ¹ is a cyclopentadienyl skeleton. R ² , R ³ and R ⁴ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups. Group, SO ₃ R group, halogen atom or hydrogen atom, k is an integer of 1 or more, and k +
1 + m + n = 4. In the present invention, in the above general formula, a metallocene compound in which at least two of R ¹ , R ² , R ³ and R ⁴ , that is, R ¹ and R ² are groups (ligands) having a cyclopentadienyl skeleton, It is preferably used. Groups having these cyclopentadienyl skeletons are alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene,
They may be bonded via a silylene group or a substituted silylene group such as dimethylsilylene, diphenylsilylene and methylphenylsilylene group. R ³ and R ⁴ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, SO ₃
R, a halogen atom or a hydrogen atom.

Specific examples of transition metal compounds in which M is zirconium will be 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, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (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)
Methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium 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 (trifluoromethanesulfonato), 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 examples, 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.

It is also possible to use a compound in which zirconium is replaced with titanium or hafnium in the zirconium compound as described above. Next, the [B] organoaluminum compound will be described.

Examples of the [B] organoaluminum compound (hereinafter sometimes referred to as “component [B]”) used in the first and second olefin polymerization catalysts according to the present invention include, for example, the following general formula: II] can be exemplified.

R ¹ _n AlX _3-n ... [II] (wherein R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, and X is
Is a halogen atom or a hydrogen atom, and n is 1 to 3. ) In the above general formula [II], R ¹ has 1 to 1 carbon atoms.
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

As the above [B] organoaluminum compound, the following compounds are specifically used. 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.

Among the organoaluminum compounds represented by the above general formula [II], trialkylaluminum is preferable, and trialkylaluminum having 4 or more carbon atoms is most preferable.

As the organoaluminum compound [B], a compound represented by the following general formula [III] can also be used. R ¹ _n AlY _3-n ... [III] (In the formula, R ¹ is the same as the above general formula [II], and Y is −
OR ² group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR
⁵ ₂ group, a -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 and the like, R ⁵ is a hydrogen atom,
A methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group and the like, and R ⁶ and R ⁷ are a methyl group, an 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 , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum 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 (OSiMe ₃ ),
(iso-Bu) ₂ Al (OSiEt ₃ ), etc .; (3) Compounds represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso- Bu)
_{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 , _{^{etc.; (5) R 1 n Al}} (SiR 6 3) a compound represented by _3-n, e.g.
(iso-Bu) ₂ AlSiMe _{3 and the} like; (6) a compound represented by R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n , for example, 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 formula [III], the general formulas R ¹ _n Al (OR ² ) _3-n and R ¹
A compound represented by _n Al (OA1R ⁴ ₂ ) _3-n is preferable, and a compound in which R is an isoalkyl group and n = 2 is particularly preferable.

The first olefin polymerization catalyst according to the present invention comprises the above-mentioned [A] transition metal compound (catalyst component),
[B] A catalyst component [C] comprising an organoaluminum compound (catalyst component) and a contact product of a (C-1) magnesium compound and (C-2) electron donor as described below (hereinafter referred to as "component [C]"). It may be described as "."). The second olefin polymerization catalyst according to the present invention is a [A] transition metal compound (catalyst component) as described above,
[B] An organoaluminum compound (catalyst component), and a catalyst component comprising a contact product of a (C-1) magnesium compound, a (C-2) electron donor, and a (C-3) organometallic compound as described below [ C ′] (hereinafter sometimes referred to as “component [C ′]”).

As the (C-1) magnesium compound constituting the component [C] used in the first olefin polymerization catalyst and the component [C '] used in the second olefin polymerization catalyst according to the present invention, , Magnesium compounds having reducing ability and magnesium compounds having no reducing ability.

Examples of the magnesium compound having reducing ability include organomagnesium compounds represented by the following formula. During X _n MgR _2-n formulas, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group, X is a halogen. n is 0 ≦ n <2, and when n is 0, 2
The R's may be the same or different.

Specific examples of the organomagnesium compound having such reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
Dialkyl magnesium compounds such as dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium and ethyl butyl magnesium, alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride and amyl magnesium chloride Examples thereof include alkyl magnesium alkoxides such as halides, butyl ethoxy magnesium, ethyl butoxy magnesium, and octyl butoxy magnesium, and butyl magnesium hydride.

Specific examples of the magnesium compound having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, magnesium methoxy chloride, ethoxy magnesium chloride, isopropoxy. Alkoxy magnesium halides such as magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, phenoxy magnesium chloride, allyloxy magnesium halides such as methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethyl Alkoxy magnesium such as hexoxy magnesium, phenoxy magnesium, dimethyl phenoxy magnesium, etc. Examples include magnesium carboxylates such as allyloxy magnesium, magnesium laurate, and magnesium stearate. In addition, magnesium metal and magnesium hydride can also be used.

The magnesium compound having no reducing ability may be a compound derived from the above-mentioned magnesium compound having reducing ability or a compound derived at the time of preparation of the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is used as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen. It may be brought into contact with a containing compound or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compound having a reducing ability and the magnesium compound having no reducing ability are the (C-3) organometallic compounds described later, for example, other metals such as aluminum, zinc, boron, beryllium, sodium and potassium. It may form a complex compound or a complex compound with, or may be a mixture with another metal compound. Further, the magnesium compound may be used alone, or two or more kinds of the above compounds may be combined, and may be used in a liquid state or a solid state.

Among these magnesium compounds, magnesium halide is preferable, and magnesium chloride is particularly preferable. Further, the magnesium compound having no reducing ability may be derived from another substance.

As an electron donor (C-2) constituting the component [C] used in the first olefin polymerization catalyst and the component [C '] used in the second olefin polymerization catalyst according to the present invention. Includes alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, diethers, acid amides, acid anhydrides, alkoxysilanes, etc. Oxygen-containing electron donors; ammonia, amines,
Nitrogen-containing electron donors such as nitriles, pyridines and isocyanates can be mentioned.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, and halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; phenol, cresol, xylenol, ethylphenol , Propylphenol,
C6 to C20 phenols which may have a lower alkyl group such as nonylphenol, cumylphenol and naphthol; C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone Acetaldehyde, propionaldehyde, octylaldehyde,
Aldehydes having 2 to 15 carbon atoms such as benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate,
Carbon number 2 to 1 such as ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarinphthalide, ethyl carbonate
Organic acid esters of 8; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, C2-C20 ethers such as diphenyl ether; acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide; trimethylamine, triethylamine, tributylamine, Amines such as Ribenzylamine and Tetramethylethylenediamine; Nitriles such as Acetonitrile, Benzonitrile and Trinitrile; Pyridines such as Pyridine, Methylpyridine, Ethylpyridine, Dimethylpyridine; Acetic anhydride, Anhydrous Tal acid, and the like can be exemplified acid anhydride such as benzoic anhydride.

As the organic acid ester, polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a preferred example.

[0041]

[Chemical 1]

(Wherein R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted or It is an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴
And may be connected to each other to form a ring structure.
When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent is
Containing a heteroatom such as N, O, S, for example, C—O—C,
_{COOR, COOH, OH, SO 3} H, -C-N-C
It has a group such as-, NH ₂ . ) Specific examples of such polycarboxylic acid ester include aliphatic polycarboxylic acid ester, alicyclic polycarboxylic acid ester, aromatic polycarboxylic acid ester, and heterocyclic polycarboxylic acid ester. To be

Preferred specific examples are n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-phthalate. Butyl, di-2-phthalate
Examples thereof include ethylhexyl and dibutyl 3,4-furandicarboxylate.

Examples of particularly preferable polycarboxylic acid esters include phthalic acid esters. Further, examples of the polyether compound include compounds represented by the following general formula.

[0045]

[Chemical 2]

(Where n is an integer of 2 ≦ n ≦ 10,
R ^{1 to} R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any R ^{1 to} R ²⁶ ,
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ) As preferred specific examples, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1,3-dimethoxypropane etc. can be illustrated.

Two or more kinds of the above-mentioned (C-2) electron donors can be used in combination. The component [C ′] used in the second olefin polymerization catalyst according to the present invention is constituted (C-
3) Examples of the organometallic compound include [B] organoaluminum compounds as described above, complex alkyl compounds of Group I metal and aluminum, organometallic compounds of Group II metal, and the like.

Examples of complex alkylated products of Group I metals and aluminum include compounds represented by the following general formula. M ¹ AlR ^j ₄ (wherein M ¹ is Li, Na, K, and R ^j is 1 to 1 carbon atoms.
Specifically, LiAl (C ₂ H ₅ ).
₄ , LiAl (C ₇ H ₁₅ ) _{4 and the} like.

Examples of the organometallic compound of Group II metal include compounds represented by the following general formula. R ^k R ^l M ² (wherein R ^k is a hydrocarbon group having 1 to 15 carbon atoms or halogen, R ^l is a hydrocarbon group having 1 to 15 carbon atoms. M ² is Mg, Zn or Cd Specific examples include diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, butylmagnesium chloride and the like.

These organometallic compounds may be used alone or in combination of two or more. The component [C] used in the first olefin polymerization catalyst according to the present invention is a contact product of the above-mentioned (C-1) magnesium compound and (C-2) electron donor. Such components [C] include (C-1) magnesium compound and (C-2)
Complexes consisting of electron donors are preferred. Among these,
Complexes of alcohols, carboxylic acids or amines are preferred. Specific examples include magnesium chloride / 2-ethylhexyl alcohol complex, magnesium chloride / ethanol complex, and the like.

The component [C '] used in the second olefin polymerization catalyst according to the present invention is (C-1) a magnesium compound, (C-2) an electron donor, and (C-3) an organometallic compound. It is a contact object. As such a component [C ′], specifically, a contact product of a complex composed of (C-1) a magnesium compound and (C-2) an electron donor, and (C-3) an organometallic compound, or ( Examples include a contact product of C-1) a magnesium compound, (C-2) an electron donor, and (C-3) an organometallic compound.

Contact of a complex composed of (C-1) magnesium compound and (C-2) electron donor with (C-3) organometallic compound, or (C-1) magnesium compound, (C-2) ) The contact between the electron donor and the (C-3) organometallic compound can be carried out in an organic solvent.

When the complex consisting of the (C-1) magnesium compound and the (C-2) electron donor is brought into contact with the (C-3) organometallic compound, the (C-1) magnesium compound and the (C-1) -2) It is preferable to bring the (C-3) organometallic compound into contact with the complex consisting of the electron donor in an amount of 0.1 to 1000 times by mole. The contact temperature at the time of contact is -70 to 200.
C., preferably 10 to 150.degree. C., and the contact time is 0.1 second to 10 hours, preferably 1 second to 1 hour.

The first olefin polymerization catalyst according to the present invention comprises the above-mentioned [A] transition metal compound (catalyst component),
It is formed by bringing [B] an organoaluminum compound (catalyst component) and component [C] into contact with each other. The contact of the component [A], the component [B] and the component [C] can be carried out inside the polymerization system or outside the polymerization system.

Component [A], component [B] and component [C]
When contacting, the component [A] and the component [B] are first contacted, and then the component [C] is contacted, or the component [B] and the component [C] are contacted first, and then It is preferable to contact the component [A].

The contact temperature for contacting the catalyst component [A], the component [B] and the component [C] is -80 to 200.
C., preferably 10 to 150.degree. C., and the contact time is 0.1 second to 10 hours, preferably 1 second to 1 hour.

The second olefin polymerization catalyst according to the present invention comprises the above-mentioned [A] transition metal compound (catalyst component),
It is formed by bringing the [B] organoaluminum compound (catalyst component) and the component [C ′] into contact with each other. The contact of the component [A], the component [B] and the component [C ′] can be performed inside or outside the polymerization system.

The order of contacting the component [A], the component [B] and the component [C '] is arbitrary, but the component [A] and the component [B] are contacted first, and then the component [C]. It is preferable that the component [B] and the component [C ′] are contacted first, and then the component [A] is contacted. Of these, it is particularly preferable to contact the component [A] and the component [B] first, and then contact the component [C ′].

The contact temperature for contacting the catalyst component [A], the component [B] and the component [C '] is -80 to 200.
C., preferably 10 to 150.degree. C., and the contact time is 0.1 second to 10 hours, preferably 1 second to 1 hour.

The olefin polymerization catalyst of the present invention may contain other components useful for olefin polymerization in addition to the above components. Such first and second olefin polymerization catalysts according to the present invention can polymerize olefins with excellent polymerization activity.

In the olefin polymerization method according to the present invention, the olefin is polymerized in the presence of the above olefin polymerization catalyst. Examples of the olefin used in the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, and specific examples of the α-olefin having 3 to 20 carbon atoms include 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 can be mentioned.

Further, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4
It is also possible to use a, 5,8,8a-octahydronaphthalene, styrene, vinylcyclohexane, dienes and the like.

In the polymerization, the component [A] is the same as the component [A].
Converted to the transition metal atom therein, usually 0.0001 to 10.0 mmol, preferably 0.0 per liter of polymerization volume.
Used in an amount of 01-5.0 mmol.

The component [B] is usually 0.0 per 1 liter of polymerization volume in terms of aluminum atom in the component [B].
It is used in an amount of 08 to 800 mmol, preferably 0.08 to 80 mmol.

Component [C] and component [C '] are usually 0.0001 to 1000 mmol per 1 liter of polymerization volume in terms of magnesium atom in component [C] or magnesium atom in component [C']. , Preferably 0.0
Used in an amount of 01-100 mmol.

In the polymerization, the component [B] is usually a gram atomic ratio (Al / M) of the aluminum atom (Al) in the component [B] and the transition metal (M) in the component [A], and is usually It is used in an amount of 1-10000, preferably 1-1000.

The component [C] and the component [C ′] are the same as the magnesium atom (M) in the component [C] or the component [C ′].
The gram atomic ratio (Mg / M) between g) and the transition metal (M) in the component [A] is usually 0.5 to 1000, preferably 1
Used in an amount of -100.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.
When the polymerization is carried out by a liquid phase polymerization method, as a polymerization solvent, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; cyclopentane, cyclohexane, methylcyclopentane Alicyclic hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These may be used alone or in combination. Also, the olefin itself can be used as a solvent.

The olefin polymerization temperature is usually from -50 to
It is in the range of 150 ° C, preferably 0 to 100 ° C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably under conditions of normal pressure to 50 kg / cm ^2.

The polymerization can be carried out by any of batch, semi-continuous and continuous methods. Further, the polymerization can be carried out in two or more stages under different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.

In the olefin polymerization catalyst according to the present invention, an olefin may be prepolymerized in the above-mentioned component [A], component [B] and component [C]. Olefin may be prepolymerized to [B] and component [C ′].

[0072]

The olefin polymerization catalyst according to the present invention is
Olefin can be polymerized with excellent polymerization activity without using an organoaluminum oxy compound. Further, it is inexpensive because it does not use an expensive organoaluminum oxy compound.

In the olefin polymerization method according to the present invention, the olefin is polymerized in the presence of such an olefin polymerization catalyst, so that the olefin polymer can be produced in high yield.

[0074]

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.

[0075]

Example 1 [Preparation of component C1] 95.2 g of anhydrous magnesium chloride,
Decane 442 ml and 2-ethylhexyl alcohol 3
90.6 g was reacted at 130 ° C. for 2 hours to obtain a uniform solution.

[Polymerization] In a glass-made polymerization vessel substituted with nitrogen,
1000 ml of toluene was added, the mixture was heated to 75 ° C., and ethylene was introduced. Charge triisobutylaluminum (0.4 mmol in terms of aluminum atoms) and component C1 (0.05 mmol in terms of magnesium atoms) to the polymerization vessel, and after 2 minutes, ethylenebis (indenyl) zirconium dichloride. (0.005 mmol in terms of zirconium atom) was added to initiate polymerization. Three
After polymerization for 0 minutes, a small amount of isobutyl alcohol was added to stop the polymerization. The reaction product was poured into a large amount of methanol to precipitate the whole amount of polymer, hydrochloric acid was added, and the polymer was collected by filtration with a glass filter. The obtained polymer was vacuum dried for 10 hours to obtain 9.75 g of polyethylene.

The intrinsic viscosity (hereinafter abbreviated as “[η]”) of this polyethylene, which was determined in decalin at 135 ° C., was 1.
It was 66 dl / g.

[0078]

Example 2 Example 1 was repeated except that the catalyst components were added to the polymerization vessel in the order of triisobutylaluminum, ethylenebis (indenyl) zirconium dichloride, and after 2 minutes, the component C1. Polymerization was performed in the same manner to obtain 1.48 g of polyethylene. The [η] of this polyethylene was 1.69 dl / g.

[0079]

Comparative Example 1 As in Example 1, except that the catalyst components were added to the polymerization vessel in the order of component C1, ethylenebis (indenyl) zirconium dichloride, and triisobutylaluminum after 2 minutes. Polymerization was performed in the same manner to obtain 0.93 g of polyethylene.

[0080]

Example 3 [Preparation of Component C2 Solution] Triisobutylaluminum (92.4) was added to a toluene solution of magnesium chloride-3-ethylhexyl alcohol complex (26.4 mmol) with stirring.
Toluene solution of (mmol) was added dropwise to prepare a component C2 solution.

[Polymerization] In a nitrogen-substituted glass polymerization vessel,
1000 ml of toluene was added, the mixture was heated to 75 ° C., and ethylene was introduced. Triisobutylaluminum (0.4 mmol in terms of aluminum atoms) and a component C2 solution (0.5 mmol in terms of magnesium atoms) were added to the polymerization vessel, and after 2 minutes, ethylenebis (indenyl) zirconium dichloride. (0.005 mmol in terms of zirconium atom) was added to initiate polymerization. 6
After polymerization for 0 minutes, a small amount of isobutyl alcohol was added to stop the polymerization, and the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer. Then, hydrochloric acid was added and the mixture was filtered through a glass filter. The obtained polymer was vacuum dried for 10 hours to obtain 11.30 g of polyethylene. The [η] of this polyethylene was 1.91.

[0082]

Example 4 Polymerization was carried out in the same manner as in Example 3 except that the component C2 solution was used in an amount of 0.05 mmol converted to magnesium atoms to obtain 42.30 g of polyethylene. . [Η] of this polyethylene is 2.3
It was 4 dl / g.

[0083]

Example 5 Polymerization was carried out in the same manner as in Example 3 except that the component C2 solution was used in an amount of 0.015 mmol converted to magnesium atoms to obtain 48.25 g of polyethylene. . The [η] of this polyethylene is 2.
It was 40 dl / g.

[0084]

Example 6 Polyethylene 4 was polymerized in the same manner as in Example 3 except that tridecylaluminum was used in place of triisobutylaluminum.
3.20 g was obtained. [Η] of this polyethylene is 2.4
It was 6 dl / g.

[0085]

Example 7 [Preparation of Al Removing Component C3 Solution] A glass reactor was equipped with a cooling tube, a dropping funnel and a stirring rod, and purged with nitrogen. Toluene and MgCl ₂ · 2.61 under nitrogen atmosphere
C ₂ H ₅ OH (25 mmol) was added, and triisobutylaluminum (75 mmol) was slowly added dropwise while stirring. Then, the temperature of the oil bath was raised to 80 ° C. and the reaction was carried out for 1 hour. After completion of the reaction, solids were collected by filtration with a glass filter in a nitrogen atmosphere, washed with toluene, and then a suspension of toluene was used as an Al-removing component C3 liquid.

[Polymerization] Example 3 except that the Al removing component C3 liquid (0.05 mmol in terms of magnesium atom) was used in place of the component C2 solution in Example 3.
Polymerization was carried out in the same manner as above to obtain 10.2 g of polyethylene.

[0087]

Example 8 Example 7 was repeated except that the catalyst components were added to the polymerization vessel in the order of triisobutylaluminum, ethylenebis (indenyl) zirconium dichloride, and after 2 minutes, the Al removing component C3 liquid. Polymerization was performed in the same manner as in 7 to obtain 5.63 g of polyethylene.

[0088]

[Example 9] Polymerization was performed in the same manner as in Example 7 except that the Al-removing component C3 solution was used in an amount of 0.4 mmol calculated as magnesium atoms to obtain 4.75 g of polyethylene. It was

[0089]

Example 10 Polymerization was carried out in the same manner as in Example 7 except that 0.015 mmol of the Al-removing component C3 solution was used in terms of magnesium atoms, and 11.0 g of polyethylene was obtained.

[Brief description of drawings]

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

Claims (4)

[Claims] 1. A transition metal compound of Group IVB of the periodic table containing a ligand having an [A] cyclopentadienyl skeleton, an organoaluminum compound [B], and a magnesium compound [C] (C-1). And (C-2) a contact material with an electron donor, and a catalyst for olefin polymerization. 2. A transition metal compound of Group IVB of the periodic table containing [A] a ligand having a cyclopentadienyl skeleton, [B] an organoaluminum compound, and [C ′] (C-1) magnesium. An olefin polymerization catalyst comprising a compound, (C-2) an electron donor, and (C-3) a contact product of an organometallic compound. 3. A transition metal compound of group IVB of the periodic table containing a ligand having an [A] cyclopentadienyl skeleton, an organoaluminum compound [B], and a magnesium compound [C] (C-1). And (C-2) a contact material with an electron donor, and a olefin polymerization method comprising polymerizing an olefin in the presence of an olefin polymerization catalyst. 4. A transition metal compound of group IVB of the periodic table containing a ligand having an [A] cyclopentadienyl skeleton, an organoaluminum compound [B], and [C ′] (C-1) magnesium. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of an olefin polymerization catalyst comprising a compound, (C-2) an electron donor and (C-3) a contact product of an organometallic compound.