JPH10298216A - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst which has excellent olefin polymerization activity and gives a high-molecular-weight polymer by using as the constituents a specified transition metal amide compound and compound(s) selected from an organometal compound, an organoaluminum oxy compound and a compound that reacts with a transition metal amide compound to form an ion pair. SOLUTION: The transition metal amide compound used is represented by the formula [wherein M is an atom of any one of groups 3 to 6 transition metals; R<1> to R<10> are each H, halogeno, a (halogenated) hydrocarbon group, organosilyl, alkoxy, aryloxy, etc., provided that at least one of R<1> to R<5> and R<6> to R<10> respectively is a group other than H; m is 0 to 2; n is 4 or 5; A is an atom of any one of groups 13 to 16 elements; E is a substituent having at least one atom selected from C, H, O, a halogen atom, N, S, P, B and Si; p is 0 to 4; and X is H, a halogen atom, a 1-20C (halogenated) hydrocarbon group, an O-containing group, an S-containing group, or an Si-containing group]. Examples of at least one compound selected include trimethylaluminum, aluminoxane and trifluoroborane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst for olefin polymerization.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Olefin polymerization catalysts include:
So-called Kaminsky catalysts are well known. This catalyst is characterized by a very high polymerization activity and a polymer having a narrow molecular weight distribution.

As a transition metal compound used for such a Kaminsky catalyst, for example, bis (cyclopentadienyl) zirconium dichloride (JP-A-58-19)
309) and ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (Japanese Unexamined Patent Publication No.
No. 130314). It is also known that when the transition metal compound used for the polymerization is different, the olefin polymerization activity and the properties of the obtained polyolefin are greatly different.

Further, as a new catalyst for olefin polymerization, for example, Japanese Patent Application Laid-Open No. 8-245713 has proposed an olefin polymerization catalyst comprising a titanium amide compound having a titanium-nitrogen bond and aluminoxane.

Also, Organometallics 1996, 15,562-569
Describes an organometallic complex of Group 4 of the periodic table having a bis (borylamide) ligand represented by [Mes ₂ BNCH ₂ CH ₂ NBMes ₂ ] ^-2 , and this complex shows a slight ethylene polymerization activity. Is described.

[0006] Polyolefins are generally used in various fields such as for molded articles because of their excellent mechanical properties. However, in recent years, the demand for physical properties of polyolefins has been diversified, and polyolefins having various properties have been developed. Is desired. It is also desired to improve productivity.
Under these circumstances, there has been a demand for an olefin polymerization catalyst and an olefin polymerization method capable of producing a polyolefin having excellent olefin polymerization activity and excellent properties.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an olefin polymerization catalyst having excellent olefin polymerization activity and a method for polymerizing olefins using the catalyst.

[0008]

The catalyst for olefin polymerization according to the present invention comprises (A) a transition metal amide compound represented by the following general formula (I), (B) an organometallic compound (B-1), and (B-2) It is characterized by comprising an organic aluminum oxy compound and (B-3) at least one compound selected from compounds which react with the transition metal amide compound (A) to form an ion pair.

[0009]

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(Wherein M represents a transition metal atom belonging to Groups 3 to 6 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen atom, hydrocarbon group, an organic silyl group, an alkoxy group, an aryloxy ^{group, -COOR 11, -N (R 12} ) C (O)
^{R 13, -OC (O) R} 14, -CN, -NR 15 2 , or -
^{N (R 16) S (O} 2) R 17 ( provided that, R ¹¹ to R ¹⁷ in. Of an alkyl group having 1 to 5 carbon atoms) indicates, R ¹ ~
At least one of R ⁵ is a group other than a hydrogen atom,
And at least one of R ^{6 to} R ¹⁰ is a group other than a hydrogen atom, and two or more of the groups represented by R ^{1 to} R ⁵ may be linked to each other to form a ring. Well, R ⁶
Two or more groups among the groups represented by to R ¹⁰ are linked to each other may form a ring, m is an integer of 0 to 2, n is 4 or 5, A May be the same or different from each other, and represent an atom of Groups 13 to 16 of the periodic table, and E is carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
A substituent having at least one element selected from phosphorus, boron and silicon; and when a plurality of Es are present, the plurality of Es may be the same or different from each other;
May be linked to each other to form a ring, p represents an integer of 0 to 4, X represents a hydrogen atom, a halogen atom, a carbon atom having 1 to 20 carbon atoms. Hydrogen group,
Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group, and when p is 2 or more, a plurality of groups represented by X may be the same or different. Is also good. The method for polymerizing an olefin according to the present invention is characterized in that the olefin is polymerized in the presence of the catalyst as described above.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the catalyst for olefin polymerization according to the present invention and a method for polymerizing olefins using the catalyst will be described in detail.

The catalyst for olefin polymerization according to the present invention comprises (A) a transition metal amide compound represented by the following general formula (I), (B) (B-1) an organometallic compound, and (B-2) an organic metal compound. It is formed from an aluminum oxy compound and (B-3) at least one compound selected from compounds which react with the transition metal amide compound (A) to form an ion pair.

First, each component forming the olefin polymerization catalyst of the present invention will be described. (A) Transition metal amide compound The (A) transition metal amide compound used in the present invention is a compound represented by the following general formula (I).

[0014]

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In the formula, M represents a transition metal atom belonging to Groups 3 to 6 of the periodic table, and is preferably a transition metal atom belonging to Group 4 of the periodic table such as titanium, zirconium, or hafnium, and titanium is particularly preferred.

R ^{1 to} R ¹⁰ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group, an alkoxy group, an aryloxy group, —COOR ¹¹ , N (R ¹² ) C (O)
^{R 13, -OC (O) R} 14, -CN, -NR 15 2 , or -
N (R ¹⁶ ) S (O ₂ ) R ¹⁷ is shown. However, R ^{1 to} R ⁵
At least one is a group other than hydrogen and R ⁶
At least one of R ¹⁰ is a group other than hydrogen.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. As the hydrocarbon group, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and other straight or branched carbon atoms having 1 to 20 carbon atoms. Alkyl groups; aryl groups having 6 to 20 carbon atoms such as phenyl, naphthyl and anthryl; and 1 to 5 substituents such as the alkyl groups having 1 to 20 carbon atoms are substituted on these aryl groups. A substituted aryl group; a cycloalkyl group such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; an alkenyl group such as vinyl, propenyl and cyclohexenyl; an arylalkyl group such as benzyl, phenylethyl, and phenylpropyl.

Examples of the halogenated hydrocarbon group include groups in which the above hydrocarbon group is substituted with halogen. Specific examples of the organic silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, phenylsilyl, diphenylsilyl, triphenylsilyl, dimethylphenylsilyl,
Methyldiphenylsilyl and the like.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Specifically as the aryloxy group, phenoxy, 2,
6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like.

-COOR ¹¹ , -N (R ¹² ) C (O)
^{R 13, -OC (O) R} 14, -CN, -NR 15 2 , or -
Examples of the group represented by N (R ¹⁶ ) S (O ₂ ) R ¹⁷ (where R ^{11 to} R ¹⁷ represent an alkyl group having 1 to 5 carbon atoms) include —COOCH ₃ and —N (CH ₃ ) C (O) CH
_{3, -OC (O) CH 3} , -CN, -N (C
_{2 H 5) 2, -N (} CH 3) S (O 2) such as CH ₃ and the like.

Further, two or more of the groups represented by R ^{1 to} R ⁵ , preferably adjacent groups are connected to each other to form a ring such as an aromatic ring or an aliphatic ring together with the carbon atom to which each is bonded. Two or more of the groups represented by R ^{6 to} R ¹⁰ , preferably an aromatic ring, an aliphatic ring, etc. May form a ring.

M is an integer of 0 to 2. n is 4 or 5. A may be the same or different from each other, and represents an atom belonging to Groups 13 to 16 of the periodic table, and specifically includes a boron atom, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, and a germanium Examples include an atom, a selenium atom, and a tin atom, and a carbon atom or a silicon atom is preferable.

E is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and is preferably selected from carbon, hydrogen, nitrogen and silicon. At least one
Substituents containing species of elements. Also indicated by E
Two or more groups may be connected to each other to form a ring.

Specific examples of such a group for bonding two nitrogen atoms include the following divalent bonding groups.

[0025]

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[0026]

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In the above examples, Me represents a methyl group, and tBu represents a tert-butyl group. p is an integer of 0 to 4.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a silicon-containing group. When p is 2 or more, a plurality of groups represented by X may be the same or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and an aryl group. More specifically, methyl, ethyl, propyl, butyl, and hexyl Alkyl groups such as octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
And aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; and an arylalkoxy group such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include a substituent in which the oxygen of the above-mentioned oxygen-containing group is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. Sulfonate groups such as benzoate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p -Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl and triphenylsilyl. Trialkyl-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon such as trimethylsilylphenyl And a substituted aryl group.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferred. Hereinafter, specific examples of the transition metal amide compound represented by the general formula (I) will be shown, but the invention is not limited thereto.

[0034]

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[0035]

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In the above examples, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, and tBu represents a tert-butyl group. In the present invention, a transition metal amide compound in which titanium is replaced with zirconium or hafnium in the above-described compounds can also be used.

These compounds may be used alone,
Two or more kinds may be used in combination. (B-1) Organometallic compound As the (B-1) organometallic compound used in the present invention, specifically, the following Periodic Table Groups 1 and 2 and Groups 12 and 1
A group 3 organometallic compound is used.

[0038] (B-1a) formula _{^{R a m Al (OR b)}} n H
_p X _q (wherein, R ^a and R ^b may be the same or different and each have 1 to 15 carbon atoms, preferably 1
And X represents a halogen atom;
Is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0039] (B-1b) Formula M ² AlR ^a ₄ (wherein, M
² represents a Li, Na or K, R ^a is the number of carbon atoms is 1
-15, preferably 1-4 hydrocarbon groups. A) a complex alkylated product of a Group 1 metal and aluminum;

(B-1c) Formula R ^a R ^b M ³ (wherein R
^a and R ^b may be the same or different from each other;
1-15 carbon atoms, preferably an 1-4 hydrocarbon group, M ³ represents a Mg, Zn or Cd. A dialkyl compound of a Group 2 or 12 metal represented by the formula:

Examples of the organoaluminum compound belonging to (B-1a) include the following compounds. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organic aluminum compound represented by the formula: R ^a _m AlH _3-m (where R ^a has 1 to 15 carbon atoms, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3,
And m + n + q = 3. The organoaluminum compound represented by).

More specifically, aluminum compounds belonging to (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like. Tri-n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum,
3-methylbutylaluminum, tri-2-methylpentylaluminum, tri3-methylpentylaluminum, tri
Tri-branched alkyl aluminum such as 4-methylpentyl aluminum, tri 2-methylhexyl aluminum, tri 3-methylhexyl aluminum, tri 2-ethylhexyl aluminum; tricyclohexyl aluminum;
Tricycloalkyl aluminum such as tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride and diisobutyl aluminum hydride; (i-C ₄ H ₉ ) _x Al _y (C Alkenyl aluminum such as isoprenyl aluminum represented by ₅ H ₁₀ ) _z (where x, y, and z are positive numbers and z ≧ 2x); isobutylaluminum methoxide;
Alkylaluminum alkoxides such as isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquitox such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide An alkoxide; a partially alkoxylated alkylaluminum having an average composition represented by ^Ra _2.5 Al (OR ^b ) _{0.5 and the} like; diethylaluminum phenoxide,
Diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutyl aluminum (2,6-di-t- Alkyl aluminum aryloxides such as butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide Dialkylaluminum halides, such as diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; ethylaluminum dichloride, propylaluminium Partially halogenated alkyl aluminum such as alkylaluminum dihalide such as mudichloride and butylaluminum dibromide; dialkylaluminum hydride such as diethylaluminum hydride and dibutylaluminum hydride; alkylaluminum such as ethylaluminum dihydride and propylaluminum dihydride Other partially hydrogenated alkyl aluminums such as dihydrides; partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

Compounds similar to (B-1a) can also be used, and examples thereof include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the above (B-1b) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) _{4 and the} like.

Furthermore, (B-1) the organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, and propylmagnesium bromide. , Propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

Further, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyl lithium or a combination of aluminum halide and alkyl magnesium can also be used.

Of these, organoaluminum compounds are preferred. The above-mentioned (B-1) organometallic compounds are used alone or in combination of two or more.

(B-2) Organoaluminum oxy compound The (B-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. May be a benzene-insoluble organic aluminum oxy compound.

A conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

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

Specific examples of the organoaluminum compound used for preparing the aluminoxane include the above-mentioned (B-1a)
And the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are exemplified. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

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

(B-3) Reaction with a transition metal amide compound
Compound that forms an on-pair The compound (B-3) (hereinafter, referred to as an “ionized ionic compound”) that forms an ion pair by reacting with the transition metal amide compound (A) used in the present invention is specifically described. Kaiping 1
JP-A-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179
No. 006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc., Lewis acids, ionic compounds, borane compounds and carborane compounds.

Specifically, as the Lewis acid, BR is used.
₃ (R is a phenyl group or a fluorine atom which may have a substituent such as fluorine, a methyl group, and a trifluoromethyl group.), For example, trifluoroboron, triphenylboron, Tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o- Tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include a compound represented by the following general formula (II).

[0058]

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[0059] In the formula, examples of R ^14, H ^+, carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

R ^{15 to} R ¹⁸ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, a tributylammonium cation, and a tri (n-butyl) ammonium cation; Nium cation, N,
N, N-dialkylanilinium cations such as N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation No.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ¹⁴ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

As ionic compounds, trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts,
Dialkylammonium salts, triarylphosphonium salts and the like can also be mentioned.

Specific examples of trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tri (n-butyl) ammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditri Fluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (III) or (IV) can also be mentioned.

[0069]

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(In the formula, Et represents an ethyl group.)

[0071]

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Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and bis [tri (n-butyl) ammonium ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-
Salts of anions such as butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) Borate) salts of metal borane anions such as nickelate (III).

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

The (B-3) ionized ionic compound as described above is used alone or in combination of two or more. Further, the catalyst for olefin polymerization according to the present invention comprises the above transition metal amide compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound,
(B-3) A particulate carrier (C) as described below can be used together with at least one compound (B) selected from ionized ionic compounds, if necessary.

(C) Fine Particle Carrier The (C) fine particle carrier used as necessary in the present invention is an inorganic or organic compound having a particle size of 10 to 3
A granular or particulate solid of 00 μm, preferably 20-200 μm, is used. Of these, a porous oxide is preferable as the inorganic compound, specifically, SiO ₂ ,
Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , C
aO-, ZnO, BaO, etc. ThO _2, or a mixture containing them, for example, SiO ₂ -MgO, SiO ₂ -Al ₂
O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO _2-
Examples thereof include Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. Among them, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable.

The above inorganic oxide contains a small amount of Na._TwoC
O_Three, K_TwoCO_Three, CaCO_Three, MgCO_Three, Na_TwoS
O_Four, Al_Two(SO_Four)_Three, BaSO_Four, KNO_Three, Mg (
NO _Three)_Two, Al (NO_Three)_Three, Na_TwoO, K_TwoO, Li_Two
Contains carbonate, sulfate, nitrate and oxide components such as O
You can do it even if you are.

Although the properties of the fine particle carrier (C) vary depending on the kind and the production method, the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g.
Preferably, it is in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 2.5 cm ³ / g. The carrier is optionally at 100 to 1000 ° C,
Preferably, it is used by firing at 150 to 700 ° C.

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

The catalyst for olefin polymerization according to the present invention comprises the above transition metal amide compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3) It comprises at least one compound (B) selected from ionized ionic compounds and, if necessary, a particulate carrier (C). FIG. 1 shows an example of a process for preparing the olefin polymerization catalyst according to the present invention.

In the polymerization, the method of use and the order of addition of each component are arbitrarily selected, and the following methods are exemplified. (1) Component (A) and at least one component (B) selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound Simply referred to as "component (B)") in any order. (2) A method in which the catalyst in which the component (A) and the component (B) are brought into contact in advance is added to the polymerization reactor. (3) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (4) A method in which the catalyst component in which the component (A) is supported on the fine-particle carrier (C) and the component (B) are added to the polymerization vessel in an arbitrary order. (5) A method in which a catalyst in which the component (A) and the component (B) are supported on the fine particle carrier (C) is added to a polymerization reactor. (6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the fine particle carrier (C) and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the components (B) may be the same or different. (7) A method in which the catalyst component in which the component (B) is supported on the fine particle carrier (C) and the component (A) are added to the polymerization reactor in an arbitrary order. (8) A method in which the catalyst component in which the component (B) is supported on the particulate carrier (C), the component (A), and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different.

The solid catalyst component in which the component (A) and the component (B) are supported on the fine particle carrier (C) may be preliminarily polymerized with an olefin. In the olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing an olefin in the presence of an olefin polymerization catalyst as described above.

In the present invention, the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. Specifically as the inert hydrocarbon medium used in the liquid phase polymerization method, propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, and xylene; ethylene chloride and chlorin Examples thereof include halogenated hydrocarbons such as benzene and dichloromethane, and mixtures thereof, and olefin itself can be used as a solvent. Among these inert hydrocarbon media, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred. It is also preferable to use the olefin itself used for the polymerization as a solvent. Of these, aliphatic hydrocarbons, alicyclic hydrocarbons and olefins themselves are preferred.

In conducting olefin polymerization using the olefin polymerization catalyst as described above, component (A)
The amount is usually 10 ^-8 to 10 ^-2 mol, preferably 10 ^-7 to 10 ^-3 mol, per 1 liter of the reaction volume.

The component (B-1) is composed of the component (B-1) and the component (A)
The molar ratio with the transition metal atom (M) in [(B-1) / M] is
Usually 0.01 to 5000, preferably 0.05 to 200
It is used in such an amount that it becomes zero. Component (B-2) is replaced by component (B
-2) has a molar ratio [(B-2) / M] of the transition metal atom (M) in the component (A) of usually 10 to 5
000, preferably 20 to 2,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) of usually 1 to 10, preferably 1 to 10. It is used in such an amount as to be 1 to 5.

The polymerization temperature of olefin using such an olefin polymerization catalyst is usually -50 to 200.
° C, preferably in the range of 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to
Under a condition of 50 kg / cm ² , the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by adding hydrogen to the polymerization system or changing the polymerization temperature. Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene,
4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-
Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl
-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-
Α-olefins having 2 to 20 carbon atoms such as tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; styrene, dimethylstyrenes, allylbenzene,
Aromatic vinyl compounds such as allyltoluenes, vinylnaphthalenes, and allylnaphthalenes; alicyclic vinyl compounds such as vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, and allylnorbornane; cyclopentene, cycloheptene, norbornene, and 5-methyl-2 -
Norbornene, tetracyclododecene, 2-methyl-1,4,
Examples thereof include cyclic olefins such as 5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

[0087]

The catalyst for olefin polymerization according to the present invention comprises:
An olefin polymer having high polymerization activity and high molecular weight can be obtained.

The olefin polymerization method of the present invention can provide an olefin polymer having a high polymerization activity and a high molecular weight.

[0089]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In this example, the intrinsic viscosity ([η]) was measured at 135 ° C. in decalin.

[0091]

Example 1 60 ml of heptane was charged into a 200 ml-volume glass autoclave sufficiently purged with nitrogen, and then 40 ml of 1-hexene was charged. The temperature was maintained at 50 ° C., and thereafter, 1 mmol of methylaluminoxane in terms of aluminum atom and subsequently 0.002 mmol of a titanium compound (A-1) represented by the following formula (a) were added to initiate polymerization. After polymerization was performed at 50 ° C. for 5 minutes under a nitrogen atmosphere at normal pressure, a small amount of methanol was added to terminate the polymerization. The polymerization reaction solution was added to a large excess of a methanol-hydrochloric acid solution, and the obtained polymer was dried under reduced pressure at 130 ° C. for 12 hours. As a result, [η] polymer of 0.34 dl / g
2 g were obtained.

[0092]

Embedded image

[0093]

Example 2 60 ml of heptane was charged into a 200 ml-volume glass autoclave which had been sufficiently purged with nitrogen, and then 40 ml of 1-hexene was charged. This was kept at 50 ° C., after which 0.5 mmol of triisobutylaluminum, 0.002 mmol of the titanium compound (A-1) represented by the formula (a), and triphenylcarbenium tetrakispentafluorophenyl borate were added. Polymerization was started by adding 0.003 mmol in this order. After polymerization was performed at 50 ° C. for 5 minutes under a nitrogen atmosphere at normal pressure, a small amount of methanol was added to terminate the polymerization. The polymerization reaction solution was added to a large excess of methanol-hydrochloric acid solution, and the obtained polymer was heated at 130 ° C.
For 12 hours under reduced pressure. As a result, [η] 1.
2.5 g of 36 dl / g polymer were obtained.

[0094]

Example 3 1-octene was polymerized in the same manner as in Example 1 except that 40 ml of 1-octene was used instead of 1-hexene. as a result,
[Η] 2.0 g of a polymer with 0.30 dl / g was obtained.

[0095]

Comparative Example 1 60 ml of toluene was charged into a 200 ml-volume glass autoclave sufficiently purged with nitrogen, and then 40 ml of 1-hexene was charged. This was kept at 50 ° C., and thereafter, 1 mmol of methylaluminoxane in terms of aluminum atom and subsequently 0.002 mmol of bis (cyclopentadienyl) zirconium dichloride were added to initiate polymerization. After performing polymerization at 50 ° C. for 5 minutes under a nitrogen atmosphere at normal pressure, a small amount of water was added to stop the polymerization.
After washing the polymerization reaction solution with aqueous hydrochloric acid, toluene and unreacted 1-hexene were distilled off from the organic phase under reduced pressure to obtain a liquid polymer 1.9.
g was obtained. As a result of analyzing the product by gas chromatography, it was found to be a dimer to pentamer oligomer.

[Brief description of the drawings]

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

Claims (2)

[Claims] (1) (A) a transition metal amide compound represented by the following general formula (I): (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B- 3) An olefin polymerization catalyst comprising at least one compound selected from compounds which form an ion pair by reacting with a transition metal amide compound (A); (Wherein, M represents a transition metal atom belonging to Groups 3 to 6 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon, Group, organic silyl group, alkoxy group, aryloxy group,
-COOR ¹¹ , -N (R ¹² ) C (O) R ¹³ , -OC
^{(O) R 14, -CN,} -NR 15 2 or -N (R ¹⁶⁾ S
(O ₂ ) R ¹⁷ (where R ^{11 to} R ^{17 each} have 1 to 1 carbon atoms)
5 represents an alkyl group. ), Wherein at least one of R ^{1 to} R ⁵ is a group other than a hydrogen atom, and R ^{6 to} R 5
At least one of the ¹⁰ is a group other than a hydrogen atom and may form a ring by linking together two or more of the groups represented by R ¹ ~R ^5, R ⁶ ~ Two or more of the groups represented by R ¹⁰ may be linked to each other to form a ring, m is an integer of 0 to 2, n is 4 or 5, and A is May be the same or different from each other.
Represents an atom belonging to Group 3 to 16; E represents a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon; In the formula, a plurality of Es may be the same or different from each other, and two or more groups represented by E may be connected to each other to form a ring, and p is an integer of 0 to 4. X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group,
When p is 2 or more, a plurality of groups represented by X may be the same or different from each other. ) 2. A method for polymerizing an olefin, comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.