JP2001011111A - Olefin polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin polymerization catalyst having excellent olefin polymerization activity by including a specific transition metal compound and a compound selected from organometallic compound, organic aluminumoxy compound, and the like. SOLUTION: The objective catalyst contains (A) a transition metal compound of formula I [M is a transition metal of groups 3-10 of the periodic table; R1 to R6 are each H, a halogen, a (halogenated)hydrocarbon group, an organic silyl, an ester, or the like; (n) is 1 or 2; A is an atom of groups 13-16 of the periodic table; (m) is 0-2; E is a substituent containing C, H, O, a halogen, or the like; (p) is valence of M; X is H, a halogen, a 1-20C (halogenated) hydrocarbon group, an O-containing group, or the like; two or more X groups may be bonded together to form a ring] (e.g. the compound of formula II), (B) a compound selected from (i) an organometallic compound, (ii) an organic aluminumoxy compound and (iii) a compound reactive with the component A to form an ion pair, and as necessary, (C) a fine particulate carrier.

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. Examples of the transition metal compound used in such a Kaminsky catalyst include bis (cyclopentadienyl) zirconium dichloride (Japanese Patent Application Laid-Open No. 58-19309) and ethylenebis (4,5,
(7,7-tetrahydroindenyl) zirconium dichloride (JP-A-61-130314) and the like are known. 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 Nos.
JP-A-1-60624, JP-A-11-80232, JP-A-11-49813, JP-A-10-32
4710, JP-A-10-324709, JP-A-10-298225, JP-A-10-8170
No. 8, JP-A-8-245713, WO98 /
46651, WO98 / 42665, WO98 / 426
64, WO98 / 30609, WO97 / 45434, etc., have proposed olefin polymerization catalysts containing a chelate compound having a transition metal-nitrogen bond as a component.

Also, Organometallics, Vol. 15, p. 2672 (1996), Journal
f Chemical Society, Dalt
OnTransactions, p. 2487, 1997, describes an olefin polymerization catalyst comprising a chelate compound having a transition metal-nitrogen bond as a component.

[0005] Incidentally, polyolefins are generally used in various fields, such as for various 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 is a demand for an olefin polymerization catalyst that is excellent in olefin polymerization activity and that can produce a polyolefin having excellent properties.

[0006]

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.

[0007]

According to the present invention, (A) a transition metal compound represented by the following general formula (I) and (B) (B-1)
For olefin polymerization comprising at least one compound selected from an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound which reacts with the transition metal compound (A) to form an ion pair. A catalyst is provided.

[0008]

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(Wherein M represents a transition metal atom belonging to Groups 3 to 10 of the periodic table, and R ^{1 to} R ⁶ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, A halogenated hydrocarbon group, an organic silyl group, an alkoxy group, an aryloxy group, an ester group, an acyl group, an amide group, an amino group, a sulfonamide group, a sulfonyl group, a nitrile group or a nitro group; The above may combine with each other to form a ring, n represents 1 or 2, A represents an atom belonging to Groups 13 to 16 of the periodic table, and when n is 2, a plurality of A May be the same or different from each other, m represents an integer of 0 to 2, and E represents at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. A substituent having the formula: If the number of a plurality of E may also form a may be the same or different, also with two or more groups connected to each other represented by E ring, p is
X is a number that satisfies the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
Represents a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, and a silicon-containing group, and when p is 2 or more, X
May be the same or different from each other, and two or more Xs may be connected to each other to form a ring. )

According to the present invention, there is further provided an olefin polymerization method for polymerizing or copolymerizing an olefin in the presence of the catalyst.

[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.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The olefin polymerization catalyst according to the present invention comprises:
(A) a transition metal compound, (B) an organometallic compound (B-1), (B-2) an organoaluminum oxy compound, and (B-3)
It is formed from at least one compound selected from compounds that form an ion pair by reacting with the transition metal compound (A).

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

[0015]

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In the formula, M represents a transition metal atom belonging to Groups 3 to 10 of the periodic table, and is preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron, cobalt, or nickel. MN represents a chemical bond or a coordination bond.

R ^{1 to} R ⁶ 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, an ester group, an acyl group. Amide group, amino group, sulfonamide group, sulfonyl group, nitrile group or nitro group.

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, anthryl and the like;
An alkyl group of 20, an aryl group having 6 to 20 carbon atoms, a halogenated hydrocarbon group, an organic silyl group, an alkoxy group, an aryloxy group, an ester group, as described below;
A substituted aryl group in which 1 to 5 substituents such as an acyl group, an amide group, an amino group, a sulfonamide group, a sulfonyl group, a nitrile group, and a nitro group are substituted; a cycloalkyl group such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; Alkenyl groups such as vinyl, propenyl and cyclohexenyl; and arylalkyl groups 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.

Specific examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like. Specific examples of the acyl group include formyl, acetyl, propionyl, butyryl, valeryl, palmitoyl, stearoyl, oleoyl, benzoyl, toluoyl, salicyloyl, cinnamoyl, naphthoyl, furoyl and the like.

Specific examples of the amide group include acetamido, N-methylacetamido, N-methylbenzamide and the like. Specific examples of the amino group include dimethylamino, ethylmethylamino, diphenylamino and the like.

Specific examples of the sulfonamide group include phenylsulfonamide, N-methylphenylsulfonamide, N-methyl-p-toluenesulfonamide and the like. Specific examples of the sulfonyl group include mesyl, ethanesulfonyl, methoxysulfonyl, benzenesulfonyl, and tosyl.

Of these, R ^{1 to} R ⁴ are preferably a hydrogen atom, a hydrocarbon group, or an organic silyl group. Also,
R ⁵ is preferably a hydrocarbon group or an organic silyl group, and among the hydrocarbon groups, particularly, phenyl, cyclohexyl, a substituted aryl group in which 1 to 5 alkyl groups having 1 to 20 carbon atoms are substituted, A substituted cyclohexyl group in which 1 to 11 alkyl groups having 1 to 20 carbon atoms are substituted is preferable. R ⁶ is preferably a hydrocarbon group, an organic silyl group, an acyl group, or a sulfonyl group, and particularly preferably a substituted aryl group in which 1 to 5 alkyl groups having 1 to 20 carbon atoms are substituted. Note that two or more of the groups represented by R ^{1 to} R ⁶ , 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 atoms to which they are bonded. May be.

N is 1 or 2. A 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,
Examples thereof include a sulfur atom, a germanium atom, a selenium atom, and a tin atom, and a carbon atom or a silicon atom is preferable. When n is 2, a plurality of A may be the same or different from each other.

M is an integer of 0 to 2. E is carbon,
A substituent having at least one element selected from hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, preferably containing at least one element selected from carbon, hydrogen, nitrogen and silicon Is a substituent. When a plurality of Es are present, the 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.

Specific examples of such a group represented by-((E _m ) A) _n- include -CH _2- , -C (Me) _2- , -C
(Ph) _2- , -Si (Me) _2- , -Si (Ph)
_{2 -, - Si (Me)} (Ph) -, - CH 2 CH 2 -, -
_{CH 2 Si (Me) 2 -} ,

[0028]

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[0029]

Embedded image And the like.

In the above examples, Me represents a methyl group and Ph represents a phenyl group. These-((E _m )
A) _n - of the group represented by, n is 1, A is a carbon atom or a silicon atom, m is 2, E is carbon,
A group which is a substituent containing at least one element selected from hydrogen, nitrogen and silicon is preferable.

P is a number satisfying the valence of M,
Is an integer. 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 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 silyls substituted with monohydrocarbons such as methylsilyl and phenylsilyl; silyls substituted with dihydrocarbons 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. When p is 2 or more, two or more Xs may be connected to each other to form a ring. Hereinafter, specific examples of the transition metal compound represented by the general formula (I) are shown, but the invention is not limited thereto.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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In the above examples, Me represents a methyl group, Et represents an ethyl group, nPr represents an n-propyl group, iPr represents an isopropyl group, iBu represents an isobutyl group, and tBu represents a tert- group. Ph represents a butyl group, and Ph represents a phenyl group. In the present invention, a transition metal compound in which zirconium is replaced with titanium or hafnium in the above compounds may be used. These compounds may be used alone or in combination of two or more.

(B-1) Organometallic Compounds As the (B-1) organometallic compounds used in the present invention, specifically, the following Periodic Groups 1, 2 and 12, 1
A group 3 organometallic compound is used.

[0044] (B-1a) In the formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <m
≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <
The number is 3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0045] (B-1b) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a Group 1 metal and aluminum represented by the formula:

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

As the organoaluminum compound belonging to the above (B-1a), the following compounds can be exemplified. 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, the aluminum compound belonging to (B-1a) includes trimethylaluminum, triethylaluminum, trin-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 sesquis such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide alkoxide; diethylaluminum _{^{phenoxide,; R a 2.5 Al (OR}} b) an alkylaluminum which is partly alkoxylated with an average composition represented by like _0.5
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 (B-1b) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) ₄ .

Further, (B-1) 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 alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.

Of these, organoaluminum compounds are preferred. The organometallic compounds (B-1) as described above 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.

The 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 in 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.

As the organic aluminum oxy compound used in the present invention, an organic aluminum oxy compound containing boron represented by the following general formula (II) can also be mentioned. During _{^{R 12 2 AlOB (R 11)}} OAlR 12 2 (II) formula, R ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹² may be the same or different, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

The organoaluminum oxy compound containing boron represented by the above general formula (II) is represented by the following general formula (II)
An alkylboronic acid represented by I) and R ¹¹ B (OH) ₂ (III) (wherein R ¹¹ represents the same group as described above) are mixed with an organic aluminum compound under an inert gas atmosphere in an inert solvent. The reaction can be carried out at -80 ° C to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (III) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

Specific examples of such an organoaluminum compound to be reacted with an alkylboronic acid are described above (B
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to -1) can be mentioned.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

The above-mentioned (B-2) organoaluminum oxy compounds are used alone or in combination of two or more.

(B-3) Reaction with Transition Metal Compound to Form Ion Pair
Reacts with the transition metal compound used in the compounds present invention to form the compound (A) to form an ion pair (B-3) (hereinafter. Referred to as "ionizing ionic compound") include, JP-1- 50
1950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-20
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 7,704, US Pat. No. 5,321,106. further,
Heteropoly compounds and isopoly compounds can also be mentioned.

[0068] More specifically, as the Lewis acid, BR ¹³ ₃
(R ¹³ may be the same or different from each other, and is a phenyl group or a fluorine which may have a substituent such as a 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 compounds represented by the following general formula (IV). ^{[R 14] + [BR 15} 4] - ··· (IV) wherein the [R ^{14] +} is, H ^+, carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation And a ferrocenium cation having a transition metal.

R ¹⁵ may be the same or different and is 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 trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation; and N, N-dimethylanilyl. Cation, N, N-diethylanilinium cation, N, N-
N, N such as 2,4,6-pentamethylanilinium cation
Dialkylanilinium cations; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

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.

Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt 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-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (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 pentaphenylcyclo A pentadienyl complex and a boron compound represented by the following formula (V) or (VI) can also be mentioned.

[0079]

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

[0080]

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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 heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangustovanadate acid, phosphomolybdatovantovanadate acid, germanomolybdodovantovanadate acid, phosphorus motibud tungstic acid, Phosphomolybdniobate, salts of these acids, for example metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like When Salts, and organic salts such as triphenylethyl salts, and an isopoly compound may be used,
This is not the case. The heteropoly compound and the isopoly compound are not limited to one kind among the above compounds, and two or more kinds can be used.

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 compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ion. In addition to the at least one compound (B) selected from the acidic compounds, a particulate carrier (C) as described below can be used as necessary.

(C) Particulate Carrier The (C) particulate carrier used as required in the present invention is an inorganic or organic compound, and is a granular or particulate solid. Among them, the inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral or an ion-exchange layered compound.

As the porous oxide, specifically, Si
O 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 -Cr
Examples include ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, and the like. 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 porous oxide contains a small amount of Na ₂
CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ S
O ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (N
_{O 3) 2, Al (NO} 3) 3, Na 2 O, K 2 O, Li 2 O carbonates such as, sulfates, nitrates, may safely be contained oxide component.

The properties of such a porous oxide vary depending on the kind and the manufacturing method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 300 μm.
And a specific surface area of 50 to 1000 m ^2.
/ G, preferably in the range of 100 to 700 m ² / g, and the pore volume is desirably in the range of 0.3 to 2.5 cm ³ / g. Such a carrier may be used, if necessary, for 10 hours.
It is used by firing at 0 to 1000 ° C, preferably 150 to 700 ° C.

As inorganic halides, MgCl ₂ ,
MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used.
The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Also, those treated with a solvent such as alcohol, for example,
After dissolving the inorganic halide, it is also possible to use one that is precipitated in fine particles by a precipitant.

The clay used in the present invention is usually composed mainly of a clay mineral. Further, the ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces constituted by ionic bonds and the like are stacked in parallel with weak bonding force to each other, and the ions contained therein are exchangeable. . Most clay minerals are ion-exchangeable layered compounds. Examples of the clay, clay mineral or ion-exchangeable layered compound include ionic crystalline compounds having a layered crystal structure such as hexagonal dense packing type, antimony type, CdCl ₂ type and CdI ₂ type. As these clays, clay minerals, and ion-exchangeable layered compounds, not only natural products but also artificial synthetic products can be used.

Specific examples of such clays and clay minerals include kaolin, bentonite, Kibushi clay, gairome clay, allophane, hisingelite, pyrophyllite, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, Kaolinite, nacrite, dickite, halloysite, and the like, and examples of the ion-exchange layered compound include α-Zr (HAs
O ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (K
PO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti
(HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H
₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ ,
A crystalline acidic salt of a polyvalent metal such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O may be used.

The clay, the clay mineral and the ion-exchangeable layered compound preferably have a pore volume of 20 Å or more as measured by mercury porosimetry with a pore volume of 0.1 cc / g or more, preferably 0.3 to 5 cc / g. g are particularly preferred.
Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter with a pore radius in the range of 20 to ³ × 10 ⁴ Å. When a compound having a radius of 20 angstroms or more and a pore volume of less than 0.1 cc / g is used, high polymerization activity tends to be hardly obtained.

The clay and clay mineral used in the present invention can be subjected to a chemical treatment. As the chemical treatment, both a surface treatment for removing impurities adhering to the surface and a treatment for affecting the crystal structure of the clay can be used. Specific examples include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In salt treatment and organic matter treatment,
Form ion complexes, molecular complexes, organic derivatives, etc.
The surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention utilizes the ion-exchange property to exchange the exchangeable ion between layers with another large bulky ion, thereby obtaining a layered compound in which the layers are expanded. You can also. Here, the bulky ions play a pillar-like role of supporting the layered structure, and are called pillars. Introducing another substance (guest compound) between layers of the layered substance is called intercalation.

The guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; Ti (OR) ₄ , Zr (OR) ₄ and PO (O
_{R) 3, B (OR)} 3, (R is a metal alcoholate etc.) hydrocarbon _{radical; [Al 13 O 4 (OH} ) 24] 7+, [Zr 4
Metal hydroxide ions such as (OH) ₁₄ ] ²⁺ and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds are used alone or in combination of two or more. Also, when intercalating these compounds,
Polymers obtained by hydrolyzing metal alcoholates such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group), colloidal inorganic compounds such as SiO _2, etc. They can coexist. Other examples of pillars include oxides generated by intercalating the hydroxide ions between layers and then heating and dehydrating.

The clay, clay mineral and ion-exchange layered compound used in the present invention may be used as they are, or may be used after being subjected to a treatment such as pulverization by a ball mill and sieving. Further, it may be used after newly adding and adsorbing water or performing a heat dehydration treatment. Further, they may be used alone or in combination of two or more. Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.

The organic compound has a particle size of 10 to 300.
Granular or particulate solids in the range of μm can be mentioned. Specifically, ethylene, propylene, 1-
Butene, 4-methyl-1-pentene, etc. having 2 to 2 carbon atoms
Examples thereof include (co) polymers formed mainly with the olefin of No. 14, vinylcyclohexane, (co) polymers formed mainly with styrene, and modified products thereof.

The catalyst for olefin polymerization according to the present invention comprises the above-mentioned transition metal 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 catalyst component are arbitrarily selected, but 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 or copolymerizing an olefin in the presence of the 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 olefins used for polymerization can be used as a solvent.

Of these inert hydrocarbon media, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred. It is also preferable to use an olefin, an alicyclic vinyl compound, or a cyclic olefin itself used as a solvent for the polymerization.

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. Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) to transition metal atom (M) in component (A) of usually 0.0%.
It is used in an amount of 1 to 5000, preferably 0.05 to 2000. Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) to the transition metal atom (M) in component (A) of usually 10 to 10. It is used in an amount of 5000, preferably 20-2000. 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 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 it is in the range of 0 to 170C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 k
g / cm ² , and 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 resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

The olefins that can be polymerized with such olefin polymerization catalysts include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 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-
2 to 20 carbon atoms such as ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene Α-olefins; aromatic vinyl compounds such as styrene, dimethylstyrenes, allylbenzene, allyltoluenes, vinylnaphthalenes, allylnaphthalenes; alicyclics such as vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allylnorbornane Vinyl compound; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,
Cyclic olefins such as 4a, 5,8,8a-octahydronaphthalene; butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1 1,4-hexadiene, 1,5-hexadiene, 1,
6-octadiene, 1,7-octadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene,
A chain polyene having 4 to 20 carbon atoms such as 5,9-dimethyl-1,4,8-decatriene; 5-ethylidene norbornene;
Cyclic polyenes such as vinyl norbornene and dicyclopentadiene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo
Α, β- such as (2,2,1) -5-heptene-2,3-dicarboxylic acid
Unsaturated carboxylic acids and their sodium, potassium,
Metal salts such as lithium, zinc, magnesium, and calcium; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-acrylate
-Butyl, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,
Isopropyl methacrylate, n-butyl methacrylate,
Α, β-unsaturated carboxylic acid esters such as isobutyl methacrylate; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and maleic anhydride and their acid anhydrides; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate , Vinyl laurate, vinyl stearate,
Vinyl esters such as vinyl trifluoroacetate; unsaturated glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate; and halogen-containing olefins such as vinyl chloride and vinyl fluoride. These olefins can be used alone or in combination of two or more.

[0107]

The olefin polymerization catalyst according to the present invention has a high polymerization activity and an olefin having a narrow molecular weight distribution.
A polymer can be obtained, and an olefin copolymer having a narrow composition distribution can be obtained when two or more olefins are copolymerized.

The olefin polymerization method according to the present invention can obtain an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution. When two or more olefins are copolymerized, an olefin copolymer having a narrow composition distribution can be obtained. A polymer can be obtained.

[0109]

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

(Example 1) Internal volume 5 sufficiently purged with nitrogen
250 ml of toluene in a 00 ml glass autoclave
and ethylene was allowed to flow at 100 liters / hour, and the mixture was allowed to stand at 25 ° C. for 10 minutes. Thereafter, 1 mmol of methylaluminoxane was converted into aluminum atom,
Subsequently, a transition metal compound represented by the following formula (a) (A-
2 μmol of 1) was added to initiate polymerization. 10 ethylene gas
0 liter / hour, continuously supplied at normal pressure, 25
After polymerization at 30 ° C. for 30 minutes, a small amount of methanol was added to terminate the polymerization. The polymerization reaction solution was treated with a large excess of methanol
The resulting polymer was added to a hydrochloric acid solution at 130 ° C. for 12 hours.
Dry under reduced pressure for hours. As a result, the polymer 0.84
g was obtained.

[0111]

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(Example 2) Internal volume 5 sufficiently purged with nitrogen
250 ml of toluene in a 00 ml glass autoclave
and ethylene was allowed to flow at 100 liters / hour, and the mixture was allowed to stand at 25 ° C. for 10 minutes. Then, 0.5 mmol of triisobutylaluminum was added to the above formula (a)
2 μmol of the transition metal compound (A-1) and 3 μmol of triphenylcarbenium tetrakispentafluorophenyl borate were added in this order to initiate polymerization. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was carried out at 25 ° C. for 30 minutes under normal pressure, and then 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, 0.46 g of a polymer was obtained.

(Example 3) Internal volume 5 sufficiently purged with nitrogen
250 ml of toluene in a 00 ml glass autoclave
and mixed gas of ethylene and propylene (60 liter / hour and 40 liter / hour, respectively)
And allowed to stand at 25 ° C. for 10 minutes. Thereafter, 1 mmol of methylaluminoxane was converted into aluminum atom, followed by the transition metal compound represented by the formula (a).
2 μmol of (A-1) was added to initiate polymerization. After a mixed gas of ethylene and propylene was continuously supplied and polymerization was carried out at 25 ° C. for 30 minutes under 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, 0.63 g of a polymer having an ethylene content of 93 mol% was obtained.

Example 4 In the polymerization of Example 1, except that the transition metal compound (A-2) represented by the following formula (b) was used instead of the transition metal compound (A-1). Ethylene was polymerized in the same manner as in Example 1. As a result, the polymer 0.1.
32 g were obtained.

[0115]

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[0116]

Example 5 In the polymerization of Example 1, a transition metal compound was used.
Ethylene was polymerized in the same manner as in Example 1 except that a transition metal compound (A-3) represented by the following formula (c) was used instead of (A-1). As a result, 0.17 g of a polymer was obtained.

[0117]

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[0118]

Example 6 In the polymerization of Example 1, a transition metal compound was used.
Ethylene was polymerized in the same manner as in Example 1 except that a transition metal compound (A-4) represented by the following formula (d) was used instead of (A-1). As a result, 0.39 g of a polymer was obtained.

[0119]

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[0120]

Example 7 [Preparation of decane slurry of methylaluminoxane] 500 m in inner volume equipped with a stirring blade under a nitrogen atmosphere
100 ml of a toluene solution of methylaluminoxane (1.5 mol / l in terms of aluminum atom) is charged into a 1 l glass reactor, and 100 ml of nitrogen-substituted decane is added dropwise with stirring at room temperature over 1 hour. did.
From the resulting solid methylaluminoxane slurry, toluene was distilled off under reduced pressure (45 ° C., 10 mmHg).
Decane was added to this to prepare a decane slurry of methylaluminoxane (0.9 mol / liter in terms of aluminum atom). The specific surface area of the obtained methylaluminoxane was 182 m ² / g.

[Polymerization] Internal volume 500 sufficiently purged with nitrogen
250 ml of decane was charged into a ml autoclave made of glass, and ethylene was passed through the autoclave at 100 liter / hour, and the mixture was allowed to stand at 25 ° C. for 10 minutes. Thereafter, the decane slurry of methylaluminoxane obtained above was added to 0.28 m
1, followed by a transition metal compound represented by the following formula (e)
2 m of a heptane solution (1 mmol / l) of (A-5)
1 to start polymerization. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was carried out at 25 ° C. for 30 minutes under normal pressure, and then 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, 1.13 g of a polymer was obtained.

[0122]

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[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.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Terunori Fujita 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture F-term in Mitsui Chemicals, Inc. (reference) 4J028 AA01A AB00A AB01A AC01A AC18A AC19A AC29A AC31A AC37A AC38A AC46A AC47A AC48A BA00A BA01B BA02B BA03B BB00A BB01B BB02B BC05B BC08B BC09B BC12B BC15B BC16B BC17B BC18B BC24B BC25B BC27B BC29B

Claims (2)

[Claims] (1) (A) a transition metal 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, which comprises at least one compound selected from compounds that form an ion pair by reacting with the transition metal compound (A); (Wherein, M represents a transition metal atom belonging to Groups 3 to 10 of the periodic table, and R ^{1 to} R ⁶ may be the same or different from each other;
Hydrogen atom, halogen atom, hydrocarbon group, halogenated hydrocarbon group, organic silyl group, alkoxy group, aryloxy group, ester group, acyl group, amide group, amino group, sulfonamide group, sulfonyl group, nitrile group or nitro group And two or more of these may be linked to each other to form a ring, n represents 1 or 2,
Represents an atom belonging to Groups 13 to 16 of the periodic table, and when n is 2, a plurality of As may be the same or different from each other; m represents an integer of 0 to 2; A substituent having at least one element selected from the group consisting of carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon; and when a plurality of Es are present, the plurality of Es may be the same or different. And two or more groups represented by E may be connected to each other to form a ring, p is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Halogenated hydrocarbon groups, oxygen-containing groups, sulfur-containing groups,
A silicon-containing group, when p is 2 or more, a plurality of groups represented by X may be the same as or different from each other, or two or more Xs may be linked to each other to form a ring Good. ) 2. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1.