JP2001048911A - PRODUCTION OF alpha-OLEFIN RANDOM COPOLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing an α-olefin random copolymer in high productivity by using a catalyst containing a transition metal compound. SOLUTION: An α-olefin random copolymer is produced by copolymerizing at least two kinds of α-olefins selected from α-olefins having carbon number of >=3 in the presence of a catalyst composed of (A) a transition metal compound of formula (M is Ti, Zr or the like; R1 to R5 are each a halogen, a hydrocarbon group or the like; A is carbon or the like; (m) and (n) are each an integer of 0-2; E is a substituent containing C, N or the like; (p) is a number satisfying the valence of M; X is a halogen or the like) and (B) at least one kind of compound selected from (B1) an organometallic compound, (B2) an organic aluminoxy compound and (B3) a compound reacting with the transition metal compound A to form an ion pair.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an α-olefin random copolymer, and more particularly, to a method for preparing an α-olefin having 3 or more carbon atoms in the presence of a catalyst containing a specific transition metal compound. The present invention relates to a method for producing an α-olefin copolymer by copolymerizing at least two or more α-olefins.

[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 recent new olefin polymerization catalyst, for example, JP-A-8-245713 discloses an olefin polymerization catalyst comprising a titanium amide compound having a titanium-nitrogen bond and aluminoxane, WO 98/466.
No. 51 proposes an olefin polymerization catalyst comprising a zirconium amide compound having a zirconium-nitrogen bond and a boron compound.

Also, Organometallics, Vol. 15, p. 2672 (1996), Journal
f Chemical Society, Dalton
Transactions 1997, p. 2487, describes an olefin polymerization catalyst comprising a zirconium amide compound having a zirconium-nitrogen bond as a component.

[0006] Incidentally, polyolefins are generally used in various fields such as molding because of their excellent mechanical properties. However, in recent years, the demands for physical properties of polyolefins have been diversified, and polyolefins having various properties have been developed. Is desired. It is also desired to improve productivity.
Under these circumstances, a method for producing a polyolefin having high polymerization activity and excellent properties, particularly an α-olefin random copolymer obtained from two or more α-olefins, using a catalyst containing a transition metal compound under such circumstances. The emergence of is desired.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides a method for producing an α-olefin random copolymer with high productivity using a catalyst containing a transition metal compound. It is intended to provide.

[0008]

SUMMARY OF THE INVENTION The method for producing an α-olefin random copolymer according to the present invention comprises (A) a transition metal compound represented by the following general formula (I) and (B) (B-1) an organometallic compound. , (B-
2) in the presence of a catalyst comprising an organoaluminum oxy compound and (B-3) at least one compound selected from compounds which react with the transition metal compound (A) to form an ion pair, It is characterized in that at least two kinds of α-olefins selected from three or more α-olefins are copolymerized.

[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 ⁵ may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, Represents 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; May be connected to each other to form a ring, A may be the same as or different from each other, represents an atom of Group 13 to 16 of the periodic table, and m and n represent 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; and 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 linked to each other to form a ring;
Is a number satisfying the valence of M, and X is 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, sulfur, And when p is 2 or more, a plurality of groups represented by X may be the same or different from each other, and two or more Xs are connected to each other to form a ring. May be. )

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing an α-olefin random copolymer according to the present invention will be specifically described. In the present invention, when copolymerizing at least two or more α-olefins selected from α-olefins having 3 or more carbon atoms, (A) a transition metal compound represented by the following general formula (I) is used as a catalyst. And (B) an organometallic compound, (B-2) an organoaluminumoxy compound, and (B-3) a transition metal compound (A), which reacts with at least one selected from compounds that form an ion pair. One compound is used.

First, each component forming the catalyst used in 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).

[0013]

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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 particularly preferably zirconium and titanium. . MN represents a chemical bond or a coordination bond.

R ^{1 to} R ⁵ 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.

The halogen atom includes 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, adamantyl; And alkenyl groups such as propenyl and cyclohexenyl; and arylalkyl groups such as benzyl, phenylethyl and phenylpropyl.

Examples of the halogenated hydrocarbon groups include groups in which the above hydrocarbon groups are 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, and N-methyl-p-toluenesulfonamide. Specific examples of the sulfonyl group include mesyl, ethanesulfonyl, methoxysulfonyl, benzenesulfonyl, and tosyl.

Of these, R ^{1 to} R ³ are preferably a hydrogen atom, a hydrocarbon group, or an organic silyl group. Also,
R ⁴ and R ⁵ are 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. In addition, 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 atoms to which they are bonded. May be.

A may be the same as 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, and a sulfur atom. Atom, germanium atom, selenium atom, tin atom and the like, and preferably a carbon atom or a silicon atom.

M and n are integers from 0 to 2. E
Is carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus,
It is a substituent having at least one element selected from boron and silicon, and is preferably a substituent containing at least one element selected from carbon, hydrogen, nitrogen and silicon. When a plurality of Es are present, the plurality of Es may be the same or different from each other, and 2
Two or more groups may be connected to each other to form a ring.

Such-(E) _m A- and-(E) _n
A- specifically, examples of the group represented by -CH ₂ -, - C
(Me) _2- , -C (Ph) _2- , -Si (Me) _2- ,
-Si (Ph) _2-, -Si (Me) (Ph)-,

[0026]

Embedded image And the like.

In the above examples, Me represents a methyl group and Ph represents a phenyl group.

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 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. 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.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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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, nBu represents an n-butyl group, and iBu represents an n-butyl group. Represents an isobutyl group, and tBu is tert
-Represents a butyl group, and Ph represents a phenyl group. In the present invention, in the above compounds, a transition metal compound in which zirconium is replaced by titanium or hafnium, and a transition metal compound in which vanadium is replaced by niobium or tantalum can also be used. These compounds may be used alone or in combination of two or more.

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

[0041] (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).

[0042] (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 (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 and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, and q is 0 ≦ q
<3, and m + n + q = 3. The organoaluminum compound represented by).

The following are more specific examples of the aluminum compound belonging to (B-1a). Trimethyl aluminum,
Triethyl aluminum, tri n-butyl aluminum,
Tri-n-alkyl aluminums such as tripropyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum. Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4 -Methylpentyl aluminum, Tri 2-
Tribranched alkyl aluminum such as methylhexyl aluminum, tri-3-methylhexyl aluminum and tri-2-ethylhexyl aluminum. Tricycloalkyl aluminums such as tricyclohexyl aluminum and tricyclooctyl aluminum; Triaryl aluminum such as triphenyl aluminum and tolyl aluminum; diisobutyl aluminum hydride,
Dialkyl aluminum hydride such as diisobutyl aluminum hydride. (I-C ₄ H ₉ ) _x Al _y (C
₅ H ₁₀ ) _z (where x, y, and z are positive numbers, and z ≧ 2)
x. And alkenyl aluminum such as isoprenyl aluminum. Alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide. ^Ra _2.5 Al (OR ^b ) _0.5
Partially alkoxylated alkyl aluminum having an average composition represented by, for example, diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl aluminum bis (2,6- Di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide) Such as alkyl aluminum aryloxide. Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide. Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; and other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride. Partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide can be mentioned.

Further, a compound similar to (B-1a) can also be used, and examples thereof include an organic aluminum compound 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) 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 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 those described in the above (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.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of 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. R ¹² in _{^{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)
The 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 organoaluminum compound under an inert gas atmosphere. In an inert solvent,
It can be produced by reacting at a temperature of -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 preferred, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferred. These are used alone or in combination of two or more.

The above-mentioned organoaluminum oxy compounds (B-2) 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.

Specifically, as the Lewis acid, BR133
(R13 may be the same or different, and is a phenyl group or a fluorine which may have a substituent such as a fluorine, a methyl group, and a trifluoromethyl group). , 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 (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, and 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. And 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.

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 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-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, dicyclohexylammonium tetra (phenyl) boron and the like.

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

[0076]

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

[0077]

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Specific examples of the borane compound include, for example, decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, 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-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, 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) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate)
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 consisting 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 above (B-3) ionized ionic compounds are used alone or in combination of two or more. In the method for producing an α-olefin random copolymer according to the present invention, the transition metal compounds (A), (B-1) and (B-2) organoaluminum oxy compounds of Groups 3 to 6 of the periodic table are used. In addition to the at least one compound (B) selected from (B-3) and the ionized ionic compound, a particulate carrier (C) as described later can also be used, if 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 above 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.

Although such porous oxides have different properties depending on the kind and the production method, 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 100~700m2 / g, it is desirable that the pore volume is in the range of 0.3~2.5cm 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
Is kaolin, bentonite, Kibushi clay,
Soil, allophane, hisingelite, pyrophyllite, cormorant
Nmo group, Montmorillonite group, vermiculite, Ryo
Kudeites, Palygorskite, Kaolinite, Nakura
Site, dickite, halloysite, etc.
As the on-exchangeable layered compound, α-Zr (HAs
O_Four)_Two・ H_TwoO, α-Zr (HPO_Four)_Two, Α-Zr (K
PO_Four)_Two・ 3H_TwoO, α-Ti (HPO_Four)_Two, Α-Ti
(HAsO_Four)_Two・ H_TwoO, α-Sn (HPO_Four)_Two・ H
_TwoO, γ-Zr (HPO _Four)_Two, Γ-Ti (HPO_Four)_Two,
γ-Ti (NH_FourPO_Four)_Two・ H_TwoCrystals of polyvalent metals such as O
And acidic acid salts.

Such clays, clay minerals, ion exchange properties
The layered compound has a radius of 20 Å measured by the mercury intrusion method.
With a pore volume of 0.1 cc / g or more
It is particularly preferably 0.3 to 5 cc / g.
Here, the measurement of the pore volume uses a mercury porosimeter.
20 to 3 × 10 ^FourOh
It is measured in the range of 20 Angs radius
Pore volume above trome smaller than 0.1 cc / g
When a compound is used, it is difficult to obtain a high polymerization activity.
There is a direction.

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 ions between the 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.

Examples of the guest compound 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
(OH) _14] 2 +, and the like _{[Fe 3 O (OCOCH 3)} 6] + metal hydroxide ions such as. 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 with 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.

In the present invention, examples of the α-olefin having 3 or more carbon atoms supplied to the polymerization reaction include 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 Hydrocarbon monomers such as -1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; acrylic acid, methacrylic acid, fumaric acid, anhydride Α, such as maleic acid, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid,
β-unsaturated carboxylic acids and metal salts thereof such as sodium, potassium, lithium, zinc, magnesium, calcium; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylic Α, β-unsaturation such as isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate Carboxylic acid esters; 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; and unsaturated glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate. Among these, a hydrocarbon monomer having 3 to 10 carbon atoms is preferable. In the present invention, such α-olefins having 3 or more carbon atoms are used in combination of at least two or more.

In the present invention, if necessary, a diene such as 1,4-hexadiene and 5-ethylidene norbornene;
It is also possible to copolymerize trienes such as 1,5,9-decatriene.

In the method for producing an α-olefin random copolymer according to the present invention, at least two or more α-olefins selected from α-olefins having 3 or more carbon atoms are copolymerized in the presence of the above-mentioned catalyst. Polymerize. FIG. 1 shows a process for preparing an olefin polymerization catalyst used in the present invention.

In the polymerization, the method of use and the order of addition of each catalyst 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 present invention, the copolymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method, and preferably, a liquid phase polymerization method is employed.

Specific examples of the inert hydrocarbon medium used in the copolymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof; The α-olefin used itself can be used as a solvent.

Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons are preferred. It is also preferable to use the α-olefin used for polymerization as a solvent.

In carrying out the copolymerization, the component (A) is used in an amount of usually 10 -8 to 10 -2 mol, preferably 10 -7 to 10 -3 mol, per liter of 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 composition of the α-olefin random copolymer obtained in the present invention is such that one α-olefin component of at least two α-olefins is usually from 0.2 to 99%.
8 mol%, preferably 0.5 to 99.5 mol%,
The other α-olefin component is usually in the range of 0.2 to 99.8 mol%, preferably 0.5 to 99.5 mol%.
The intrinsic viscosity [η] of the α-olefin random copolymer obtained in the present invention measured in a decalin solvent at 135 ° C.
Is desirably 0.01 to 10 dl / g.

[0105]

According to the method for producing an α-olefin random copolymer of the present invention, an α-olefin random copolymer can be obtained with high polymerization activity. Further, the obtained α-olefin random copolymer has a narrow molecular weight distribution.

[0106]

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

[0107]

Example 1 250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen.
A mixed gas of propylene and 1-butene (10
0 liter / hour, 5 liter / hour)
It was left at 5 ° C. for 10 minutes. Thereafter, 2 mmol of methylaluminoxane in terms of aluminum atom and then 4 μmol of a transition metal compound (A-1) represented by the following formula (a) were added to initiate polymerization. After a mixed gas of propylene and 1-butene was continuously supplied and polymerization was performed at 25 ° C. for 30 minutes under normal pressure, a small amount of methanol was added to stop the polymerization. The polymerization reaction solution was poured into an aqueous solution of dilute hydrochloric acid, and the toluene layer was concentrated and dried at 130 ° C. for 12 hours under reduced pressure. As a result, 1.29 g of a polymer having a propylene content of 98 mol% was obtained.

[0108]

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[0109]

Example 2 Into a 200 ml glass autoclave having a 200 ml internal volume sufficiently purged with nitrogen, 95 ml of toluene and then 5 ml of 1-octene were charged, and propylene was allowed to flow at a rate of 30 liter / hour and kept at 25 ° C. for 20 minutes. Was. In addition, methylaluminoxane is converted to aluminum atom by 2
Then, 4 μmol of the transition metal compound (A-1) represented by the formula (a) was added to initiate the polymerization. Propylene gas was continuously supplied at a rate of 30 liters / hour, polymerization was performed at 25 ° C. for 30 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymerization reaction solution was poured into an aqueous solution of dilute hydrochloric acid, and the toluene layer was concentrated.
Dry under reduced pressure for 2 hours. As a result, 1.08 g of a polymer having a propylene content of 96 mol% was obtained.

[0110]

EXAMPLE 3 A glass autoclave having a 200 ml internal volume and sufficiently purged with nitrogen was charged with 95 ml of toluene and then with 5 ml of 1-octene, and propylene was allowed to flow at a rate of 30 liter / hour and kept at 25 ° C. for 20 minutes. I left it. 0.5 mmol of triisobutylaluminum, 4 μmol of the transition metal compound (A-1) represented by the formula (a), and 6 μmol of triphenylcarbeniumtetrakispentafluorophenylborate were added thereto in this order, followed by polymerization. Started. Propylene gas was continuously supplied at a rate of 30 liters / hour, polymerization was performed at 25 ° C. for 30 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymerization reaction solution was poured into an aqueous solution of dilute hydrochloric acid, and the toluene layer was concentrated and dried at 130 ° C. for 12 hours under reduced pressure.
As a result, a polymer having a propylene content of 94 mol% of 0.8
4 g were obtained.

[0111]

Example 4 In the polymerization of Example 2, a transition metal compound was used.
Propylene and 1-octene were copolymerized in the same manner as in Example 2 except that 4 μmol of the transition metal compound (A-2) represented by the following formula (b) was used instead of (A-1). Was. As a result, 0.37 g of a polymer having a propylene content of 97 mol% was obtained.
was gotten.

[0112]

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[Brief description of the drawings]

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

Continued on the front page F term (reference) 4J028 AA01A AB01A AC02A AC08A AC09A AC26A AC27A AC37A AC38A BA00A BA01B BA02B BA03B BB00A BB01B BB02B BB03B BC00C BC12B BC13B BC14B BC15B BC16B BC24C30 CA30 EBCA EB26 EC02 EC04 EC06 FA02 GA06

Claims (1)

[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) ) In the presence of a catalyst comprising at least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (A),
A method for producing an α-olefin random copolymer, comprising copolymerizing at least two kinds of α-olefins selected from α-olefins having 3 or more carbon atoms; (Wherein, M represents a transition metal atom belonging to Groups 3 to 6 of the periodic table, and R ^{1 to} R ⁵ 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 connected to each other to form a ring, A may be the same or different, and represents an atom belonging to Group 13 to 16 of the periodic table; n represents an integer of 0 to 2; E represents a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon; In this case, a plurality of Es may be the same or different from each other, and two or more groups represented by E may be linked to each other to form a ring, and p is a valence of M Is a number that satisfies 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. )