JPH05155923A - Catalyst for polymerization of olefin and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a polymer having a narrow molecular weight distribution by using a catalyst prepared by combining a specified transition metal catalyst component with an organoaluminum(oxy) compound. CONSTITUTION:A transition metal complex compound of formula I [wherein M is Zr or Hf; R<1> is 6C or higher aryl, naphthyl, fluorene or CR<11>R<12>R<13>; R<11> to R<13> are each H, alkyl, aryl or aralkyl, at least two of them are alkyl, aryl or aralkyl provided that the above alkyl, aryl or naphthyl may be substituted with alkyl or aryl or may have a substituent containing a heteroatom such as halogen, O, N, P, S or Si; R<2> and R<3> are each R<1>, halogen or SO3R<5>; R<4> is halogen or SO3R<5>; R<5> is (halogen-substituted) alkyl, aryl or the like; c<=1, and (a+b+c)=3] is combined with an organoaluminumoxy compound of formula II (wherein R<6> is alkyl; (n) is an integer), which may be branched or cyclic, and/or an oragnoaluminum compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel olefin polymerization catalyst and a method for polymerizing olefins in the presence of this catalyst, and more specifically to a specific transition metal complex component and an organoaluminum oxy compound component. The present invention relates to an olefin polymerization catalyst comprising an organic aluminum compound component and / or an olefin polymerization method in the presence of the catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a method for producing an α-olefin polymer has been carried out in the presence of a titanium catalyst comprising a titanium compound and an organoaluminum compound or a vanadium catalyst comprising a vanadium compound and an organoaluminum compound. , A method of copolymerizing ethylene and α-olefin is known.

Generally, an ethylene / α-olefin copolymer obtained with a titanium catalyst has a broad molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. In addition, the ethylene / α-olefin copolymer obtained with the vanadium-based catalyst has a narrower molecular weight distribution and composition distribution than those obtained with the titanium-based catalyst,
And, the transparency, the surface non-tackiness and the mechanical properties are considerably improved, but they are still insufficient for the applications in which these performances are required. -A catalyst that can obtain an α-olefin copolymer is required.

On the other hand, as a new Ziegler type olefin polymerization catalyst, a catalyst comprising a zirconium compound and aluminoxane has been proposed in recent years. For example, JP-A-5
8-19309, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35.
JP-A No. 008, JP-A-61-130314, and JP-A No. 2-41303 disclose transition metal compounds having a pentadienyl group such as a cyclopentadienyl group as a ligand, an alkyl group and / or a halogen atom. It is described that the catalyst system in which the metallocene compound and the aluminoxane are combined is highly active in the polymerization of α-olefin and the obtained polymer has excellent properties.

Under these circumstances, it has been desired to develop a new olefin polymerization catalyst which is excellent in olefin polymerization activity and excellent in properties of the obtained polyolefin.

[0006]

An object of the present invention is to provide a catalyst for olefin polymerization which comprises a transition metal complex component and an organoaluminum oxy compound component and / or an organoaluminum compound component, and which has excellent polymerization activity and stability. It is an object. Further, it is an object of the present invention to provide a method for polymerizing an olefin in the presence of a catalyst comprising a transition metal complex component and an organoaluminum oxy compound component and / or an organoaluminum compound component.

[0007]

[1]

(A) Transition metal complex component represented by the following general formula [I] R ² _a R ³ _b R ⁴ _c M (OR ¹ ) ... [I] (wherein, M is zirconium or hafnium.

R ¹ has 6 or more carbon atoms and is an aryl group, naphthyl group, fluorene group or --CR ¹¹ R ¹² R ¹³
And R ¹¹ , R ¹² , and R ¹³ are hydrogen, an alkyl group, an aryl group, or an aralkyl group, and may be the same or different, and at least two of R ¹¹ , R ¹² , and R ¹³ are It is an alkyl group, an aryl group or an aralkyl group.

The above-mentioned alkyl group, aryl group and naphthyl group may be substituted with an alkyl group or an aryl group, and a substituent containing a hetero atom such as halogen, oxygen, nitrogen, phosphorus, sulfur or silicon may be substituted. You may have.

R ² and R ³ are --OR ¹ , halogen or --SO ₃ R ⁵ , and R ⁴ is halogen or --SO 3.
₃ R ⁵ . R ⁵ is an alkyl group, an alkyl group substituted with halogen, an aryl group, a halogen atom or an aryl group substituted with an alkyl group.

When two or more --OR ^1's are present, two --OR ^1's are alkylene group, substituted alkylene group, silylene group, substituted silylene group, oxygen,
It may be linked via sulfur. Further, c ≧ 1 and a + b + c = 3. ) And [2] (B) Organoaluminum oxy compound component represented by the following general formula [II]

[0012]

[Chemical 3]

(In the formula, R ⁶ is an alkyl group, n is an integer, and this compound may be branched or may form a ring.) And / or (C) organoaluminum. It is characterized by being composed of compound components.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized in the presence of the catalyst as described above. When an olefin is polymerized using such a catalyst and a polymerization method, the polymerization activity is high,
A polymer having a narrow molecular weight distribution can be obtained. Further, when two or more kinds of monomers are copolymerized, a copolymer having a narrow composition distribution can be obtained.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method according to the present invention will be specifically described below.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may be used not only as a homopolymer but also as a copolymer. May be used to mean coalesce.

[Transition Metal Complex] The transition metal complex component (A) used in the present invention is a transition metal complex represented by the following general formula [I].

R ² _a R ³ _b R ⁴ _c M (OR ¹ ) ... [I] (In the formula, M is zirconium or hafnium.
¹ has 6 or more carbon atoms, an aryl group, a naphthyl group,
A fluorene group or —CR ¹¹ R ¹² R ¹³ ; R ¹¹ and R
¹² , R ¹³ are hydrogen, an alkyl group, an aryl group or an aralkyl group, which may be the same or different,
At least two of R ¹¹ , R ¹² , and R ¹³ are alkyl groups, aryl groups, or aralkyl groups.

The above-mentioned alkyl group, aryl group and naphthyl group may be substituted with an alkyl group or an aryl group, and a substituent containing a hetero atom such as halogen, oxygen, nitrogen, phosphorus, sulfur or silicon may be substituted. You may have.

R ² and R ³ are --OR ¹ , halogen or --SO ₃ R ⁵ , and R ⁴ is halogen or --SO 3.
₃ R ⁵ . R ⁵ is an alkyl group, an alkyl group substituted with halogen, an aryl group, a halogen atom or an aryl group substituted with an alkyl group.

When two or more —OR ^1's are present, two of the —OR ^1's are an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, oxygen,
It may be linked via sulfur. Further, c ≧ 1 and a + b + c = 3. ) —OR ¹ in the above general formula [I] can be derived mainly from a compound having a hydroxyl group, and specific examples thereof include the following.

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

(In the formula, t-Bu represents a tert-butyl group.) Of these, [I-18], [I-19],
A phenoxy group having a substituent at the 2- and 6-positions such as [I-20] or a fluorenyl group such as [I-33], [I-34] and [I-35] is preferable.

When the transition metal complex has two or more groups represented by --OR ¹ as described above, two --OR ¹ of them are an alkylene group, a substituted alkylene group, a silylene group or a substituted group. They may be linked via a silylene group, oxygen, sulfur or the like. Examples of the alkylene group include ethylene group and propylene group, examples of the substituted alkylene group include isopropylidene group and diphenylmethylene group, and examples of the substituted silylene group include dimethylsilylene group.

R ² and R ³ are —OR ¹ as defined above,
Halogen or -SO ₃ R ^5, R ⁴ is halogen or -SO ₃ R ^5. R ⁵ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, a halogen atom or an aryl group substituted with an alkyl group.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group and butyl group, and examples of the aryl group include phenyl group and tolyl group.

Halogen is fluorine, chlorine, bromine or iodine, and particularly preferred is fluorine. Specific examples of the transition metal complex used in the present invention include the following compounds.

[0030]

[Chemical 7]

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[Method for Producing Transition Metal Complex] In order to prepare the transition metal complex used in the present invention, specifically, the following method can be adopted.

(1) A compound represented by the general formula MX ₄ (hereinafter sometimes referred to as “compound [III]”) and a compound represented by the general formula AOR ¹ (hereinafter referred to as “compound [IV]”). There is)) and the reaction in a solvent.

[0035]

[Chemical 10]

(Wherein M and R ¹ are the same as defined in the formula [I], X is halogen, A is hydrogen, 1
Group or Group 2 typical metal or silyl group or substituted silyl group. Further, 1 ≦ n ≦ 3. ) That is, A
By reacting a compound having a hydroxyl group represented by OR ¹ (wherein A is hydrogen) with a tetravalent zirconium compound or a hafnium compound, preferably a tetravalent zirconium halide or a hafnium halide. Transition metal complexes can be prepared. Also, H
The compound having a hydroxyl group represented by OR ¹ is lithium,
Conversion to a Group 1 typical metal such as sodium or potassium, or a Group 2 typical metal salt such as magnesium or calcium, or a compound having a silyl group or a substituted silyl group,
A compound represented by AOR ¹ (wherein A is a group 1 or group 2 typical metal or a silyl group or a substituted silyl group) is reacted with a tetravalent zirconium compound or a hafnium compound to make a transition. Metal complexes can be prepared.

The reaction conditions in this reaction differ depending on the composition of the compound to be obtained, but the compound [IV] is used in an amount of 1 to 3 times the mole of the transition metal of the compound [III]. It The reaction temperature is -20 to 180.
It is desirable that the temperature is 0 ° C, preferably 0 to 130 ° C, and the reaction time is 0.5 to 48 hours, preferably 2 to 12 hours.

As the solvent used in the reaction, aliphatic hydrocarbons such as hexane and decane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform and methylene chloride, Examples thereof include ketones such as acetone and methyl isobutyl ketone, ethers such as ethyl ether and tetrahydrofuran, acetonitrile and the like. Of these, benzene, toluene and xylene are particularly preferable. Such a solvent is generally used in an amount of 1 to 1000 times, preferably 50 to 500 times the amount of the compound [III].

(2) The transition metal complex [V] obtained in the above (1) is further mixed with a compound represented by the general formula LSO ₃ R ² (hereinafter sometimes referred to as "compound [VI]") in a solvent. The reaction can be performed to prepare a transition metal complex having —OR ¹ and —SO ₃ R ⁵ .

In the compound [VI], L is a Group 1 typical metal such as lithium, sodium, potassium or silver, and R ⁵ is the same as defined in the formula [I]. The reaction conditions in this reaction differ depending on the composition of the compound to be obtained, but the compound [VI] is 1 to 3 times the molar amount of the transition metal of the transition metal complex [V] obtained in (1). Used in molar amounts. The reaction temperature is -20 to 180.
It is desirable that the reaction temperature is 0.5 ° C, preferably 0 to 130 ° C, and the reaction time is 0.5 to 48 hours, preferably 2 to 12 hours.

Examples of the solvent used in the reaction include the same solvents as those used in the above (1). Of these, benzene, toluene and xylene are particularly preferable. Such a solvent is usually used in an amount of 1 to 1000 times, preferably 50 to 500 times the amount of the transition metal complex [V].

(3) A method of reacting the compound [III] with the compound [VI] to obtain a transition metal complex [VII], and then reacting the transition metal complex [VII] with the compound [IV]. That is, first, the compound [III] and the compound [VI] are reacted in a solvent.

[0043]

[Chemical 11]

(In the formula, M and R ⁵ are the same as the definitions in the formula [I], X is the same as the definition in the formula (i), and L is 1 of lithium, sodium, potassium or the like.
It is a group typical metal or silver. Further, 1 ≦ m ≦ 4. The reaction conditions at this time vary depending on the composition of the compound to be obtained, but the compound [VI] is used in an amount of 1 to 4 times, preferably 1 to 2 times the mol of the compound [III]. To be done. The reaction temperature is −20 to 180 ° C., preferably 0 to 130 ° C., and the reaction time is 0.5 to 48 hours, preferably 2 to 12 hours.

As the solvent used in the reaction, the same solvents as those used in the above (1) can be mentioned. Of these, benzene, toluene and xylene are particularly preferable. Such a hydrocarbon solvent is usually used in an amount of 1 to 1000 times, preferably 5 times, with respect to 1 mol of the metal of the transition metal complex.
It is used in an amount of 0 to 500 times.

Then, the reaction system is filtered, and the solvent of the obtained filtrate is distilled off under reduced pressure. After that, the transition metal complex [VII] obtained above and the compound [IV] are reacted in a solvent to prepare a transition metal complex having —OR ¹ and —SO ₃ R ⁵ .

The reaction conditions at this time vary depending on the composition of the compound to be obtained, but the compound [IV] is used in an amount of 1 to 3 times the mol of the starting compound [III]. The reaction temperature is −20 to 180 ° C., preferably 0.
~ 130 ° C is desirable, and reaction time is 0.5-
Desirably, it is 48 hours, preferably 2 to 12 hours.

As the solvent used in the reaction, the same solvent as used in the above (1) can be mentioned. Of these, benzene, toluene and xylene are particularly preferable. Such a hydrocarbon solvent is usually 1 to 1000 times, preferably 50 to 500 times the amount of the compound [III].
Used in double amount.

(4) A compound represented by the general formula MX _4-p R ⁷ _p (hereinafter sometimes referred to as "compound [VIII]").
And a compound [IV] in a solvent.

[0050]

[Chemical 12]

(Wherein M and R ¹ are the same as defined in the formula [I], X is halogen, A is hydrogen, 1
Group 7 or Group 2 typical metal, a silyl group or a substituted silyl group, and R ⁷ is an alkyl group having 1 to 10 carbon atoms, an aryl group or a benzyl group. Also, 1 ≦
p ≦ 3. That is, a transition metal complex can be prepared by reacting a compound having a hydroxyl group represented by AOR ¹ (wherein A is hydrogen) with a tetravalent alkylzirconium compound or an alkylhafnium compound. You can

The reaction conditions in this reaction differ depending on the composition of the compound to be obtained, but the compound [IV] is used in an amount of 1 to 3 times the mol of the transition metal of the compound [VIII]. It The reaction temperature is -20 to 180.
It is desirable that the temperature is 0 ° C, preferably 0 to 130 ° C, and the reaction time is 0.5 to 48 hours, preferably 2 to 12 hours.

As the solvent used in the reaction, the same solvent as used in the above (1) can be mentioned. Of these, benzene, toluene and xylene are particularly preferable. Such a solvent is usually used in an amount of 1 to 1000 times, preferably 50 to 500 times the amount of the transition metal complex [VIII].

The transition metal complex can be produced in good yield by the production method as described above. The transition metal complex thus obtained can be filtered and the filtrate obtained can be taken out by distilling off the solvent under reduced pressure. Further, it can be recrystallized, or isolated and purified by a method such as sublimation.

[Cocatalyst] The organoaluminum oxy compound component (B) used as a catalyst for olefin polymerization together with the (A) transition metal complex component according to the present invention is an organoaluminum oxy compound usually used for olefin polymerization. Used as is.

Such an organoaluminum oxy compound is represented by the following general formula [II].

[0057]

[Chemical 13]

(In the formula, R ⁶ is an alkyl group, and n is an integer. This compound may be branched or may form a ring.) Such an organoaluminum oxy compound is conventionally known. It may be a known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

The conventionally known aluminoxane can be produced, for example, by the following method. Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first chloride
A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension such as cerium hydrate and reacting it.

Benzene, toluene, ethyl ether,
A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as tetrahydrofuran to recover it as a hydrocarbon solution.

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 organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for producing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and triisopropylaluminum
n-butyl aluminum, triisobutyl aluminum,
Tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum, tricyclooctylaluminum and other trialkylaluminums; dimethylaluminium chloride, diethylaluminum chloride, Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; Dialkyl aluminum such as diethyl aluminum phenoxide Mini Umm Ali Loki Sid, and the like.

Of these, trialkylaluminum is particularly preferable. Further, isoprenylaluminum represented by the following general formula [X] can also be used as the organoaluminum compound used when producing the aluminoxane.

(I-C ₄ H ₉ ) x Aly (C ₅ H ₁₀ ) z [X] (In the formula, x, y, and z are positive numbers, and z ≧ 2x.) As described above. Such organoaluminum compounds are used alone or in combination.

As the solvent used in the production of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane, hexane,
Aliphatic hydrocarbons such as heptane, octane, decane, dodecane, hexadecane, octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromas. Examples thereof include halides of group hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, and particularly hydrocarbon solvents such as chlorinated compounds and brominated compounds. Other,
Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The organoaluminum compound component (C) used as a catalyst for olefin polymerization together with the transition metal complex component (A) according to the present invention is an organoaluminum compound used in producing a solution of aluminoxane, and is preferably Are trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

The organoaluminum compound component (C) is generally diluted with a hydrocarbon solvent such as hexane or decane before use. The above (A) transition metal complex component, (B)
At least one component selected from the organoaluminum oxy compound component and the (C) organoaluminum compound component may be used by supporting it on a carrier such as silica, alumina, silica-alumina or zirconia.

[Polymerization Method] The olefin polymerization method according to the present invention comprises the above-mentioned (A) transition metal complex component,
The olefin is polymerized in the presence of (B) the organoaluminum oxy compound component and / or (C) the organoaluminum compound component.

Examples of olefins applicable to the polymerization method of the present invention include the following types. Ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-
Butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
Cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned.

It is also possible to use styrene, vinylcyclohexane, or non-conjugated dienes such as dicyclopentadiene and 5-ethylidene norbornene. In the present invention, it is possible to copolymerize two or more components using the above-mentioned olefins. For example, ethylene / propylene, ethylene / 1-butene, ethylene / propylene /
Diene, ethylene / tetracyclododecene and the like.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. In the liquid phase polymerization, an inert hydrocarbon solvent or olefin itself can be used as a solvent. Specific examples of the hydrocarbon solvent include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic groups such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane. Aromatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene; gasoline, kerosene,
Examples include petroleum fractions such as light oil.

In the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. When carrying out the liquid phase polymerization method, the polymerization temperature is usually 0 to 250 ° C., preferably 20 to 200 ° C.
When carrying out the gas phase polymerization method, the polymerization temperature is usually 0.
It is desirable to be in the range of 120 to 120 ° C, preferably 20 to 100 ° C.

In the present invention, when the olefin is polymerized by the slurry polymerization method, the solution polymerization method or the gas phase polymerization method,
The transition metal complex component (A) has a concentration of the transition metal atom in the polymerization reaction system of usually 10 ^-8 to 10 ^-1 gram atom / liter, preferably 10 ^{-7 to} 5 × 10 ^-2 gram atom / liter. Is preferably used in an amount of The atomic ratio (Al / transition metal) of the transition metal in the component (A) to the aluminum in the component (B) and / or the component (C) is usually 1 to 10000, preferably 1 to 5000, and more preferably Is preferably 1 to 1000.

The polymerization pressure is usually from atmospheric pressure to 100 kg.
/ Cm ² , preferably under normal pressure to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. At the time of olefin polymerization, α-olefin may be prepolymerized with an olefin polymerization catalyst.

[0077]

The (A) transition metal complex component and (B) organoaluminum oxy compound component and / or
Alternatively, by polymerizing various olefins in the presence of the organoaluminum compound component (C), a polymer having high polymerization activity and a narrow molecular weight distribution can be obtained. Further, when two or more kinds of monomers are copolymerized, a copolymer having a narrow composition distribution can be obtained.

[0078]

EXAMPLES The olefin polymerization catalyst and the olefin polymerization method according to the present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

[Synthesis of Transition Metal Complex Catalyst]

[0080]

Experimental Example 1 (Production of Compound [Z-1]) Zirconium chloride (2.48 g, was added to a 200 ml four-necked round bottom flask purged with nitrogen.
(10.6 mmol) and benzene (50 ml) were added, and the mixture was stirred at 50 ° C. 2,6-di-tert-butylphenol (2.2
A solution of 0 g, 10.6 mmol) in benzene (10 ml) was slowly added dropwise. After completion of dropping, reflux was performed. After 6 hours, the reaction was stopped, the temperature was returned to room temperature, filtration was performed, and the solvent of the filtrate was distilled off under reduced pressure to obtain a transition metal complex.

[0081]

Experimental Example 2 (Production of Compound [Z-1 ′]) Sodium hydride (40
% Oil, 770 mg) and sodium 2,6-di-tert-butylphenol (2.063 g, 10.0 mmol) 2,
6-di-tert-butylphenoxide was prepared. Zirconium chloride (2.33 g, 10.0 mmol) and 50 ml of benzene were added to a 200 ml four-neck round bottom flask with nitrogen substitution, and the benzene slurry of sodium 2,6-di-tert-butylphenoxide was added thereto. Refluxed.
After 6 hours, the reaction was stopped, the temperature was returned to room temperature, filtration was performed, and the solvent of the filtrate was distilled off under reduced pressure to obtain a transition metal complex.

[0082]

Experimental Example 3 (Production of Compound [Z-1 ″]) Sodium hydride (75
mmol) and 2,6-di-tert-butylphenol (10.3
Sodium 2,6-di-tert-butylphenoxide was prepared from 1 g, 50.0 mmol). To this THF solution was added trimethylsilyl chloride (6.53 ml, 50.0 mmol). The mixture was stirred overnight at room temperature and filtered, and the solvent of the filtrate was evaporated under reduced pressure to synthesize trimethylsilyl 2,6-di-tert-butylphenoxide.

Zirconium chloride (2.421 g, 10.39 mmo) was placed in a 200 ml four-neck round bottom flask which had been purged with nitrogen.
l) and 40 ml of benzene were added, and trimethylsilyl was added at room temperature.
2,6-di-tert-butylphenoxide (2.89 g, 10.
A solution of 39 mmol) in benzene (20 ml) was slowly added dropwise. After completion of dropping, reflux was performed. After 8 hours, the reaction was stopped, the temperature was returned to room temperature, filtration was performed, and the solvent of the filtrate was distilled off under reduced pressure to obtain a transition metal complex.

[0084]

Experimental Example 4 (Production of compound [Z-2]) Nitrogen-substituted 200 ml 4
Zirconium chloride (3.57 g, 1
5.32 mmol) and 60 ml of benzene were added, and 2,6-
Di-phenylphenol (3.773g, 15.32mmo
A solution of l) in benzene (40 ml) was slowly added dropwise. After completion of dropping, reflux was carried out for 4 hours, filtration was performed, and the insoluble solid was dried under reduced pressure to obtain a transition metal complex.

[0085]

Experimental Example 5 (Production of compound [Z-3]) Nitrogen-substituted 200 ml 4
Zirconium chloride (2.70 g, 1
(1.59 mmol) and benzene (50 ml) were added, and triphenylcarbinol (3.016 g, 11.59 mmol) was added at room temperature.
Benzene (10 ml) solution was slowly added dropwise. After completion of dropping, reflux was carried out for 3.5 hours, filtration was performed, and the insoluble solid was dried under reduced pressure to obtain a transition metal complex.

[0086]

Experimental Example 6 (Production of compound [Z-4]) Nitrogen-substituted 200 ml 4
Zirconium chloride (2.052 g,
8.805 mmol) and diethyl ether (50 ml) were added, and silver trifluoromethanesulfonate (2.2
A solution of 62 g (8.805 mmol) in benzene (50 ml) was added, and the reaction was carried out in the dark. After 2 hours, the solution was filtered and the filtrate was evaporated under reduced pressure. Then benzene (40m
l) was added, and 2,6-di-phenylphenol (2.
A solution of 169 g (8.805 mmol) in benzene (40 ml) was slowly added dropwise. After completion of dropping, reflux was carried out for 10 hours, then the temperature was returned to room temperature, filtration was carried out, and the solvent of the filtrate was distilled off under reduced pressure to obtain a transition metal complex.

[Olefin Polymerization]

[0088]

Example 1 200 ml of purified toluene was put into a glass flask having an inner volume of 500 ml, which had been sufficiently replaced with nitrogen, and kept at 60 ° C. for 10 minutes while flowing ethylene at 100 liter / hr.

Then, 2 mg of methylaluminoxane (manufactured by Schling) was inserted in terms of aluminum atom. Further, the temperature was set to 60 ° C., and the transition metal complex obtained in Experimental Example 1 was inserted with 0.02 milligram atom in terms of zirconium atom. After carrying out the polymerization at 60 ° C. for 15 minutes, the polymerization was stopped by adding a large amount of methanol.

A small amount of dilute hydrochloric acid was added to the obtained polymer suspension and the mixture was filtered through a glass filter to remove toluene as a solvent, washed with acetone and dried under reduced pressure. The results of the polymerization are shown in Table 1.

[0091]

Examples 2 to 5 Example 1 was repeated except that the transition metal complex shown in Table 1 was used instead of the transition metal complex obtained in Experimental Example 1 and the time polymerization was changed as shown in Table 1. Ethylene was polymerized in the same manner.

The results of the polymerization are shown in Table 1.

[0093]

Example 6 200 ml of purified toluene was placed in a glass flask having an inner volume of 500 ml which had been sufficiently replaced with nitrogen, and the mixture was kept at 60 ° C. for 10 minutes while flowing ethylene at 100 liter / hr.

Then, a hexane solution of triethylaluminum was inserted by 0.4 mg atom in terms of aluminum atom. Further, the temperature was set to 60 ° C., and the transition metal complex obtained in Experimental Example 1 was inserted with 0.04 milligram atom in terms of zirconium atom. After carrying out the polymerization at 60 ° C. for 15 minutes, the polymerization was stopped by adding a large amount of methanol.

A small amount of dilute hydrochloric acid was added to the obtained polymer suspension and the mixture was filtered through a glass filter to remove toluene as a solvent, washed with acetone and dried under reduced pressure. The results of the polymerization are shown in Table 1.

[0096]

Examples 7 to 11 Example 6 was repeated except that the transition metal complex shown in Table 1 was used in place of the transition metal complex obtained in Experimental Example 1 and the time polymerization was changed as shown in Table 1. Ethylene was polymerized in the same manner.

The results of the polymerization are shown in Table 1.

[0098]

[Table 1]

Continued Front Page (72) Inventor Shuji Minami 580-32, Takuji Nagaura, Sodegaura City, Chiba Prefecture 32 Mitsui Petrochemical Industry Co., Ltd.

Claims (4)

[Claims] 1. A transition metal complex component represented by the following general formula [I]: R ² _a R ³ _b R ⁴ _c M (OR ¹ ) ... [I] (wherein M is zirconium or hafnium). Yes, R
¹ has 6 or more carbon atoms, an aryl group, a naphthyl group,
A fluorene group or —CR ¹¹ R ¹² R ¹³ ; R ¹¹ and R
¹² , R ¹³ are hydrogen, an alkyl group, an aryl group or an aralkyl group, which may be the same or different,
At least two of R ¹¹ , R ¹² , and R ¹³ are alkyl groups, aryl groups, or aralkyl groups. Further, the above alkyl group, aryl group and naphthyl group may be substituted with an alkyl group or an aryl group, and also has a hetero atom-containing substituent such as halogen, oxygen, nitrogen, phosphorus, sulfur and silicon. May be. R ² and R ³ are —OR ¹ , halogen or —SO ₃ R ⁵ , and R ⁴ is halogen or —SO ₃ R ⁵ . R ⁵ is an alkyl group, an alkyl group substituted with halogen, an aryl group, a halogen atom or an aryl group substituted with an alkyl group. In addition, -OR
^When two or more ^1's exist, two of them -O
R ¹ may be linked via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, oxygen or sulfur. Further, c ≧ 1 and a + b + c = 3. ) And (B) an organoaluminum oxy compound component represented by the following general formula [II]: (In the formula, R ⁶ is an alkyl group, and n is an integer. This compound may be branched or may form a ring.)
An olefin polymerization catalyst comprising: 2. A transition metal complex component represented by the following general formula [I]: R ² _a R ³ _b R ⁴ _c M (OR ¹ ) ... [I] (wherein M is zirconium or hafnium). Yes, R
¹ has 6 or more carbon atoms, an aryl group, a naphthyl group,
A fluorene group or —CR ¹¹ R ¹² R ¹³ ; R ¹¹ and R
¹² , R ¹³ are hydrogen, an alkyl group, an aryl group or an aralkyl group, which may be the same or different,
At least two of R ¹¹ , R ¹² , and R ¹³ are alkyl groups, aryl groups, or aralkyl groups. The above-mentioned alkyl group, aryl group and naphthyl group may be substituted with an alkyl group or an aryl group, and have a hetero atom-containing substituent such as halogen, oxygen, nitrogen, phosphorus, sulfur and silicon. May be. R ² and R ³ are —OR ¹ , halogen or —SO ₃ R ⁵ , and R ⁴ is halogen or —SO ₃ R ⁵ . R ⁵ is an alkyl group, an alkyl group substituted with halogen, an aryl group, a halogen atom or an aryl group substituted with an alkyl group. In addition, -OR
^When two or more ^1's exist, two of them -O
R ¹ may be linked via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, oxygen or sulfur. Further, c ≧ 1 and a + b + c = 3. ) And (C) an organoaluminum compound component. 3. A transition metal complex component represented by the following general formula [I]: R ² _a R ³ _b R ⁴ _c M (OR ¹ ) ... [I] (wherein M is zirconium or hafnium). Yes, R
¹ has 6 or more carbon atoms, an aryl group, a naphthyl group,
A fluorene group or —CR ¹¹ R ¹² R ¹³ ; R ¹¹ and R
¹² , R ¹³ are hydrogen, an alkyl group, an aryl group or an aralkyl group, which may be the same or different,
At least two of R ¹¹ , R ¹² , and R ¹³ are alkyl groups, aryl groups, or aralkyl groups. The above-mentioned alkyl group, aryl group and naphthyl group may be substituted with an alkyl group or an aryl group, and have a hetero atom-containing substituent such as halogen, oxygen, nitrogen, phosphorus, sulfur and silicon. May be. R ² and R ³ are —OR ¹ , halogen or —SO ₃ R ⁵ , and R ⁴ is halogen or —SO ₃ R ⁵ . R ⁵ is an alkyl group, an alkyl group substituted with halogen, an aryl group, a halogen atom or an aryl group substituted with an alkyl group. In addition, -OR
^When two or more ^1's exist, two of them -O
R ¹ may be linked via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, oxygen or sulfur. Further, c ≧ 1 and a + b + c = 3. ) (B) Organoaluminum oxy compound component represented by the following general formula [II]: (In the formula, R ⁶ is an alkyl group, and n is an integer. This compound may be branched or may form a ring.)
And a catalyst for olefin polymerization, which comprises (C) an organoaluminum compound component. 4. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.