JPH06239913A - Catalyst for polymerizing olefin and method for polymerizing olefin - Google Patents

Abstract

(57) [Summary] [Structure] A transition metal compound represented by the following formula and (M ¹ is a transition metal, Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton, R is a hydrocarbon group having 4 or more carbon atoms, and may have a substituent such as an alkyl group. May have a substituent bonded to each other to form a ring.) An olefin polymerization catalyst comprising an organoaluminum oxy compound. A method for polymerizing an olefin in which an olefin is polymerized in the presence of the above catalyst. [Effect] Excellent polymerization activity, large molecular weight and dispersity (Mw
A polyolefin having a small / Mn) is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for polymerizing an olefin, and more specifically, an olefin polymerization catalyst comprising a specific transition metal compound and an organoaluminum oxy compound, and an olefin in the presence of this catalyst. It relates to a method of polymerizing.

[0002]

BACKGROUND OF THE INVENTION As a conventional method for producing an olefin (co) polymer, there is known a method of polymerizing an olefin using a catalyst comprising a transition metal compound and an organometallic compound, a so-called Ziegler type catalyst. ing. For example, a titanium-based catalyst composed of a titanium compound and an organoaluminum compound, or a vanadium-based catalyst composed of a vanadium compound and an organoaluminum compound is known.

Generally, an olefin (co) polymer obtained with a titanium catalyst has excellent physical properties, but has a wide molecular weight distribution (dispersion degree, Mw / Mn) and composition distribution, and also has transparency and surface Adhesiveness and mechanical properties are not sufficient.
Olefin-based (co) polymers obtained with vanadium-based catalysts have narrower molecular weight distribution and composition distribution than those obtained with titanium-based catalysts, and transparency, surface non-adhesion and mechanical properties are significantly improved. However, they are still insufficient for applications where these performances are required, and there is a demand for a catalyst that can obtain an olefin (co) polymer with improved performance.

Further, a catalyst composed of a metallocene compound such as zirconocene and an aluminoxane (organoaluminumoxy compound) is known. For example, JP-A-58-19309, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35.
JP-A-61-130314 and JP-A-2-41303 disclose a combination of a metallocene compound of a transition metal compound having an alkyl group and / or a halogen atom as a ligand with an aluminoxane. It is described that the above catalyst systems are highly active in the polymerization of α-olefins, and the properties of the obtained polymers are excellent. However, the polymer obtained by such a catalyst has a narrow molecular weight distribution, but has a problem of low molecular weight.

Under these circumstances, the advent of a catalyst having excellent olefin polymerization activity and excellent properties of the obtained polyolefin, particularly a new olefin polymerization catalyst capable of obtaining a polyolefin having a large molecular weight, and a method for producing the same are desired. .

[0006]

The present invention has excellent olefin polymerization activity,
Moreover, it is an object of the present invention to provide an olefin polymerization catalyst and a method for polymerizing an olefin that can obtain a polyolefin having a large molecular weight and a narrow molecular weight distribution.

[0007]

SUMMARY OF THE INVENTION An olefin polymerization catalyst according to the present invention comprises (A) a transition metal compound represented by the following formula [I]:

[0008]

[Chemical 3]

(In the formula, M ¹ is a transition metal of Group IVB of the periodic table, Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and these have a cyclopentadienyl skeleton. The group may have a substituent, and C
p ¹ and Cp ² may be bonded via an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group.
R is a saturated or unsaturated hydrocarbon group having 4 or more carbon atoms, and may have a substituent such as an alkyl group, an aryl group, a silyl group, a stannyl group, and a germyl group,
These substituents may be bonded to each other to form a ring, and the ring may have a double bond. (B) An organoaluminum oxy compound.

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

[0011]

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

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

The olefin polymerization catalyst according to the present invention is formed from a transition metal compound (A) represented by the following formula [I] and an organoaluminum oxy compound (B). First, the transition metal compound (A) will be described.

The transition metal compound (A) used in the present invention
Is a transition metal compound represented by the following formula [I].

[0015]

[Chemical 4]

In the above formula [I], M ¹ is a transition metal of Group IVB of the Periodic Table, specifically, zirconium, titanium or hafnium. Cp ¹ and Cp
² is a group having a cyclopentadienyl skeleton, and examples of the group having a cyclopentadienyl skeleton include cyclopentadienyl group; methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclo Examples include alkyldisubstituted cyclopentadienyl groups such as pentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group; indenyl group, fluorenyl group and the like.

Of these, cyclopentadienyl group is preferred. These groups having a cyclopentadienyl skeleton, Cp ¹ and Cp ² , may be bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like.

Examples of the alkylene group include ethylene group and propylene group, and examples of the substituted alkylene group include:
Examples thereof include an isopropylidene group and a diphenylmethylene group, and examples of the substituted silylene group include a dimethylsilylene group.

The ring skeleton represented by R is a saturated or unsaturated hydrocarbon group having 4 or more carbon atoms, preferably 4 to 10 carbon atoms. Specifically, a saturated hydrocarbon group such as a tetramethylene group; butenylene And unsaturated hydrocarbon groups such as groups.

The hydrocarbon group forming the ring skeleton represented by R may have a substituent such as an alkyl group, an aryl group, a silyl group, a stannyl group and a germyl group. When it has more than one ring, two substituents may be bonded to each other to form a ring such as a five-membered ring or a six-membered ring, and this ring may have a double bond. Moreover, this ring may contain O, N, S, P, and Si atoms.

Examples of the alkyl group substituting for R include an alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group and decyl group. Exemplified, these groups may be substituted with halogen.

Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as phenyl group, tolyl group and naphthyl group. These groups are halogen, or alkyl groups having 1 to 10 carbon atoms, or It may be substituted with an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

As the silyl group, SiR ^a R ^b R ^C (R ^a ,
R ^b and R ^C can be exemplified by a group represented by an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and specific examples include a trimethylsilyl group and a triphenylsilyl group. Can be mentioned.

Examples of the stannyl group include SnR ^a R ^b R
A group represented by ^C (R ^a , R ^b , and R ^C are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 12 carbon atoms) can be exemplified, and specifically, trimethylstannyl Group, triphenylstannyl group and the like.

As the germyl group, GeR ^a R ^b R
A group represented by ^C (R ^a , R ^b , and R ^C are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 12 carbon atoms) can be exemplified, and specifically, trimethylgermyl Group, triphenylgermyl group and the like.

As the group represented by R in the formula [I],
More specifically, the groups represented by the following formulas [i] to [vi] can be exemplified.

[0027]

[Chemical 5]

[Wherein R¹~ R^FourAre the same or different
May be a hydrogen atom or an atom having 1 to 10 carbon atoms.
C 1 to 1 carbon atoms substituted with a rualkyl group or a halogen atom
0 alkyl group, aryl group having 6 to 10 carbon atoms,
Substituted with a rogen atom, alkyl group, or alkoxy group
An aryl group having 6 to 40 carbon atoms, or M²R^aR
^bR^CGroup (M²Is Si, Sn or Ge, and R^a,
R^b, R^CIs an alkyl group having 1 to 12 carbon atoms or carbon
And an aryl group having 6 to 12 atoms). Also R¹When
R ², And / or R³And R^FourConnect to each other to form a ring
May be formed, and this ring may have a double bond.
Good. ]

[0029]

[Chemical 6]

[In the formula, X is a hydrocarbon group having 3 to 20 carbon atoms and may contain O, N, Si, S, and P atoms. R ⁵ and R ⁶ may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, and 6 to 6 carbon atoms. 10 aryl groups, halogen atoms,
An alkyl group or an aryl group having 6 to 40 carbon atoms which is substituted with an alkoxy group, or an M ² R ^a R ^b R ^C group (M ²
Is Si, Sn or Ge, and R ^a , R ^b and R ^C are alkyl groups having 1 to 12 carbon atoms or 6 to 12 carbon atoms.
The aryl group of is shown. ]

[0031]

[Chemical 7]

[Wherein R⁷~ R¹⁴Are the same or different
May be a hydrogen atom or an atom having 1 to 10 carbon atoms.
C 1 to 1 carbon atoms substituted with a rualkyl group or a halogen atom
0 alkyl group, aryl group having 6 to 10 carbon atoms,
Substituted with a rogen atom, alkyl group, or alkoxy group
An aryl group having 6 to 40 carbon atoms, or M²R^aR
^bR^CGroup (M²Is Si, Sn or Ge, and R^a,
R^b, R^CIs an alkyl group having 1 to 12 carbon atoms or carbon
And an aryl group having 6 to 12 atoms). Also R⁷(Also
Is R⁸) And R⁹(Or R^Ten), And / or R
¹¹(Or R¹²) And R¹³(Or R¹⁴) Are bound to each other
To form a ring, and this ring has a double bond
You may stay. ]

[0033]

[Chemical 8]

[In the formula, Y is a hydrocarbon group having 3 to 20 carbon atoms and may contain O, N, Si, S, and P atoms. R ^{15 to} R ²⁰ may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, or 6 to 10 carbon atoms. 10 aryl groups, halogen atoms,
An alkyl group or an aryl group having 6 to 40 carbon atoms which is substituted with an alkoxy group, or an M ² R ^a R ^b R ^C group (M ²
Is Si, Sn or Ge, and R ^a , R ^b and R ^C are alkyl groups having 1 to 12 carbon atoms or 6 to 12 carbon atoms.
The aryl group of is shown. Also, R ¹⁵ (or R ¹⁶ ) and R
¹⁷ , and / or R ¹⁸ and R ¹⁹ (or R ²⁰ ) may be bonded to each other to form a ring, and the ring may have a double bond. ]

[0035]

[Chemical 9]

[In the formula, R^{twenty one}~ R²⁶Are the same or different
May be a hydrogen atom or an atom having 1 to 10 carbon atoms.
C 1 to 1 carbon atoms substituted with a rualkyl group or a halogen atom
0 alkyl group, aryl group having 6 to 10 carbon atoms,
Substituted with a rogen atom, alkyl group, or alkoxy group
An aryl group having 6 to 40 carbon atoms, or M²R^aR
^bR^CGroup (M²Is Si, Sn or Ge, and R^a,
R^b, R^CIs an alkyl group having 1 to 12 carbon atoms or carbon
And an aryl group having 6 to 12 atoms). Also, R^{twenty one}And R
^{twenty two}, And / or R^{twenty three}(Or R^{twenty four}) And R^{twenty five}(Or
R²⁶) May combine with each other to form a ring.
The ring may have a double bond. ]

[0037]

[Chemical 10]

[In the formula, Z is a hydrocarbon group having 3 to 20 carbon atoms and may contain O, N, Si, S and P atoms. R ^{27 to} R ³⁰ may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, or 6 to 6 carbon atoms. 10 aryl groups, halogen atoms,
An alkyl group or an aryl group having 6 to 40 carbon atoms which is substituted with an alkoxy group, or an M ² R ^a R ^b R ^C group (M ²
Is Si, Sn or Ge, and R ^a , R ^b and R ^C are alkyl groups having 1 to 12 carbon atoms or 6 to 12 carbon atoms.
The aryl group of is shown. Also, R ²⁹ (or R ³⁰ ) and R
²⁸ may be bonded to each other to form a ring, and this ring may have a double bond. ] Specific examples of the transition metal compound represented by the above formula [I] are shown below.

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

In the above example, zirconium is
A compound in which titanium or hafnium is replaced can also be used. [Production Method] The transition metal compound represented by the above formula [I] is, for example, the following (A-1), (A-2) and (A-3)
It can be prepared by contacting a compound selected from the group consisting of (hereinafter sometimes referred to as “group A”) and a hydrocarbon compound having a double bond or a triple bond in a solvent. (A-1) Compound represented by the following formula [II]

[0043]

[Chemical 14]

(In the formula, Cp ¹ , Cp ² and M ¹ are the same as defined in the formula [I], and R ³¹ and R ³² are
It is an alkyl group having 2 to 10 carbon atoms. (A-2) A compound represented by the following formula [III] is added to Na / Hg,
Compounds obtained by reduction with Na / naphthalene, Mg / HgCl _2, etc.

[0045]

[Chemical 15]

(In the formula, Cp ¹ , Cp ² and M ¹ are the same as defined in the formula [I], and X ¹ and X ² are halogen atoms.) (A-3) The following formula [IV ] The compound obtained by photolyzing the compound represented by

[0047]

[Chemical 16]

(In the formula, Cp ¹ , Cp ² and M ¹ are the same as defined in the formula [I].) More specifically, the transition metal compound represented by the formula [I] will be described later. It can be prepared by such a method. (1) When the transition metal compound is a compound represented by the following formula [Ii],

[0049]

[Chemical 17]

(In the formula, Cp ¹ , Cp ² and M ¹ are the same as the definition in the formula [I], and R ^{1 to} R ⁴ are the same as the definition in the formula [i].) For example, A above. It can be prepared by contacting a compound selected from the group with a compound or mixture represented by the following [V] in a solvent.

R ¹ -C≡C-R ² and / or R ³ -C≡C-R ⁴ ... [V] (wherein R ^{1 to} R ⁴ are the same as defined in the formula [i]. ) (2) When the transition metal compound is a compound represented by the following formula [I-ii],

[0052]

[Chemical 18]

(In the formula, Cp ¹ , Cp ² and M ¹ are the same as defined in the formula [I], and R ⁵ , R ⁶ and X
Is the same as the definition in formula [ii]. ) For example, it can be prepared by contacting a compound selected from Group A above with a compound represented by the following formula [VI] in a solvent.

R ⁵ -C≡C—X—C—C—R ⁶ ... [VI] (In the formula, R ⁵ , R ⁶ and X have the same definitions as in formula [ii].) (3) When the transition metal compound is a compound represented by the following formula [I-iii],

[0055]

[Chemical 19]

(In the formula, Cp ¹ , Cp ² and M ¹ are the same as defined in the formula [I], and R ^{7 to} R ¹⁴ are the same as those in the formula [i.
The definition is the same as in [ii]. ) For example, it can be prepared by contacting a compound selected from Group A above with a compound or mixture represented by the following [VII] in a solvent.

[0057]

[Chemical 20]

(In the formula, R ^{7 to} R ¹⁴ are the same as defined in the formula [iii].) (4) When the transition metal compound is a compound represented by the following formula [I-iv]: ,

[0059]

[Chemical 21]

(In the formula, Cp ¹ , Cp ² and M ¹ are the same as defined in the formula [I], and R ^{15 to} R ²⁰ and Y
Is the same as the definition in formula [iv]. ) For example, it can be prepared by contacting a compound selected from Group A above with a compound represented by the following formula [VIII] in a solvent.

[0061]

[Chemical formula 22]

(In the formula, R ^{15 to} R ²⁰ and Y are represented by the formula [iv]
Is the same as the definition in. (5) When the transition metal compound is a compound represented by the following formula [Iv],

[0063]

[Chemical formula 23]

(In the formula, Cp ¹ , Cp ² and M ¹ are the same as the definition in the formula [I], and R ^{21 to} R ²⁶ are the same as the definition in the formula [v].) For example, A above. Mixture [IX] of a compound selected from the group, a compound represented by the following [IX ′], and a compound represented by the following formula [IX ″]
It can be prepared by contacting and in a solvent.

[0065]

[Chemical formula 24]

(In the formula, R ^{21 to} R ²⁶ are the same as defined in the formula [v].) (6) When the transition metal compound is a compound represented by the following formula [I-vi] ,

[0067]

[Chemical 25]

(In the formula, Cp ¹ , Cp ² and M ¹ are the same as defined in the formula [I], and R ^{27 to} R ³⁰ and Z
Is the same as the definition in formula [vi]. ) For example, it can be prepared by contacting a compound selected from Group A above with a compound represented by the following formula [X] in a solvent.

[0069]

[Chemical formula 26]

(Wherein R ^{27 to} R ³⁰ and Z are represented by the formula [vi]
Is the same as the definition in. ) When the compound selected from the group A and the compound or mixture selected from the above [V] to [X] are brought into contact with each other, it varies depending on the composition of the transition metal compound to be obtained. The compound or mixture selected from X] is used in an amount of 1 to 10 times mol, preferably 1 to 2 times mol, relative to 1 mol of the transition metal of the compound selected from Group A above.

The reaction temperature is -10 to 180 ° C,
The reaction time is preferably -80 to 120 ° C, and the reaction time is 0.1 to 48 hours, preferably 0.5 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, Ethers such as diethyl ether and tetrahydrofuran are used. Of these, tetrahydrofuran is 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 selected from the group A.

The transition metal compound can be prepared in good yield by the above-mentioned production method. The transition metal compound thus obtained can be filtered and recrystallized by concentrating the obtained filtrate under reduced pressure, or can be isolated and purified by a method such as sublimation.

For these reactions, Tetrahedoron L
etters, 27 , (25), 2829-2832 (1986), and Journal of A
American Chemical Society, 111 , 3336-3346 (1989), Jou
rnalof American Chemical Society, 96 , 5936-5937 (197
4) and so on. Furthermore, Cp ₂ ZrPh ₂ ,
For the method of preparing from a transition metal compound represented by Cp ₂ Zr (CH ₃ ) Cl or Cp ₂ Zr (H) Cl, see Chemical.
Reviews, 88 , (7), 1047-1058 (1988).

Next, the organoaluminum oxy compound (B) used together with the above transition metal compound (A) in the olefin polymerization catalyst of the present invention will be explained. Organoaluminum oxy compound (B) used in the present invention
May be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

The conventionally known aluminoxane can be prepared, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same.

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

(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 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 preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum 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; and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

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

[0082] _{(i-C 4 H 9)} X Al y (C 5 H 10) Z ... [XI] ( wherein, x, y and z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds are used alone or in combination.

Solvents used for preparing 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. Hydrocarbons, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons,
Alicyclic hydrocarbon halides, especially hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The benzene-insoluble organoaluminum oxy compound which can be used in the present invention is obtained by a method of bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound, or the above-mentioned organoaluminum compound and water. Can be obtained by a method of contacting with. Such a benzene-insoluble organoaluminum oxy compound has an Al component soluble in benzene at 60 ° C. of 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atom, and is insoluble in benzene. Alternatively, it is poorly soluble.

The organoaluminum oxy compound (B) as described above is usually commercially available or handled as a toluene solution. The organoaluminum oxy compound (B) used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum.

The olefin polymerization catalyst composed of the transition metal compound (A) and the organoaluminum oxy compound (B) has excellent olefin polymerization activity, and the olefin polymer obtained has a large molecular weight and a molecular weight distribution (Mw). /
Mn) is narrow.

The above transition metal compound (A)
And / or organoaluminum oxy compound (B)
May be supported on a carrier before use. The olefin polymerization catalyst according to the present invention is formed from the transition metal compound (A) and the organoaluminum oxy compound (B) as described above, and together with the organoaluminum compound (C), if necessary. May be.

Such an organoaluminum compound (C)
For example, an organoaluminum compound represented by the following formula [XII] can be exemplified. During ^{_{R m n AlX 3-n ...}} [XII] ( wherein, R ^m is a hydrocarbon group having 1 to 12 carbon atoms,
X is a halogen atom or a hydrogen atom, and n is 1 to
It is 3. ) In the above formula [XII], R ^m is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n -Propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

As the organoaluminum compound (C),
Specifically, the following compounds are used. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum,
Trialkyl aluminum such as trioctyl aluminum and tri-2-ethylhexyl aluminum; alkenyl aluminum such as isoprenyl aluminum; dialkyl aluminum halide such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide; methyl aluminum Alkyl aluminum sesquihalides such as sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminium Alkylaluminum dihalides such as Mujiburomido diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (C), a compound represented by the following formula [XIII] can be used. During ^{_{R d n AlW 3-n ...}} [XIII] ( wherein, R ^d is the same as above, W is, -OR
^e group, -OSiR ^f ₃ group, -OAlR ^g ₂ group, -NR ^h ₂ group,-
SiR ⁱ ₃ group or —N (R ^j ) AlR ^k ₂ group, and n is
1-2, R ^e , R ^f , R ^g and R ^k are methyl groups,
It is an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., R ^h is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ⁱ and R ^j are Examples include a methyl group and an ethyl group. ) Specific examples of the organoaluminum compound represented by the above formula [XIII] include the following compounds. (1) A compound represented by R ^d _n Al (OR ^e ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (2) R ^d _n Al (OSiR ^f ₃ ) _{3 -n} , such as Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OS
iMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc .; (3) Compounds represented by R ^d _n Al (OAlR ^g ₂ ) _3-n , such as Et ₂ AlOAiLet ₂ , (iso-Bu) ₂ AlOAl (iso-
Bu) _{2, ^{etc.; (4) R d n Al}} (NR h 2) a compound represented by _3-n, e.g., _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlNHE
t, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiM
e ₃ ) _{2 and the} like; (5) a compound represented by R ^d _n Al (SiR ⁱ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe _{3 and the} like; (6) R ^d _n Al (N (R ^j ) A compound represented by AlR ^k ₂ ) _3-n , for example, Et ₂ AlN (Me) AlEt ₂ , (iso-Bu)
₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Among the organoaluminum compounds represented by the above formulas [XII] and [XIII], R ^d ₃ Al and R ^d _n Al
A compound represented by (OR ^e ) _3-n and R ^d _n Al (OAlR ^g ₂ ) _3-n is preferable, and R is an isoalkyl group, and n
Compounds with = 2 are preferred.

[Polymerization Method] The olefin polymerization method according to the present invention is carried out in the presence of the above-mentioned transition metal compound (A), organoaluminum oxy compound (B) and, if necessary, an organoaluminum compound (C). Polymerize olefins.

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.

Specifically as the hydrocarbon medium, butane,
Isobutane, pentane, hexane, octane, decane,
Aliphatic hydrocarbons such as dodecane, hexadecane, octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cyclooctane; 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 compound (A) is usually added at a concentration of 10 in the polymerization reaction system. It is desirable to use ^-8 to 10 ^-1 gram atom / liter, preferably 10 ^{-7 to} 5 × 10 ^-2 gram atom / liter. Atomic ratio of transition metal in transition metal compound (A) to aluminum in organoaluminum oxy compound (B) (Al / transition metal)
Is usually 10 to 10,000, preferably 20 to 5,000.
Is desirable. In addition, an aluminum atom (Al-
C) and the aluminum atom (Al-B) atomic ratio (Al-C / Al-B) of the organoaluminum oxy compound (B) are usually in the range of 0.02 to 3, preferably in the range of 0.05 to 1.5. Is.

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. The olefins that can be polymerized by the olefin polymerization method according to the present invention include ethylene and α-C3-20.
Olefins 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; 3 to 20 carbon atoms
Cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,
Examples include 3,4,4a, 5,8,8a-octahydronaphthalene. Furthermore, styrene, vinyl cyclohexane,
Various dienes and the like can also be used.

In the present invention, α-olefin may be preliminarily polymerized with the olefin polymerization catalyst in the polymerization of olefin. In the prepolymerization, the olefin polymer is 0.05 to 500 g, preferably 0.1 to 300 g, and more preferably 0.2 to 100 g per 1 g of the olefin polymerization catalyst.
Is preferably prepolymerized in an amount of.

As the olefin for the prepolymerization, ethylene and α-olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,
Examples thereof include 1-tetradecene, 3-methyl-1-butene, 3-methyl-1-pentene and the like. Of these, preferred are olefins used during polymerization.

[0101]

According to the olefin polymerization catalyst and the olefin polymerization method of the present invention, a polyolefin having excellent polymerization activity, a large molecular weight and a narrow molecular weight distribution can be obtained.

[0102]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

In the present invention, the intrinsic viscosity [η] and the molecular weight distribution are measured as follows. [Intrinsic viscosity [η]] Measured in decalin at 135 ℃, dl /
It is shown by g.

[Molecular weight distribution (dispersion degree, Mw / Mn)] It was measured by gel permeation chromatography (GPC) under conditions of o-dichlorobenzene and 140 ° C.

[0105]

[Production example]

(Synthesis of Zirconium Compound [Ia]) 10 ml of dry tetrahydrofuran (THF) and 0.88 zirconocene dichloride were placed in a glass container sufficiently purged with argon.
g (3.0 mmol) was charged and stirred at room temperature until uniform.

Then, this was cooled to −78 ° C., 3.6 ml (6.0 mmol) of n-hexane solution of n-butyllithium was added dropwise, and the mixture was stirred at the same temperature for 1 hour. 5 ml of a THF solution of 1.07 g (6.0 mmol) of diphenylacetylene was added dropwise to this reaction solution at -78 ° C, and the mixture was stirred at room temperature for 3 hours.
The reaction continued for an hour.

Then, the solvent was removed under reduced pressure, 10 ml of benzene was added, and the mixture was filtered through a glass filter under a nitrogen stream to remove the produced salt. When the obtained solid was recrystallized from toluene, 0.40 g of orange crystals were obtained (yield: 23%). The structure of the zirconium compound [Ia] was determined based on its ¹ H-NMR.

(Synthesis of Zirconium Compound [Ib]) Dry THF 1 was placed in a glass container sufficiently purged with argon.
0 ml and 0.59 g (2.0 mmol) of zirconocene dichloride were charged and stirred at room temperature until uniform.

Then, this was cooled to -78 ° C. and 2.3 ml (4.0 mmol) of n-butyllithium solution in n-hexane.
Was added dropwise, and the mixture was stirred at the same temperature for 1 hour. 1, in this reaction solution
8-bis (trimethylsilyl) -1,7-octadiyne 0.58
After g (2.0 mmol) was added dropwise at -78 ° C, the reaction was continued at room temperature for 3 hours.

Then, the solvent was removed under reduced pressure, 10 ml of benzene was added, and the mixture was filtered through a glass filter under a nitrogen stream to remove the produced salt. The obtained solid was recrystallized from n-hexane to give 0.24 g of yellow-orange crystals.
Was obtained (yield; 25%). The structure of the zirconium compound [Ib] was determined based on its ¹ H-NMR.

(Synthesis of Zirconium Compound [Ic]) Dry THF 1 was placed in a glass container sufficiently purged with argon.
0 ml and 0.59 g (2.0 mmol) of zirconocene dichloride were charged and stirred at room temperature until uniform.

Then, this was cooled to -78 ° C. and 2.5 ml (4.0 mmol) of n-butyllithium solution in n-hexane.
Was added dropwise, and the mixture was stirred at the same temperature for 1 hour. 2, in this reaction solution
2,11,11-Tetramethyl-3,9-dodecadineine 0.44g
After adding 2 ml of a THF solution of (2.0 mmol) at -78 ° C, the reaction was continued at room temperature for 3 hours.

Then, the solvent was removed under reduced pressure, 10 ml of benzene was added, and the mixture was filtered through a glass filter under a nitrogen stream to remove the produced salt. When the obtained solid was recrystallized from n-hexane, 0.31 g of orange crystals were obtained (yield: 35%). The structure of the zirconium compound [Ic] was determined based on its ¹ H-NMR.

(Synthesis of Zirconium Compound [Id]) Dry THF 1 was placed in a glass container sufficiently purged with argon.
0 ml and 0.59 g (2.0 mmol) of zirconocene dichloride were charged and stirred at room temperature until uniform.

Then, this was cooled to -78 ° C., 2.5 ml (4.0 mmol) of an n-hexane solution of n-butyllithium was added dropwise, and the mixture was stirred at the same temperature for 1 hour. To this reaction solution was added 0.27 g (2.0 mmol) of THF, 2,8-decadiyne.
After 2 ml of the solution was added dropwise at -78 ° C, the reaction was continued at room temperature for 3 hours.

Then, the solvent was removed under reduced pressure to obtain 0.45 g of a reddish brown oil (yield: 68%). The structure of the zirconium compound [Id] was determined based on its ¹ H-NMR.

(Synthesis of Zirconium Compound [Ie]) Dry THF 1 was placed in a glass container sufficiently purged with argon.
0 ml and 0.59 g (2.0 mmol) of zirconocene dichloride were charged and stirred at room temperature until uniform.

Then, this was cooled to -78 ° C., 2.5 ml (4.0 mmol) of an n-hexane solution of n-butyllithium was added dropwise, and the mixture was stirred at the same temperature for 1 hour. 0.52 g (2.0 g of 1,8-diphenyl-1,7-octadiyne) was added to the reaction solution.
After adding 2 ml of a THF solution of (mmol) at −78 ° C., the reaction was continued at room temperature for 3 hours.

Then, the solvent was removed under reduced pressure, 10 ml of benzene was added, and the mixture was filtered through a glass filter under a nitrogen stream to remove the produced salt. When the obtained solid was recrystallized from a mixture of toluene and n-hexane, 0.36 g of red crystals were obtained (yield: 38%). The structure of the zirconium compound [Ie] was determined based on its ¹ H-NMR.

[0120]

[Example 1] (Polymerization of ethylene) Internal volume of 500 m with sufficient nitrogen substitution
200 ml of purified toluene was placed in a glass flask having a volume of 1 l and the temperature was raised to 60 ° C. while flowing ethylene at 100 l / hr.

Then, methylaluminoxane (MA
O) in terms of aluminum atoms of 0.75 × 10 ⁻³ mol,
Next, the zirconium compound [Ia] prepared in the above Production Example
^Was added in an amount of 1.0 × 10 ^-6 mol to initiate polymerization.

After keeping the polymerization temperature at 60 ° C. and conducting the polymerization for 5 minutes, the polymerization was stopped by adding methanol. After adding a small amount of hydrochloric acid to the obtained polymer suspension and filtering, the obtained polyethylene was washed with acetone and dried under reduced pressure.

The yield, intrinsic viscosity and molecular weight distribution of the obtained polyethylene are shown in Table 1.

[0124]

Examples 2 to 5 (Polymerization of ethylene) In Example 1, except that the zirconium compound shown in Table 1 was used in place of the zirconium compound [Ia] and the polymerization time was changed to the time shown in Table 1, Ethylene was polymerized in the same manner as in 1.

Table 1 shows the yield, intrinsic viscosity and molecular weight distribution of the obtained polyethylene.

[0126]

[Reference Example 1] (Polymerization of ethylene) Fully nitrogen-substituted internal volume of 500 m
200 ml of purified toluene was placed in a glass flask having a volume of 1 l and the temperature was raised to 60 ° C. while flowing ethylene at 100 l / hr.

Then, methylaluminoxane was added in an amount of 0.60 × 10 ^-3 mol in terms of aluminum atom, and then bis (cyclopentadienyl) zirconium dichloride was added in an amount of 0.8 × 10 ^-6 mol to initiate polymerization.

The polymerization temperature was kept at 60 ° C., the polymerization was carried out for 2 minutes, and then the polymerization was stopped by adding methanol. A small amount of hydrochloric acid was added to the obtained polymer suspension, and after filtration, the obtained polyethylene was washed with acetone and dried under reduced pressure.

The yield, intrinsic viscosity and molecular weight distribution of the obtained polyethylene are shown in Table 1.

[0130]

[Reference Example 2] (Polymerization of ethylene) Inner volume of 500 m with sufficient nitrogen substitution
200 ml of purified toluene was placed in a glass flask having a volume of 1 l and the temperature was raised to 60 ° C. while flowing ethylene at 100 l / hr.

Then, 0.75 × 10 ^-3 mol of methylaluminoxane in terms of aluminum atom was added, and then bis (cyclopentadienyl) zirconium dimethyl was added in an amount of 1.
Polymerization was started by adding 0 × 10 ⁻⁶ mol.

The polymerization temperature was kept at 60 ° C., the polymerization was carried out for 1 minute, and then the polymerization was stopped by adding methanol. A small amount of hydrochloric acid was added to the obtained polymer suspension, and after filtration, the obtained polyethylene was washed with acetone and dried under reduced pressure.

The yield, intrinsic viscosity and molecular weight distribution of the obtained polyethylene are shown in Table 1.

[0134]

[Table 1]

[Brief description of drawings]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuji Minami 580-2 32 Takuji Nagaura, Sodegaura, Chiba Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (2)

[Claims] 1. A transition metal compound represented by the following formula [I]: (In the formula, M ¹ is a transition metal of Group IVB of the periodic table,
Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and these groups having a cyclopentadienyl skeleton may have a substituent, and Cp ¹ and Cp ² are alkylene groups. Alternatively, they may be bonded via a substituted alkylene group, a silylene group, or a substituted silylene group. R is a saturated or unsaturated hydrocarbon group having 4 or more carbon atoms,
It may have a substituent such as an alkyl group, an aryl group, a silyl group, a stannyl group, and a germyl group, and these substituents may be bonded to each other to form a ring. It may have a heavy bond. (B) An olefin polymerization catalyst comprising an organoaluminum oxy compound. 2. A transition metal compound represented by the following formula [I]: (In the formula, M ¹ is a transition metal of Group IVB of the periodic table,
Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and these groups having a cyclopentadienyl skeleton may have a substituent, and Cp ¹ and Cp ² are alkylene groups. , A substituted alkylene group, a silylene group, or a substituted silylene group may be bonded. R is a saturated or unsaturated hydrocarbon group having 4 or more carbon atoms,
It may have a substituent such as an alkyl group, an aryl group, a silyl group, a stannyl group, and a germyl group, and these substituents may be bonded to each other to form a ring. It may have a heavy bond. (B) A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of an olefin polymerization catalyst comprising an organoaluminum oxy compound.