JP3132179B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates, of the periodic table containing a phosphorus atom and to a cyclic compound having a π electron as a ligand I
The present invention relates to a catalyst system containing a transition metal compound comprising a transition metal of Group VA , an organoaluminum compound and an ionized ionic compound, and a method for producing a polyolefin in the presence of the catalyst system.

[0002]

2. Description of the Related Art Various polymerization methods and catalyst systems are known for the polymerization of olefins. A conventional Ziegler-Natta catalyst system composed of a transition metal compound using an aluminum alkyl as a co-catalyst has a high molecular weight distribution. It is known that high molecular weight polyolefins can be produced.

Recently, a catalyst system containing a transition metal compound containing a cyclopentadienyl derivative as a ligand (generally called a metallocene compound) has been developed. This catalyst system acts as a polymerization catalyst for olefins. In particular, metallocene composed of a transition metal of Group IVA of titanium, zirconium or hafnium is used for the production of polyethylene and ethylene copolymers, and aluminoxane is used as a cocatalyst. It has been found that polyolefins can be produced with high activity (for example, JP-A-58-19309).

Many studies have been made on catalyst systems containing aluminoxane and a group IVA metallocene compound having various cyclopentadienyl derivatives as ligands, and various substituents are introduced into the cyclopentadienyl group. This also revealed that the three-dimensional structure, composition distribution, production efficiency and the like of the produced polymer can be controlled (for example, JP-A-61-26491, JP-A-64-51).
408, JP-A-64-66216, JP-A-1-301704, Am. Chem. So
c. 1988, 110, 6255-62).

[0005] The polymer obtained here has characteristics such as a narrow molecular weight distribution and a uniform composition distribution during copolymerization. However, during polymerization, high activity is obtained unless a large amount of aluminoxane is used as a co-catalyst. Some problems still remain, such as not being able to obtain. Then, in order to solve these problems, the necessity of developing a new catalyst system is increasing.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve this problem, and it is an object of the present invention to provide a catalyst capable of efficiently producing a polyolefin having excellent physical properties and processability, and a method for producing a polyolefin using the same. To provide.

[0007]

Means for Solving the Problems Mercy et al. Have reported several transition metal compounds containing as a ligand a phosphoryl group having an electronic structure similar to that of a cyclopentadienyl group. Organometallics, 198.
8,7,921, IVA having a phosphoryl group
Group transition metal compounds have been reported. This compound is similar to the metallocene compound, which is the main catalyst of the above-mentioned catalyst system, in the electronic state around the central transition metal, but has not been applied to an olefin polymerization catalyst.

As a result of intensive studies, the present inventors have determined that a transition metal compound containing a heteroatom and having a π electron as a ligand is used in the presence of an organoaluminum compound and an ionized ionic compound. In, it is found that polymerization activity is expressed for olefin,
The present invention has been completed.

That is, the present invention provides a compound represented by I of the periodic table having a cyclic compound containing a phosphorus atom and having a π electron as a ligand.
Transition metal compound (A) represented by general formula (1) consisting of a transition metal of group VA

[0010]

Embedded image (Where M is a member of group IVA of the periodic table)Transition metal,
R¹, R^Two, R^ThreeAnd R^FourIs hydrogen, silyl group or charcoal
A hydrogen group;^FiveMay be the same or different
, Hydrogen, halogen, silyl group, alkyl group, aryl
Group, aralkyl group, alkoxide, amide, phosphide
Or sulfide, n is an integer of 1-3, m
Is an integer of 0 to 4) represented by the following general formula (2)
Aluminum compound (B)

[0011]

Embedded image (However, R ⁶ , R ^{6 ′} , and R ^{6 ″} may be the same or different, and each is a hydrogen, a halogen, an amide, an alkylalkoxy group, a hydrocarbon group, and at least one is a hydrocarbon group.) And a catalyst for olefin polymerization comprising an ionized ionic compound (C) comprising a cation component selected from Bronsted acid, carbonium, oxonium or sulfonium cation and an anion component which is a borate anion, and the presence of the above-mentioned olefin polymerization catalyst The present invention relates to a method for producing a polyolefin, which comprises polymerizing an olefin below.

Hereinafter, the present invention will be described in detail.

The transition metal compound (A) as a catalyst component used in the present invention contains, as a ligand, a cyclic compound containing a phosphorus atom represented by the general formula (1) and having π electrons. Where M is a transition of group IVA of the periodic table
Metal .

[0014]

R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a silyl group, or a hydrocarbon group. Examples of the silyl group include trimethylsilyl, triethylsilyl, butylsilyl, phenylsilyl, and diphenyl. silyl group, and a triphenylsilyl group such as methyl group and examples of the hydrocarbon group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a toluyl group, a cyclohexyl group, a benzyl group And the like.

Further, compounds having a cyclic carbon skeleton as shown in Chemical formulas 7 to 16, such as a phosphoindenyl group and a phosphofluorenyl group, can also be used as the ligand.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

Embedded image ( Wherein R ′ and R ″ are each hydrogen, a silyl group or a hydrocarbon group such as an alkyl group, an aryl group, an aralkyl group, etc.) The above compound is bonded to a transition metal by a phosphorus atom and / or a carbon atom. , For stabilizing the transition metal compound represented by the general formula (1).

R ⁵ may be the same or different and each represents hydrogen, a halogen, a silyl group, an alkyl group, an aryl group, an aralkyl group, an alkoxide, an aryl oxide,
Amide, a phosphide or sulfide, fluorine As an example, chlorine, bromine, iodine, trimethylsilyl group, triethylsilyl group, butylsilyl group, triphenylsilyl group, butyldiphenylsilyl, triphenylsilyl group,
Methyl, ethyl, propyl, butyl, hexyl , octyl, phenyl, toluyl, cyclohexyl, benzyl, methoxy, ethoxy, dimethylamide, dimethylphosphide, methylsulfide, etc. Can be mentioned.

As specific examples , bis (phosphoryl) titanium dimethyl, bis (phosphoryl) zirconium dimethyl, bis (phosphoryl) hafnium dimethyl, bis (phosphoryl) titanium dichloride, bis (phosphoryl) zirconium dichloride, bis (phosphoryl) hafnium Dichloride , bis (2-methylphosphoryl) titanium dimethyl, bis (2-methylphosphoryl) zirconium dimethyl, bis (2-methylphosphoryl) hafnium dimethyl, bis (2-methylphosphoryl) titanium dichloride, bis (2-methylphosphoryl) zirconium dichloride, bis (2-Mechiruhosuhoriru) hafnium dichloride, bis (3-Mechiruhosuhoriru) titanium dimethyl, bis (3-Mechiruhosuhoriru) zirconia Mujimechiru, bis (3-Mechiruhosuhoriru) hafnium dimethyl, bis (3-Mechiruhosuhoriru) titanium dichloride, bis (3-Mechiruhosuhoriru) zirconium dichloride, bis (3-Mechiruhosuhoriru) hafnium dichloride, bis (2,
3-dimethylphosphoryl) titanium dimethyl, bis (2,3-dimethylphosphoryl) zirconium dimethyl, bis (2,3-dimethylphosphoryl) hafnium dimethyl, bis (2,3-dimethylphosphoryl) titanium dichloride, bis (2,3- Dimethyl phosphoryl)
Zirconium dichloride, bis (2,3-dimethylphosphoryl) hafnium dichloride , bis (2,4-dimethylphosphoryl) titanium dimethyl, bis (2,4
-Dimethylphosphoryl) zirconium dimethyl, bis (2,4-dimethylphosphoryl) hafnium dimethyl,
Bis (2,4-dimethylphosphoryl) titanium dichloride, bis (2,4-dimethylphosphoryl) zirconium dichloride, bis (2,4-dimethylphosphoryl) hafnium dichloride , bis (2,5-dimethylphosphoryl) titanium dimethyl, bis ( 2,5-dimethylphosphoryl) zirconium dimethyl, bis (2,5
-Dimethylphosphoryl) hafnium dimethyl, bis (2,5-dimethylphosphoryl) titanium dichloride, bis (2,5-dimethylphosphoryl) zirconium dichloride, bis (2,5-dimethylphosphoryl) hafnium dichloride , bis (3,4-dimethyl Phosphoryl) titanium dimethyl, bis (3,4-dimethylphosphoryl) zirconium dimethyl, bis (3,4-dimethylphosphoryl) hafnium dimethyl, bis (3,4-
Dimethylphosphoryl) titanium dichloride, bis (3,4-dimethylphosphoryl) zirconium dichloride, bis (3,4-dimethylphosphoryl) hafnium dichloride , bis (2,3,4-trimethylphosphoryl) titanium dimethyl, bis (2,3 4-trimethylphosphoryl) zirconium dimethyl, bis (2,3,
4-trimethylphosphoryl) hafnium dimethyl, bis (2,3,4-trimethylphosphoryl) titanium dichloride, bis (2,3,4-trimethylphosphoryl)
Zirconium dichloride, bis (2,3,4-trimethylphosphoryl) hafnium dichloride , bis (2
3,5-trimethylphosphoryl) titanium dimethyl,
Bis (2,3,5-trimethylphosphoryl) zirconium dimethyl, bis (2,3,5-trimethylphosphoryl) hafnium dimethyl, bis (2,3,5-trimethylphosphoryl) titanium dichloride, bis (2
3,5-trimethylphosphoryl) zirconium dichloride, bis (2,3,5-trimethylphosphoryl) hafnium dichloride , bis (2,3,4,5-tetramethylphosphoryl) titanium dimethyl, bis (2,3
4,5-tetramethylphosphoryl) zirconium dimethyl, bis (2,3,4,5-tetramethylphosphoryl)
Hafnium dimethyl, bis (2,3,4,5-tetramethylphosphoryl) titanium dichloride, bis (2
3,4,5-tetramethylphosphoryl) zirconium dichloride, bis (2,3,4,5-tetramethylphosphoryl) hafnium dichloride and the like,
It is not limited to these.

The organoaluminum compound (B) used here is represented by the general formula (2), wherein R ⁶ , R ^{6 ′} and R ^{6 ″} may be the same or different, and may be hydrogen, halogen, amide, alkyl or the like. An alkoxy group and a hydrocarbon group, at least one of which is a hydrocarbon group, such as trimethylaluminum, triethylaluminum, tributylaluminum, triisopropylaluminum, diisopropylaluminum chloride, isopropylaluminum dichloride, triisobutylaluminum, Diisobutylaluminum chloride, isobutylaluminum dichloride, tri-t-butylaluminum, di-t-butylaluminum chloride, t
-Butyl aluminum dichloride, triamyl aluminum, diamyl aluminum chloride, amyl aluminum dichloride and the like.

The ionized ionic compound (C) used as a component of the catalyst of the present invention includes a Bronsted acid,
Carbonium, oxonium or sulfonium kathio
Consisting of a cation component and an anion component selected from
Specifically, trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, N, N-
Dimethylanilinium, N, N-diethylanilinium, N, N-2,4,5-pentamethylanilinium,
Examples of Bronsted acids represented by triphenylphosphonium, tri (o-tolyl) phosphonium, tri (p-tolyl) phosphonium, tri (mesityl) phosphonium, etc., or carbonium, oxonium or sulfonium cations containing no active proton Examples include compounds represented by phenylcarbenium, tropylium ion, and the like, but are not limited thereto.

The anion components are [AlR ₄ ⁻ ], [B
R ₄ ⁻ ], [PR ₆ ⁻ ] or [ClO ₄ ⁻ ], specifically, tetraphenyl borate, tetrakis (pentafluorophenyl) borate, tetrakis (2-fluorophenyl) borate, tetrakis ( 4-
(Fluorophenyl) borate, tetrakis (3-fluorophenyl) borate, tetrakis (3,5-difluorophenyl) borate, tetrakis (2,5-difluorophenyl) borate, tetrakis (2,6-difluorophenyl) borate, tetrakis (2 -Tolyl) borate, tetrakis (4-tolyl) borate, tetrakis (3,5-dimethylphenyl) borate, tetrakis (2,5-dimethylphenyl) borate, octadecaborate, dodecaborate, 1-carboundecaborate, 1 Borate anions such as but not limited to carbadodecaborate, but are not limited thereto.

In the catalyst of the present invention, the transition metal compound (A) and the ionized ionic compound (C) which are constituents
Is not particularly limited, but the molar ratio of the transition metal compound (A) to the ionized ionic compound (C) is preferably in the range of 1: 0.01 to 1: 1000, and particularly preferably 1: 0. .2 to 1: 200. The amount of the organoaluminum compound (B) used here is not particularly limited.

The olefin used in the polymerization reaction of the present invention is ethylene, propylene, 1-butene, 4-methyl-1-.
Α-olefins such as pentene and 1-hexene; conjugated and non-conjugated dienes such as butadiene and 1,4-hexadiene; and cyclic olefins such as styrene and cyclobutene, and a mixture of two or more of these can also be used.

The olefin polymerization in the present invention can be carried out in a liquid phase or a gas phase. If the polymerization is carried out in the liquid phase, any solvent may be used as long as it is a commonly used organic solvent.Specifically, benzene, toluene, xylene, pentane, hexane, dichloromethane and the like can be mentioned, or the olefin itself can be used. It can also be used as a solvent.

Although the polymerization temperature is not particularly limited, it is -100 to -100.
It is preferable to carry out in the range of 230 ° C.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

All reactions are performed in an inert gas atmosphere.
All solvents used in the reaction were purified by a known method in advance,
The dried and deoxidized one was used.

The molecular weight of the polyolefin obtained in the present invention can be determined by gel permeation chromatography (GP).
C) (Waters 150C type), using a column of TSK-gel GMH, a sample volume of 350 μl, a column temperature of 140 ° C., and a flow rate of 1 ml / min.

Reference Example Synthesis of "1-phenyl-2,3,4,5-tetramethylphosphol" 17.44 g of 2-butyne was added to 250 ml of dichloromethane.
Was added to a suspension of 22.7 g of aluminum chloride in 250 ml of dichloromethane and cooled to -10 ° C. The temperature of the mixed solution obtained here was raised to complete the reaction. The reaction solution was cooled again, and a solution prepared by dissolving 31.7 g of dichlorophenylphosphine in 250 ml of dichloromethane was added. further,
39 ml of n-butylphosphine was added to dichloromethane 350
The solution dissolved in ml was added to complete the reaction. After work-up and distillation under reduced pressure, 24 g of the desired product was obtained.

Synthesis of "bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride" 1-phenyl-2,3,50 ml of tetrahydrofuran was added to 50 ml of tetrahydrofuran.
2.27 g of 4,5-tetramethylphosphor was added, and 0.47 g of lithium was further added to cause a reaction to remove excess lithium. Aluminum chloride was added to the reaction solution to neutralize phenyllithium generated by the reaction, and 1.17 g of zirconium chloride suspended in 10 ml of toluene was added. 2.3 g of an orange solid was obtained from the reaction solution.

Example 1 500 ml of toluene was added to a 2 l autoclave,
To this was added 0.25 mmol of triisobutylaluminum and 1.1 mg of the above bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride. Further, 10 mg of anilinium tetrakispentafluorophenyl borate was made into a 10 ml toluene solution and added to the autoclave. After stirring this solution for several minutes, polymerization was carried out at 60 ° C. for 1 hour while supplying ethylene to the autoclave so that the ethylene pressure became 8 kg / cm ² G. As a result, 22.6 g of granular polyethylene (melting point: 137 ° C., weight average molecular weight (Mw): 640)
000).

Example 2 The procedure of Example 1 was repeated except that 11 mg of triphenylcarbonium tetrakispentafluorophenylborate was used instead of anilinium tetrakispentafluorophenylborate. As a result, 33 g of polyethylene was obtained.

Example 3 The same procedure as in Example 2 was carried out except that trimethylaluminum was used instead of triisobutylaluminum. As a result, 2.7 g of polyethylene was obtained.

Example 4 In a 5 l autoclave, 600 ml of toluene and 1
200 ml of hexene, 0.25 mmol of triisobutylaluminum and the above bis (2,2
2.2 mg of (3,4,5-tetramethylphosphoryl) zirconium dichloride was added. Further, 8.1 m of anilinium tetrakispentafluorophenyl borate
g in a 10 ml toluene solution and added to the autoclave. After stirring this solution for several minutes, polymerization was carried out at 60 ° C. for 1 hour while supplying ethylene to the autoclave so that the ethylene pressure became 8 kg / cm ² G. As a result, 6
3.7 g of a powdery polymer were obtained.

Example 5 600 ml of toluene and 1 ml were placed in a 5 l autoclave.
-Hexene (25 ml) was added thereto, and triisobutylaluminum (0.25 mmol) and the above bis (2,2
2.2 mg of (3,4,5-tetramethylphosphoryl) zirconium dichloride was added. Further, 8.1 m of anilinium tetrakispentafluorophenyl borate
g in a 10 ml toluene solution and added to the autoclave. After stirring this solution for several minutes, polymerization was carried out at 60 ° C. for 1 hour while supplying ethylene to the autoclave so that the ethylene pressure became 8 kg / cm ² G. As a result, 5
5.4 g of a granular polymer (melting point: 129 ° C., weight average molecular weight (Mw): 84,000) was obtained.

[0046]

According to the present invention, a transition metal compound belonging to the group IVA of the periodic table having a phosphorus atom-containing compound as a ligand is used as a main catalyst, and is reacted in the presence of an ionized ionic compound and an organoaluminum compound. By polymerizing an olefin, a polyolefin exhibiting high activity and having excellent shape, physical properties, and the like of the produced polymer can be produced.

Claims (2)

(57) [Claims] 1. A transition metal compound (A) represented by the general formula (1) wherein a ligand is a cyclic compound containing a phosphorus atom and having π electrons. (Where M is a transition metal of Group IVA of the periodic table,
R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a silyl group or a hydrocarbon group, and R ⁵ may be the same or different and each represents hydrogen, halogen, silyl group, alkyl group, aryl group, aralkyl Group, alkoxide, amide, phosphide or sulfide, n is an integer of 1-3, m
Is an integer of 0 to 4). An organoaluminum compound (B) represented by the following general formula (2): (However, R ⁶ , R ^{6 ′} , and R ^{6 ″} may be the same or different, and each is a hydrogen, a halogen, an amide, an alkylalkoxy group, a hydrocarbon group, and at least one is a hydrocarbon group.) An olefin polymerization catalyst comprising, as constituent components, an ionized ionic compound (C) comprising a cation component selected from a Bronsted acid, carbonium, oxonium or sulfonium cation and an anion component which is a borate anion . 2. A method for producing a polyolefin, comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.