JP3070256B2 - Method for producing olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an olefin polymer using an olefin polymerization catalyst containing a metallocene compound, an organoaluminum compound and an ionized ionic compound as constituents.

[0002]

BACKGROUND OF THE INVENTION The polymerization of ethylene or common alpha-olefins by the low pressure Ziegler process is well known in the art. Catalysts used for this purpose include transition metals mixed with organometallic compounds or hydrides of elements of Groups 1-A to 3-A of the Periodic Table (3-B of the Periodic Table).
It is generally made by operating a compound of Group II to Group 2-B) in a suspension or solution, or in the absence of a solvent or diluent.

A special class of well-known catalysts active in the polymerization of olefins is the combination of an aluminoxane and a cyclopentadienyl derivative of a metal such as titanium, zirconium or hafnium (Group 4-B). Ziegler-Natta Catalysts and Polymerization "Academic.
Press. New York (1979), Ad
v. Organomet. Chem. 1899
These catalysts have the advantage of high catalytic activity and the ability to produce stereoregular polyolefins. However, the main reason that has hindered the industrial use of these catalysts on a large scale so far is that it is basically difficult to synthesize aluminoxanes and obtain them in reproducible form, and That is, it was difficult to prepare a catalyst and polymers having reproducible characteristics.

Japanese Patent Application Laid-Open No. 3-207704 discloses a bis (cyclopentadienyl) produced by reacting a metallocene compound with an ionized ionic compound.
Metal compounds are described and it is disclosed that such complexes can be used advantageously as catalysts for olefin polymerization. However, this catalyst was not satisfactory in terms of activity.

[0005]

An object of the present invention is to provide an olefin polymerization catalyst having excellent activity.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a boron compound is added to a catalyst system comprising a metallocene compound, an organoaluminum compound and an ionized ionic compound. As a result, a catalyst system having excellent activity was obtained, and the present invention was completed. That is, the present invention
(A) Metallocene compound, (B) organoaluminum compound and (C) ionized ionic compound are constituents, and metallocene compound (A) is represented by the following general formula (1)

[0007]

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Wherein Cp ¹ and Cp ² are each independently a cyclopentadienyl or substituted cyclopentadienyl group, and R ¹ is an alkylene group having 1 to 4 carbon atoms, dialkyl
Silanediyl group, dialkylgermandiyl group, alkyl
A ruphosphinediyl group or an alkylimino group ,
R ¹ acts to bridge Cp ¹ and Cp ² , m is 0 or 1, M is titanium, zirconium or hafnium, and X is fluorine, chlorine, bromine or iodine.] Wherein the organoaluminum compound (B) is represented by the following general formula (2)

[0009]

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Wherein R ² is a halogen, hydrogen, alkyl, alkoxy or aryl group, each R ² may be the same or different, and at least one R ² is an alkyl group. And the ionized ionic compound (C) is represented by the following general formula (3)

[0011]

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[Wherein [C] is a cation and [A]
Is an anion.] In the method for producing an olefin polymer using the olefin polymerization catalyst system represented by the general formula (4), the boron compound (D) represented by the following general formula (4)

[0013]

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[Wherein R ³ is a halogen, hydrogen, alkyl, alkoxy or aryl group, and each R ³ may be the same or different] with respect to (A) the metallocene compound.
A method for producing an olefin polymer, characterized by adding 0.01 to 0.8 times mol .

Hereinafter, the present invention will be described in detail.

The metallocene compound (A) used in the present invention is represented by the general formula (1). Specific examples of these compounds include bis (cyclopentadienyl)
Titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (tetrahydroindenyl) titanium dichloride,
Isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethyl silanediyl <br/> bis (methylcyclopentadienyl) titanium dichloride, dimethyl silanediyl bis (2,4-dimethyl cyclopentadienyl) titanium dichloride, bis ( Cyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethyl silanediyl bis (methylcyclohexyl pentadienyl) zirconium dichloride, dimethyl silanediyl bis (2,4-dimethyl-cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, ethylenebis (indenyl ) Hafnium dichloride, ethylene bis (tetrahydroindenyl) hafnium dichloride, iso Ropiriden (cyclopentadienyl) (fluorenyl) hafnium dichloride, dimethyl silanediyl bis (methylcyclopentadienyl)
Hafnium dichloride, dimethyl silanediyl bis (2,4-dimethyl-cyclopentadienyl) may be mentioned hafnium dichloride and the like.

The organoaluminum compound (B) is represented by the general formula (2). Specific examples of these compounds include trimethylaluminum, triethylaluminum, triisopropylaluminum, tri (n-
Propyl) aluminum, triisobutylaluminum, tri (n-butyl) aluminum, tri (n-hexyl) aluminum, tri (n-octyl) aluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, di (n-propyl) Aluminum chloride, diisobutyl aluminum chloride, di (n-butyl)
Aluminum chloride, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum ethoxide, di (n-propyl)
Aluminum ethoxide, diisobutylaluminum ethoxide, di (n-butyl) aluminum ethoxide, dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum ethoxide, di (n-propyl) aluminum hydride, diisobutylaluminum hydride, di (n-butyl) ) Aluminum hydride and the like can be exemplified.

The ionized ionic compound (C) is represented by the general formula (3). Specific examples of these compounds include tri (n-butyl) ammonium tetrakis (p-tolyl) borate, Tri (n-butyl) ammonium tetrakis (m-tolyl) borate, tri (n-butyl) ammonium
Butyl) ammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium tetrakis (p-tolyl) borate; N, N-dimethylanilinium tetrakis (m-tolyl) borate;
N-dimethylanilinium tetrakis (2,4-dimethylphenyl) borate, N, N-dimethylanilinium tetrakis (3,5-dimethylphenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (p-tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4-dimethylphenyl) borate, triphenylcarbenium tetrakis (3,5-dimethylphenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tropylium tetrakis (p-tolyl) )
, Tropylium tetrakis (m-tolyl) borate,
Tropylium tetrakis (2,4-dimethylphenyl)
Borate, tropylium tetrakis (3,5-dimethylphenyl) borate, tropylium tetrakis (pentafluorophenyl) borate and the like can be exemplified . Et al is a boron compound (D), but is represented by the general formula (4), as these specific compounds, trifluoroborane, trichloroborane, tribromoborane, trimethyl borane, triethyl borane, tri-isopropyl borane , Tri (n-propyl) borane, triisobutylborane, tri (n-butyl) borane, triphenylborane, tri (pentafluorophenyl) borane and the like.

In the practice of the present invention, for example, a metallocene compound (A) and an organoaluminum compound (B) are mixed with an olefin. The reaction can be performed by bringing the mixture into contact with the ionized ionic compound (C) to which the boron compound (D) is added. At this time, the molar ratio of the metallocene compound (A) to the ionized ionic compound (C) is 1: 0.2 to 1: 100, preferably 1: 1 to 1:10.
Range. The amount of the boron compound (D) added is
0.01 to 0.8 times m with respect to the metallocene compound (A)
is a ol, and more preferably 0.05 to 0.5 times mo
l, which significantly enhances the activity of the catalyst system. On the other hand, the boron compound (D) is increased by 0.01 times mo
When used less than 1 or more than 0.8 times mol,
The activity of the catalyst may be extremely low.

The preferred concentration of the organoaluminum compound used in the present invention is from 10 ^-5 to 10 ^-3 mol / l.

The olefin may be any of olefins. Specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene,
Α-olefins such as octene, and a mixture of two or more of these components can be used for polymerization. Furthermore, butadiene, 1,5-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,
Copolymerization with conjugated and non-conjugated dienes such as 9-decadiene, styrene or cyclic olefins such as cyclopropene, cyclohexene, norbornene, dicyclopentadiene and the like is also possible.

The polymerization of the olefin in the present invention is carried out by a known means in the polymerization of an olefin using a metallocene compound, for example, polymerization in bulk, slurry or gas phase. The polymerization temperature is in the range of -80 to 150C, preferably 25 to 80C.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.66 mmol of triethylaluminum was added, followed by stirring for 10 minutes. To this solution, 1.3 μmol of ethylenebis (indenyl) zirconium dichloride was added as a 1 ml toluene solution, and the mixed solution was stirred for 20 minutes. 500 ml of propylene was inserted into the mixture, and the mixture was stirred for 10 minutes. 1.3 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and 0.13 μmol of tris (pentafluorophenyl) borane
Was injected into an autoclave using 10 ml of toluene, and polymerization was carried out at 40 ° C. for 1 hour. The reaction product was dried at about 70 ° C. under vacuum for 6 hours. As a result, 160 g of a propylene polymer was obtained.

Comparative Example 1 The same operation as in Example 1 was performed except that tris (pentafluorophenyl) borane was not added. As a result, 95 g of a propylene polymer was obtained.

Comparative Example 2 The same operation as in Example 1 was performed except that the amount of tris (pentafluorophenyl) borane was changed to 1.3 μmol. As a result, 21 g of a propylene polymer was obtained.

Example 2 To a 2 l autoclave was added 500 ml of toluene, and then 0.66 mmol of triethylaluminum was added, followed by stirring for 10 minutes. To this solution, 5 μmol of isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride was added as a 1 ml toluene solution, and the mixed solution was stirred for 20 minutes. To this propylene 500
ml, and stirred for 10 minutes. 6.6 .mu.mol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and 0.66 .mu.mol of tris (pentafluorophenyl) borane were pressed into an autoclave with 10 ml of toluene. Polymerization was carried out for hours. The reaction product was dried at about 70 ° C. under vacuum for 6 hours. As a result, 95 g of a propylene polymer was obtained.

Comparative Example 3 The same operation as in Example 2 was performed except that tris (pentafluorophenyl) borane was not added. As a result, 20 g of a propylene polymer was obtained.

Comparative Example 4 The same operation as in Example 2 was performed except that the amount of tris (pentafluorophenyl) borane was changed to 6.6 μmol. As a result, 15 g of a propylene polymer was obtained.

[0030]

As described above, the metallocene compound,
By adding a boron compound to an olefin polymerization catalyst comprising an organoaluminum compound and an ionized ionic compound, an olefin polymer having very high activity can be efficiently obtained.

Claims (1)

(57) [Claims] 1. A metallocene compound (A) comprising a metallocene compound (A), an organoaluminum compound (B) and an ionized ionic compound (C), and a metallocene compound (A) represented by the following general formula (1): Wherein Cp ¹ and Cp ² are each independently a cyclopentadienyl or substituted cyclopentadienyl group, and R ¹ is an alkylene group having 1 to 4 carbon atoms, a dialkylsilanediyl group, a dialkylgermandiyl group, An alkylphosphinediyl or alkylimino group, R ¹ acts to bridge Cp ¹ and Cp ² , m is 0 or 1, M is titanium, zirconium or hafnium, and X is Which is fluorine, chlorine, bromine or iodine], and the organoaluminum compound (B) is represented by the following general formula (2): Wherein R ² is a halogen, hydrogen, alkyl, alkoxy or aryl group, each R ² may be the same or different, and at least one R ² is an alkyl group. The ionic compound (C) is represented by the following general formula (3): [Wherein [C] is a cation and [A] is an anion] In a method for producing an olefin polymer using an olefin polymerization catalyst system represented by the following general formula (4): (D) boron compound Wherein, R ³ is halogen, hydrogen, alkyl, alkoxy or ants - a group, each R ³ may be the same or different] 0.01 against the metallocene compound (A)
A method for producing an olefin polymer, wherein 0.8 times mol is added.