JPH05320242A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To efficiently produce an olefin polymer at a high activity by polymerizing an olefin in the presence of a catalyst obtd. by adding a specific boron compd. to a catalyst system comprising a specific metallocene compd., a specific organoaluminum compd., and a specific ionizable compd. CONSTITUTION:An olefin is polymerized in the presence of a catalyst obtd. by adding a boron compd. of formula IV (wherein R<3> is halogen, hydrogen, alkyl, alkoxy, or aryl) to a catalyst system comprising a metallocene compd. of formula I (wherein Cp<1> and Cp<2> are each cyclopentadienyl, etc.; R<1> is 1-4C alkylene; m is 0 or 1; M is titanium, etc.; and X is fluorine, etc.), an organoaluminum compd. of formula II (wherein R<2> is fluorine, etc.), and an ioninizable compd. of formula II (wherein [C] is a cation; and [A] is an anion).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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]

Polymerization of ethylene or common α-olefins by the low pressure Ziegler method is well known in the art. The catalysts used for this purpose are transition metals mixed with organometallic compounds or hydrides of the elements of groups 1-A to 3 -A of the periodic table (table 3-B of the periodic table).
It is generally made by operating a compound of Group 2 to Group 2-B) in suspension or solution or in the absence of a solvent or diluent.

A well-known special type of catalyst active in the polymerization of olefins is the combination of an aluminoxane with a cyclopentadienyl derivative of a metal such as titanium, zirconium or hafnium (Group 4-B). Ziegler-Natta Catalyst and Polymerization "Academic.
Press. New York (1979), Ad
v. Organomet. Chem. 1899
(1980) and the like, 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, thus It was difficult to prepare catalysts and polymers that provided reproducible characteristics.

Further, in JP-A-3-207704, bis (cyclopentadienyl) produced by reacting a metallocene compound with an ionized ionic compound is disclosed.
Metal compounds are described and it is disclosed that such complexes can be advantageously used as catalysts for olefin polymerization. However, this catalyst was not satisfactory in terms of activity.

[0005]

SUMMARY OF THE INVENTION The present invention is to provide a catalyst for olefin polymerization which is excellent in activity.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a boron compound is added to a catalyst system composed of a metallocene compound, an organoaluminum compound and an ionized ionic compound. As a result, it was found that a catalyst system having excellent activity was obtained, and the present invention was completed. That is, the present invention is
(A) a metallocene compound, (B) an organoaluminum compound and (C) an ionizable ionic compound as constituent components, and the metallocene compound (A) is represented by the following general formula (1).

[0007]

[Chemical 5] [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 dialkylsilicon group, a dialkylgermanium group, an alkylphosphine group or an alkylamine group, and R ¹ is Cp ¹ and C
acting to crosslink p ² , m is 0 or 1, M is titanium, zirconium or hafnium, and X is fluorine, chlorine, bromine or iodine], an organoaluminum compound (B) is the following general formula (2)

[0008]

[Chemical 6] 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)

[0009]

[Chemical 7] [Wherein [C] is a cation and [A] is an anion] In the method for producing an olefin polymer using an olefin polymerization catalyst system, the above catalyst system is represented by the following general formula (4). (D) Boron compound

[0010]

[Chemical 8] [Wherein R ³ is a halogen, hydrogen, alkyl, alkoxy or aryl group, and each R ³ may be the same or different] is added to the method for producing an olefin polymer.

The present invention will be described in detail below.

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, dimethylsilylbis (methylcyclopentadienyl) titanium dichloride, dimethylsilylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) ) Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl Bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4-dimethylcyclo) Pentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (tetrahydroindenyl) hafnium dichloride, isopropylidene (cyclopenta) Dienyl) (fluorenyl)
Examples include hafnium dichloride, dimethylsilylbis (methylcyclopentadienyl) hafnium dichloride, dimethylsilylbis (2,4-dimethylcyclopentadienyl) 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 and tri (n-).
Propyl) aluminum, triisobutyl aluminum, tri (n-butyl) aluminum, tri (n-hexyl) aluminum, tri (n-octyl) aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum 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, diisobutyl aluminum ethoxide, di (n-butyl) aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, diisopropyl aluminum ethoxide, di (n-propyl) aluminum hydride, diisobutyl aluminum 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 tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate -N, N, N-dimethylanilinium tetrakis (p-tolyl) borate, N, N-dimethylanilinium tetrakis (m-tolyl) borate, N,
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) )
G, tropylium tetrakis (m-tolyl) borate,
Tropylium tetrakis (2,4-dimethylphenyl)
Examples thereof include borate, tropylium tetrakis (3,5-dimethylphenyl) borate and tropylium tetrakis (pentafluorophenyl) borate. Further, the boron compound (D) is represented by the general formula (4). Specific examples of these compounds include trifluoroborane, trichloroborane, tribromoborane, trimethylborane, triethylborane, triisopropylborane, and triborane. Examples thereof include (n-propyl) borane, triisobutylborane, tri (n-butyl) borane, triphenylborane and tri (pentafluorophenyl) borane.

In the practice of the present invention, for example, a metallocene compound (A) and an organoaluminum compound (B) are mixed with an olefin. This can be performed by bringing the ionized ionic compound (C) added with the boron compound (D) into contact with this mixture.

At this time, the molar ratio of the metallocene compound (A) to the ionized ionic compound (C) is 1: 0.2 to.
It is in the range of 1: 100, preferably 1: 1 to 1:10. The addition amount of the boron compound (D) is preferably 0.01 to 0.8 times mol, more preferably 0.05 to 0.5 times mol, of the metallocene compound (A). This significantly improves the activity of the catalyst system. On the other hand, when the boron compound (D) is used in an amount less than 0.01 times mol 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 10 ^-5 to 10 ^-3 mol / l.

The olefin may be any of olefins, and specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-
It is an α-olefin such as octene, and a mixed component of two or more kinds thereof can be subjected to 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.

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

[0020]

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.

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

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

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

Example 2 To 2 l of autoclave, 500 ml of toluene was added, and then 0.66 mmol of triethylaluminum was added and stirred 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. Propylene 500 to this
ml was added and stirred for 10 minutes. 6.6 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and 0.66 μmol of tris (pentafluorophenyl) borane were pressed into the autoclave with 10 ml of toluene, and the pressure was adjusted to 1 at 40 ° C. Polymerization was performed for a time. The reaction product was dried under vacuum at about 70 ° C. for 6 hours. As a result, 95 g of propylene polymer was obtained.

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

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

[0027]

As described above, the metallocene compound,
By adding the boron compound to the olefin polymerization catalyst composed of the organoaluminum compound and the ionized ionic compound, the olefin polymer can be efficiently obtained with extremely high activity.

Claims (1)

[Claims] 1. A metallocene compound (A), an organoaluminum compound (B) and an ionized ionic compound (C) as constituents, and the metallocene compound (A) is 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 dialkylsilicon group, a dialkylgermanium group, an alkylphosphine group or an alkylamine group, and R ¹ is Cp ¹ and C
acting to crosslink p ² , m is 0 or 1, M is titanium, zirconium or hafnium, and X is fluorine, chlorine, bromine or iodine], an organoaluminum compound (B) is 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 the method for producing an olefin polymer using an olefin polymerization catalyst system, the above catalyst system is represented by the following general formula (4). (D) Boron compound embedded image [In the formula, R ³ is a halogen, hydrogen, alkyl, alkoxy or aryl group, and each R ³ may be the same or different] is added, the method for producing an olefin polymer.