JP3033452B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst comprising a modified clay, a metallocene compound, and an organoaluminum compound, and a method for polymerizing an olefin using the catalyst.

[0002]

2. Description of the Related Art As a method for producing a polyolefin by polymerization of an olefin, it is already known to use a catalyst system comprising a combination of a transition metal compound and an organometallic compound. Also, according to Kaminsky et al., A catalyst system using a metallocene compound and methylaluminoxane,
It is described in JP-A-58-19309 and the like that it exhibits high activity in producing an olefin polymer containing propylene.

However, the catalyst system disclosed herein has excellent polymerization activity, but since the catalyst system is soluble in the reaction system, a solution polymerization system is often employed, and the production process is limited. Alternatively, in order to produce a polymer exhibiting industrially useful physical properties, it is necessary to use a relatively expensive methylaluminoxane in a large amount. Therefore, when these catalyst systems are used, there are problems such as cost and a problem that a large amount of aluminum remains in the polymer.

On the other hand, a catalyst system in which the above-mentioned soluble catalyst system is supported on an inorganic oxide carrier such as silica is disclosed in
No. 5006 discloses this. However,
Even when an olefin was polymerized according to the method described therein, the polymerization activity per methylaluminoxane was not sufficient.

[0005] As a method for improving these, for example, JP-A-4-8704, JP-A-4-11604,
JP-A-4-213305 discloses that a polymer having excellent polymerization activity and good particle properties can be obtained by performing gas phase polymerization using a catalyst system preliminarily polymerized using metallocene and a small amount of methylaluminoxane. Is disclosed. However, although the amount of methylaluminoxane used is small, the polymerization activity is still not satisfactory, and high activation of the catalyst system has been desired.

[0006] Recently, new cocatalysts which do not use an organoaluminum oxy compound such as methylaluminoxane have been studied. For example, Japanese Patent Application Laid-Open Nos. 1-501950 and 1-5020206 disclose a special boron catalyst. It is disclosed that the compound is an effective cocatalyst. However, these boron compounds are very complicated compounds and have not solved the problem of cost.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is inexpensive and excellent in polymerization activity without using an expensive organoaluminumoxy compound or boron compound in olefin polymerization. It is an object of the present invention to provide an olefin polymerization catalyst.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, treated a clay mineral with a compound capable of introducing a cation between its layers, and added a metallocene compound and an organic compound. It has been found that a catalyst capable of producing a polyolefin with high activity can be obtained by adding an aluminum compound, and the present invention has been completed.
That is, the present invention provides an olefin comprising a modified clay obtained by treating a clay mineral (a) with a compound (b) capable of introducing a cation between its layers, a metallocene compound (c) and an organoaluminum compound (d). An olefin is used as a polymerization catalyst or a modified clay obtained by treating a clay mineral (a) with a compound (b) capable of introducing a cation between its layers, and a catalyst component comprising a metallocene compound (c) and an organoaluminum compound (d). The present invention relates to an olefin polymerization catalyst comprising an olefin prepolymerization catalyst obtained by prepolymerization and an organoaluminum compound (e), and a method for producing a polyolefin using these catalysts. Hereinafter, the present invention will be described in detail.

The clay mineral (a) used in the present invention is fine particles mainly composed of microcrystalline silicate. Most of the clay minerals have a layered structure as a structural feature, and have various sizes of negative charges in the layer. In this point, it is greatly different from a metal oxide having a three-dimensional structure such as silica, alumina or zeolite. When the clay minerals are classified according to the magnitude of the negative charge shown above, a group of biophilite, kaolinite, dickalite, and talc in which the negative charge per chemical formula is 0, and smectite in which the negative charge is 0.25 to 0.6 group,
It can be divided into a vermiculite group of 0.6 to 0.9, a mica group of about 1 and a brittle mica group of about 2. Each group shown here contains various minerals. Examples of the smectite group include montmorillonite, beidellite, saponite, hectorite, and the like. Although these clay minerals exist in nature, those having few impurities can be obtained by artificial synthesis. In the present invention, all of the natural clay minerals shown here and clay minerals obtained by artificial synthesis can be used, and even those not mentioned above but all belonging to the definition of clay minerals can be used. .

[0010] The present invention allows introducing a cation into layers of the clay mineral used in the compound (b) is trimethyl ammonium as containing an active proton, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethyl Anilinium, N, N-
Diethylanilinium, N, N-2,4,5-pentamethylanilinium, triphenylphosphonium, tri (o-tolyl) phosphonium, tri (p-tolyl) phosphonium, tri (mesityl) phosphonium, dimethyloxonium, diethyl represented by oxonium like lube Ren slashed.nsted acid or to those not containing an active proton,
And triphenylcarbenium, tropylium ion, etc.
Carbonium, oxonium or sulfoni represented by
Cation, silver ion, ferrocenium ion
And a compound comprising an anion selected from a cation selected from the group consisting of halide ions of fluorine, chlorine, bromine and iodine , sulfate ions, hexafluorophosphate, tetrafluoroborate and tetraphenylborate.
You.

Specific examples of the above compounds include trimethylamine hydrochloride, triethylamine hydrochloride, tripropylamine hydrochloride, tributylamine hydrochloride, N, N-dimethylaniline hydrochloride, N, N-diethylaniline hydrochloride,
N, N-2,4,5-pentamethylaniline hydrochloride and their hydrofluoride, hydrobromide, hydroiodide, or triphenylphosphine hydrobromide, tri (o-tolyl) phosphine Hydrobromide,
Tri (p-tolyl) phosphine hydrobromide, tri (mesityl) phosphine hydrobromide and their hydrochlorides, hydroiodide, hydrofluoride, or bromotriphenylmethane, chlorotriphenylmethane, tropylium bromide, ferrocenium sulfate, Examples include, but are not limited to, ferrocenium hexafluorophosphate, ferrocenium tetraphenylborate, and the like.

The metallocene compound (c) used in the present invention is a compound represented by the following general formula (1) or (2).

[0013]

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[0014]

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Wherein Cp ¹ , Cp ² , Cp ³ and Cp ⁴
Are each independently a cyclopentadienyl or substituted cyclopentadienyl group, and R ¹ is a lower alkylene group, a substituted alkylene group, a dialkylsilanediyl group, a dialkylgermandiyl group, an alkylphosphinediyl group or an alkylimino group. , R ¹ act to bridge Cp ¹ and Cp ² , M is a transition metal compound of Group IVB of the periodic table, R ² , R ³ , R ⁴ , R ⁵ are each independently a hydrogen atom, A halogen atom, a hydrocarbon group having 1 to 12 carbon atoms,
In the above general formula, the halogen atom is fluorine,
Examples thereof include chlorine, bromine, and iodine, and examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.Examples of the cycloalkyl group include a cyclohexyl group.Examples of the aryl group include a phenyl group and a tolyl group. And the aralkyl group includes a benzyl group and a neophyl group; the alkoxy group includes a methoxy group and an ethoxy group; and the aryloxy group includes a phenoxy group.

Specific examples of these compounds include bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (butylcyclopentadienyl) zirconium dimethyl, bis (1,3- Dimethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, dimethylsilanediylbis (indenyl) zirconium dimethyl, ethylenebis (tetrahydro Indenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl-1-fluorenyl) zirconium dimethyl, diphenylmethylene (cyclopentadienyl-1) Fluorenyl) zirconium dimethyl, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilanediylbis (3- Methylcyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopenta Dienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (pentamethylcyclopentadienyl)
Zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-1)
-Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-1-fluorenyl) zirconium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl)
Zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium diphenyl, bis (methylcyclopentadienyl) zirconium diphenyl, bis (butylcyclopentadienyl) zirconium diphenyl, bis (1,3-dimethylcyclopentadienyl) zirconium diphenyl, bis (indenyl) ) Zirconium diphenyl, bis (pentamethylcyclopentadienyl) zirconium diphenyl, ethylenebis (indenyl) zirconium diphenyl, dimethylsilanediylbis (indenyl) zirconium diphenyl, ethylenebis (tetrahydroindenyl) zirconium diphenyl, isopropylidene (cyclopentadiene) Enyl-1-fluorenyl) zirconium diphenyl,
Diphenylmethylene (cyclopentadienyl-1-fluorenyl) zirconium diphenyl, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium diphenyl, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) Zirconium diphenyl, dimethylsilanediyl bis (3-methylcyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl,
Bis (methylcyclopentadienyl) zirconium dibenzyl, bis (butylcyclopentadienyl) zirconium dibenzyl, bis (1,3-dimethylcyclopentadienyl) zirconium dibenzyl, bis (indenyl) zirconium dibenzyl, bis ( Pentamethylcyclopentadienyl) zirconium dibenzyl, ethylenebis (indenyl) zirconium dibenzyl, dimethylsilanediylbis (indenyl) zirconium dibenzyl, ethylenebis (tetrahydroindenyl) zirconium dibenzyl, isopropylidene (cyclopentadienyl- 1-fluorenyl) zirconium dibenzyl, diphenylmethylene (cyclopentadienyl-1-fluorenyl) zirconium dibenzyl, dimethylsilanediylbis (2,4,5 Trimethylcyclopentadienyl) zirconium dibenzyl, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dibenzyl, dimethylsilanediylbis (3-methylcyclopentadienyl) zirconium dibenzyl, bis (cyclopentane Dienyl) zirconium methoxymonochloride, bis (methylcyclopentadienyl) zirconium methoxymonochloride, bis (butylcyclopentadienyl) zirconium methoxymonochloride, bis (1,3-dimethylcyclopentadienyl) zirconium methoxymonochloride , Bis (indenyl) zirconium methoxymonochloride, bis (pentamethylcyclopentadienyl) zirconium methoxymonochloride,
Ethylenebis (indenyl) zirconium methoxymonochloride, dimethylsilanediylbis (indenyl) zirconium methoxymonochloride, ethylenebis (tetrahydroindenyl) zirconium methoxymonochloride, isopropylidene (cyclopentadienyl-1-fluorenyl) zirconium methoxymonochloride , Diphenylmethylene (cyclopentadienyl-1-fluorenyl) zirconium methoxymonochloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium methoxymonochloride, dimethylsilanediylbis (2,4-dimethyl Cyclopentadienyl) zirconium methoxymonochloride, dimethylsilanediylbis (3-methylcyclopentadienyl)
Zirconium methoxymonochloride, bis (cyclopentadienyl) methylzirconium monochloride, bis (methylcyclopentadienyl) methylzirconium monochloride, bis (butylcyclopentadienyl) methylzirconium monochloride, bis (1,3-dimethyl Cyclopentadienyl) methyl zirconium monochloride, bis (indenyl) methyl zirconium monochloride, bis (pentamethylcyclopentadienyl) methyl zirconium monochloride, ethylenebis (indenyl) methyl zirconium monochloride, dimethylsilanediylbis (indenyl) Methyl zirconium monochloride, ethylenebis (tetrahydroindenyl) methyl zirconium monochloride, isopropylidene (cyclopentadienyl-1- Fluorenyl) methylzirconium monochloride, diphenylmethylene (cyclopentadienyl-1-fluorenyl) methylzirconium monochloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) methylzirconium monochloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) methyl zirconium monochloride, dimethylsilanediylbis (3-methylcyclopentadienyl) methyl zirconium monochloride and the like, and metallocene compounds in which zirconium of the above zirconium compound is replaced with titanium or hafnium Can be exemplified.

The organoaluminum compounds (d) and (e) used in the present invention are represented by the following general formula.

[0018] AlR ⁶ ₃ (wherein, R ⁶ are each identical may hydrogen atoms be different or, a halogen atom, an amide group, an alkyl group, an alkoxy group or an aryl group, and at least one is an alkyl group Specific examples of this compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, triisopropylaluminum, trinormalbutylaluminum, triisobutylaluminum, tri (t-butyl) aluminum, triamylaluminum, dimethylaluminum chloride, Diethylaluminum chloride, diisobutylaluminum chloride, di (t-butyl) aluminum chloride,
Examples include, but are not limited to, diamyl aluminum chloride, methyl aluminum chloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, t-butyl aluminum dichloride, amyl aluminum dichloride, and the like.

The catalyst for olefin polymerization of the present invention comprises a modified clay obtained by treating the above-mentioned clay mineral (a) with a compound (b). The reaction conditions of (a) and (b) are as follows. Is not particularly limited, and the ratio of the reaction amounts of (a) and (b) is not particularly limited. If a cation is present in (a) to be used, (b) Is preferably reacted. In addition, as a reaction solvent used at this time, generally used organic solvents, specifically, benzene, toluene, xylene, pentane, hexane, methylene chloride and the like are used, and water can also be used. Among them, a solvent capable of swelling the clay is particularly preferably used.

The method or order of adding the clay mineral, metallocene compound (c) and organoaluminum compound (d) modified as described above is not particularly limited, but in order to reduce the influence of impurities and the like in the clay mineral, It is preferable to contact the modified clay mineral with the organoaluminum compound (d).

In the prepolymerization, the method or order of addition of the modified clay mineral, metallocene compound (c) and organoaluminum compound (d) is not particularly limited, but the influence of impurities in the clay mineral is reduced. For this purpose, it is preferable to contact the previously modified clay mineral with the organoaluminum compound (d). At this time, the kind of the olefin to be prepolymerized is not particularly limited, but α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene are preferable.
When the prepolymerization is performed 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, methylene chloride, or the like, or olefin itself is used. It can also be used as a solvent. In this case, the reaction conditions such as the concentration of the α-olefin and the reaction temperature are not particularly limited.

Further, the amounts and ratios of the three components constituting the catalyst of the present invention are not particularly limited, but it is preferable to use a clay mineral sufficient for the metallocene compound (c) to react.

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. Polymerization of a mixture of two or more of these components. Can also. The olefin polymerization of the present invention can be carried out in a liquid phase or a gas phase. Among these, the solvent used in the polymerization in the liquid phase may be any commonly used organic solvent, specifically, benzene, toluene, xylene, pentane, hexane, methylene chloride or the like, or olefin itself as the solvent. Can also be used.
Further, the polymerization temperature is not particularly limited, but may be -100 to 30.
It is preferable to carry out in the range of 0 ° C.

[0024]

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.

The polymerization operation, the reaction and the solvent purification are as follows:
All were performed under an inert gas atmosphere. In addition, solvents and the like used in the reaction were all purified, dried and deoxygenated by a known method in advance. The compounds used in the reaction were those synthesized and identified by a known method.

The bulk density was measured by a method according to JIS K-6721.

The MFR was measured by a method according to ASTM D1238 condition E.

Example 1 [Preparation of modified clay] 0.56 g of ferrocene and 6 m of concentrated sulfuric acid
was reacted for 1 hour at room temperature. 150 ml of this solution
Of high-purity montmorillonite 3.3
water containing g (Kunipia, manufactured by Kunimine Industries)
Added to 50 ml. This was filtered, washed with water, and dried under reduced pressure at room temperature and 10 ^-5 Torr for 24 hours to obtain a modified clay.

[Polymerization] After replacing 1 l of a glass autoclave with nitrogen, 300 ml of toluene was added, then 250 mg of the modified clay synthesized by the above method was added, and then 3.8 mmol of triisobutylaluminum and then ethylenebis (indenyl) were added. 17) Zirconium dichloride was added at 17 μmol. 2.5 kg / c of ethylene
It was introduced while maintaining the pressure at m ² and polymerized at 60 ° C. for 1 hour. After the completion of the reaction, unreacted ethylene was removed, and the reaction solution was poured into ethanol to obtain 15 g of a polymer.

Example 2 [Preparation of modified clay] Dimethylanilinium hydrochloride (Me
0.55 g of ( ₂ PhNHCl) was added to 100 ml of water, and 1.9 g of synthetic high-purity montmorillonite (trade name Kunipia, manufactured by Kunimine Industries) was added thereto. This was filtered, washed with water, and dried under reduced pressure at room temperature and 10 ^-5 Torr for 24 hours to obtain a modified clay.

[Polymerization] The modified clay prepared above was mixed with 2
Polymerization was carried out in the same manner as in Example 1 except that 50 mg was used. As a result, 20 g of a polymer was obtained.

COMPARATIVE EXAMPLE 1 [Polymerization] In place of the modified clay, 2 at room temperature and 10 ^-5 Torr
Silica dried under reduced pressure for 4 hours (Fuji Silysia 94
Polymerization was carried out in the same manner as in Example 1 except that 8) was used. As a result, only 2 g of the polymer was obtained.

Comparative Example 2 [Polymerization] Instead of the modified clay, 2 at room temperature and 10 ^-5 Torr
Polymerization was carried out in the same manner as in Example 1 except that synthetic high-purity montmorillonite (trade name: Kunipia, manufactured by Kunimine Industries Co., Ltd.) dried under reduced pressure for 4 hours was used. As a result, 1.5
Only g of polymer were obtained.

Example 3 [Polymerization] After replacing a 2-liter stainless steel autoclave with nitrogen, 500 ml of toluene was added, then 14 mg of the modified clay synthesized in Example 1 was added, and then 0.6 mmol of triisobutylaluminum and then ethylene were added. 1.0 μm of bis (indenyl) zirconium dichloride
ol. Ethylene was introduced therein while maintaining the pressure at 4 kg / cm ² , and polymerization was carried out at 80 ° C. for 1 hour. After the completion of the reaction, unreacted ethylene was removed, and the reaction solution was poured into ethanol to obtain 55 g of a polymer.

Example 4 [Preparation of modified clay] 0.26 g of ferrocene and 3 m of concentrated sulfuric acid
was reacted for 1 hour at room temperature. 150 ml of this solution
Of synthetic hectorite (trade name: Laponite, manufactured by Nippon Silica Industry Co., Ltd.)
l. After filtration, washing with water, room temperature, 1
The resultant was dried under reduced pressure at 0 ^-5 Torr for 24 hours to obtain a modified clay.

[Polymerization] Polymerization was carried out in the same manner as in Example 3 except that the modified clay prepared above was used.
As a result, 89 g of a polymer was obtained.

Example 5 [Polymerization] Polymerization was carried out in the same manner as in Example 4 except that 1.0 μmol of dimethylsilanediylbis (indenyl) zirconium dichloride was used instead of ethylenebis (indenyl) zirconium dichloride. As a result, 50 g of a polymer was obtained.

Example 6 [Preparation of modified clay] Dimethylanilinium hydrochloride (Me
0.44 g of ( ₂ PhNHCl) was added to 100 ml of water, and 2.0 g of synthetic hectorite (trade name: Laponite, manufactured by Nippon Silica Industry Co., Ltd.) was added thereto. This was filtered, washed with water, and dried under reduced pressure at room temperature at 10 ^-5 Torr for 24 hours.
A modified clay was obtained.

[Polymerization] Polymerization was carried out in the same manner as in Example 3 except that the modified clay prepared above was used.
As a result, 60 g of a polymer was obtained.

Example 7 [Polymerization] The inside of a stainless steel electromagnetic stirring type autoclave having an inner volume of 2 liters was sufficiently purged with nitrogen.
200 g of dried salt over time is added as a dispersion medium for the catalyst,
The internal temperature was adjusted to 75 ° C. Next, a mixture of 40 mg of the modified clay prepared in Example 6, 3.0 μmol of dimethylsilanediylbis (indenyl) zirconium dichloride, and 5.5 mmol of triisobutylaluminum was inserted into the autoclave. Immediately introduce ethylene gas, and continuously add ethylene gas so that the internal pressure of the autoclave becomes 8 kg / cm ² G.
Polymerization was performed for 0 minutes. After completion of the polymerization, the mixture was cooled, and the unreacted gas was expelled to remove a mixture of the produced polymer and salt. The mixture was washed with pure water, dried after dissolving the salt,
37 g of polymer were obtained.

Example 8 [Polymerization] Ethylene was polymerized in the same manner as in Example 7 except that bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was used instead of dimethylsilanediylbis (indenyl) zirconium dichloride. , 25
g of polymer were obtained.

Example 9 [Preparation of Preliminary Polymerization Catalyst] After replacing 1 l of a glass autoclave with nitrogen, 300 ml of toluene was added.
1.0 g of the modified clay synthesized in Example 1 was added, and then 15.0 mmol of triisobutylaluminum and then 68 μmol of ethylenebis (indenyl) zirconium dichloride were added. 2.5 kg of ethylene
/ Cm ² while maintaining the pressure, and preliminarily polymerized at a polymerization temperature of 60 ° C. for 2 hours. After the completion of the pre-polymerization, the solvent was removed with a bridge filter, and washing was performed five times with 200 ml of hexane. As a result, a prepolymerized catalyst containing 47 g of polyethylene per 1 g of the modified clay was obtained.

[Polymerization] The inside of a stainless steel electromagnetic stirring type autoclave having an inner volume of 2 liters was sufficiently purged with nitrogen.
200 g of common salt dried at 00 ° C. for 20 hours was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Next, a mixture of the above-prepared prepolymerized catalyst (corresponding to 2.3 μmol of zirconium) and 3.0 mmol of triisobutylaluminum was inserted into the autoclave. Immediately introduce ethylene gas and the internal pressure of the autoclave is 8kg / c
Polymerization was carried out at 80 ° C. for 30 minutes while continuously adding ethylene gas so as to obtain m ² G. After completion of the polymerization, the mixture was cooled, and the unreacted gas was expelled to remove a mixture of the produced polymer and salt. The mixture was washed with pure water, dried after dissolving sodium chloride, to obtain 28 g of a polymer.

Example 10 [Preparation of Preliminary Polymerization Catalyst] After replacing 1 liter of glass autoclave with nitrogen, 300 ml of toluene was added.
0.25 g of the modified clay synthesized in Example 2 was added, and then 3.8 mmol of triisobutylaluminum and then 17 μmol of ethylenebis (indenyl) zirconium dichloride were added. Add 2 kg / c of ethylene
Introduced while maintaining the pressure at m ² , preliminary polymerization was carried out at a polymerization temperature of 60 ° C. for 1 hour. After the completion of the pre-polymerization, the solvent was removed with a bridge filter, and washing was performed five times with 200 ml of hexane. As a result, a prepolymerized catalyst containing 20 g of polyethylene with respect to 1 g of the modified clay was obtained.

[Polymerization] The inside of a stainless steel electromagnetic stirring type autoclave having an inner volume of 2 liters was sufficiently purged with nitrogen.
200 g of common salt dried at 00 ° C. for 20 hours was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Next, a mixture of the above-prepared prepolymerized catalyst (corresponding to 2.4 μmol of zirconium) and 3.0 mmol of triisobutylaluminum was inserted into an autoclave. Immediately introduce ethylene gas and the internal pressure of the autoclave is 8kg / c
Polymerization was carried out at 80 ° C. for 30 minutes while continuously adding ethylene gas so as to obtain m ² G. After completion of the polymerization, the mixture was cooled, and the unreacted gas was expelled to remove a mixture of the produced polymer and salt. The mixture was washed with pure water, dried after dissolving sodium chloride, to obtain 22 g of a polymer.

Example 11 [Polymerization] The inside of a stainless steel electromagnetic stirring type autoclave having an inner volume of 2 liters was sufficiently purged with nitrogen.
200 g of dried salt over time is added as a dispersion medium for the catalyst,
The internal temperature was adjusted to 75 ° C. Next, a mixture of the prepolymerized catalyst (corresponding to 2.4 μmol of zirconium) prepared in Example 9 and 1.5 mmol of triisobutylaluminum was inserted into the autoclave. Immediately, ethylene gas was introduced, and polymerization was carried out at 80 ° C. for 30 minutes while continuously adding ethylene gas so that the internal pressure of the autoclave became 8 kg / cm ² G. After completion of the polymerization, the mixture was cooled, and the unreacted gas was expelled to remove a mixture of the produced polymer and salt.
The mixture was washed with pure water, dried after dissolving sodium chloride, to obtain 22 g of a polymer.

Example 12 [Preparation of Preliminary Polymerization Catalyst] After replacing 1 l of a glass autoclave with nitrogen, 300 ml of toluene was added.
0.25 g of the modified clay synthesized in Example 2 was added, followed by 3.8 mmol of triisobutylaluminum and then 17 μm of bis (indenyl) zirconium dichloride.
mol. Add 1.5 kg / cm ^{2 of} ethylene
, And preliminarily polymerized at a polymerization temperature of 60 ° C. for 30 minutes. After the completion of the prepolymerization, the solvent was removed with a bridge filter, and the mixture was washed with 200 ml of hexane for 5 minutes.
I went there. As a result, a prepolymerized catalyst containing 40 g of polyethylene per 1 g of the modified clay was obtained.

[Polymerization] The inside of a stainless steel electromagnetic stirring type autoclave having an inner volume of 2 liters was sufficiently purged with nitrogen.
200 g of common salt dried at 00 ° C. for 20 hours was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Next, a mixture of the above-prepared prepolymerized catalyst (corresponding to 2.4 μmol of zirconium) and 3.0 mmol of triisobutylaluminum was inserted into an autoclave. Immediately introduce ethylene gas and the internal pressure of the autoclave is 8kg / c
Polymerization was carried out at 80 ° C. for 1 hour while continuously adding ethylene gas so as to obtain m ² G. After completion of the polymerization, the mixture was cooled, and the unreacted gas was expelled to remove a mixture of the produced polymer and salt. This mixture was washed with pure water, dried after dissolving the common salt to obtain 45 g of a polymer.

Example 13 [Preparation of Preliminary Polymerization Catalyst] After replacing 1 l of a glass autoclave with nitrogen, 300 ml of toluene was added.
0.25 g of the modified clay synthesized in Example 2 was added, and then 3.3 mmol of triisobutylaluminum and then 20 μmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride were added. To this, ethylene was introduced while maintaining the pressure at ² kg / cm ² ,
Preliminary polymerization was performed at a polymerization temperature of 1 ° C. for 1 hour. After the completion of the pre-polymerization, the solvent was removed with a bridge filter, and washing was performed five times with 200 ml of hexane. As a result, the modified clay 1
A prepolymerized catalyst containing 30 g of polyethylene per g was obtained.

[Polymerization] The inside of a stainless steel electromagnetically stirred autoclave having an inner volume of 2 liters was sufficiently purged with nitrogen.
200 g of common salt dried at 00 ° C. for 20 hours was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Next, a mixture of the prepolymerized catalyst prepared above (equivalent to 2.8 μmol of zirconium) and 2.6 mmol of triisobutylaluminum was inserted into the autoclave. Butene
1 until the pressure reaches 1 kg / cm ² , ethylene gas is immediately introduced, and the internal pressure of the autoclave is 8 kg / cm ^2.
G while continuously adding ethylene gas
The polymerization was carried out at a temperature of 1 hour. After completion of the polymerization, the mixture was cooled, and the unreacted gas was expelled to remove a mixture of the produced polymer and salt. This mixture was washed with pure water, and dried after dissolving common salt to obtain 33 g of a polymer. Melting point 116 ° C, MF
R is 0.19 g / 10 min, bulk density is 0.28 g / cc
Was a copolymer of

Example 14 [Preparation of Preliminary Polymerization Catalyst] After replacing 1 l of a glass autoclave with nitrogen, 300 ml of toluene was added.
0.25 g of the modified clay synthesized in Example 2 was added, and then 3.3 mmol of triisobutylaluminum and then 20 μmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride were added. To this, ethylene was introduced while maintaining the pressure at ² kg / cm ² ,
Preliminary polymerization was performed at a polymerization temperature of 1 ° C. for 1 hour. After the completion of the pre-polymerization, the solvent was removed with a bridge filter, and washing was performed five times with 200 ml of hexane. As a result, the modified clay 1
A prepolymerized catalyst containing 34 g of polyethylene per g was obtained.

[Polymerization] The inside of a stainless steel electromagnetic stirring type autoclave having an inner volume of 2 liters was sufficiently purged with nitrogen.
200 g of common salt dried at 00 ° C. for 20 hours was added as a catalyst dispersion medium, and the internal temperature was adjusted to 75 ° C. Next, a mixture of the prepolymerized catalyst prepared above (equivalent to 2.8 μmol of zirconium) and 2.6 mmol of triisobutylaluminum was inserted into the autoclave. Butene
1 until the pressure reaches 1 kg / cm ² , ethylene gas is immediately introduced, and the internal pressure of the autoclave is 8 kg / cm ^2.
G while continuously adding ethylene gas
Polymerization was carried out at 30 ° C for 30 minutes. After completion of the polymerization, the mixture was cooled, and the unreacted gas was expelled to remove a mixture of the produced polymer and salt. The mixture was washed with pure water, dried after dissolving sodium chloride, to obtain 28 g of a polymer. Melting point 117 ° C, MF
R is 0.53 g / 10 min, bulk density is 0.35 g / cc
Was a copolymer of

[0053]

As described above, with the novel catalyst of the present invention, olefins can be polymerized with high activity without using expensive organoaluminum oxy compounds or special boron compounds.

Claims (3)

(57) [Claims] 1. A clay mineral (a) is blended between its layers by blending.
Dodic acid, carbonium, oxonium, sulfonium, silver
Ions, a modified clay treated with cation capable of introducing a compound selected from ferrocenium ions (b), the following one
An olefin polymerization catalyst comprising a metallocene compound (c) represented by the general formula (1) or (2) and an organoaluminum compound (d) represented by the following general formula (3) . Embedded image Embedded image (Where Cp ¹ , Cp ² , Cp ³ and Cp ⁴ are each independently
Cyclopentadienyl group or substituted cyclopentadiene
R ¹ is a lower alkylene group, a substituted alkylene
Group, dialkylsilanediyl group, dialkylgermane
Diyl group, alkylphosphinediyl group or alkyl
Is an imino group, and R ¹ bridges Cp ¹ and Cp ²
M is the transition metallization of group IVB of the periodic table
And R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom,
Rogen atom, C1-C12 hydrocarbon group, alkoxy
Is a group or an aryloxy group) AlR ⁶ _{3 (3)} (wherein, R ⁶ are each hydrogen may be the same or different raw
Atom, halogen atom, amide group, alkyl group, alkoxy
Or at least one is an aryl group
Is a kill group) 2. A clay mineral (a) is blended between its layers by blending.
Dodic acid, carbonium, oxonium, sulfonium, silver
Ions, a modified clay treated with cation capable of introducing a compound selected from ferrocenium ions (b), the following one
Olefin prepolymerization obtained by prepolymerizing an olefin with a catalyst component comprising a metallocene compound (c) represented by the general formula (1) or (2) and an organoaluminum compound (d) represented by the following general formula (3) Catalyst and general formula below
An olefin polymerization catalyst comprising the organoaluminum compound (e) represented by (3) . Embedded image Embedded image (Where Cp ¹ , Cp ² , Cp ³ and Cp ⁴ are each independently
Cyclopentadienyl group or substituted cyclopentadiene
R ¹ is a lower alkylene group, a substituted alkylene
Group, dialkylsilanediyl group, dialkylgermane
Diyl group, alkylphosphinediyl group or alkyl
Is an imino group, and R ¹ bridges Cp ¹ and Cp ²
M is the transition metallization of group IVB of the periodic table
And R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom,
Rogen atom, C1-C12 hydrocarbon group, alkoxy
Is a group or an aryloxy group) AlR ⁶ _{3 (3)} (wherein, R ⁶ are each hydrogen may be the same or different raw
Atom, halogen atom, amide group, alkyl group, alkoxy
Or at least one is an aryl group
Is a kill group) 3. A method for producing a polyolefin, comprising polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1 or 2.