JPH07133309A - Olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To provide a catalyst system containing not an organoaluminumoxy compound but an ionizing agent which is inexpensive, non-corrosive, and less toxic. CONSTITUTION:The title catalyst comprises a metallocene compound and an ionic compound containing a (substituted) cyclopentadienyl anion. It may further contain an organometallic compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel olefin polymerization catalyst.

[0002]

2. Description of the Related Art Recently, as a highly active olefin polymerization catalyst capable of obtaining an olefin polymer having a narrow molecular weight distribution and a narrow composition distribution in copolymerization and excellent physical properties, titanium, zirconium, hafnium, vanadium, etc. Metallocene-type homogeneous catalysts of Group IV or V transition metals of the periodic table are attracting attention. However, the above homogeneous catalyst is an organoaluminum oxy compound as a co-catalyst,
Particularly, expensive methylalumoxane is required for thousands to tens of thousands times the metal atom, and various improvement methods have been proposed so far. JP 61-31404, 61-276805, 61
-108610, 61-296008, Tokusho 63-501368, Tokukaihei 1-207303, Tokuhei 1-503715, 2-503687, Tokukai Hei 2-170805, Tokuhei 3 -502210 and JP-A-3-2347
No. 10 publications, a transition metal compound in the porous inorganic compound,
Alternatively, a catalyst system in which the amount of aluminum oxy compound used can be reduced or not used at all by supporting a transition metal compound and an organoaluminum oxy compound and / or an organoaluminum compound is disclosed.

In addition, special table 1-501950, 1-502036,
JP-A-3-63088 and JP-A-3-139504 disclose a combination of an amine salt of an anionic boron compound containing an active proton as an activator or an ionizing agent and a metallocene compound without using an organoaluminumoxy compound. A catalyst system having olefin polymerization activity is disclosed. In Japanese Patent Laid-Open No. 3-179006, a triphenylcarbonium salt of an anionic boron compound containing no active proton,
No. 3-207703 discloses a catalyst system further containing organoaluminum. However, in the catalyst system using these ionic compounds, toxicity and corrosiveness due to the fact that the anionic boron compound contains elemental fluorine are problems. In addition, in any of the above proposed improvement methods, there is a problem that the polymerization activity is not high enough to be industrially adopted.

[0004]

It is an object of the present invention to provide a catalyst system which does not use an organoaluminum oxy compound, is inexpensive, is not corrosive, and uses an ionizing agent having minimal toxicity.

[0005]

[Technical Means for Solving Problems] The present invention provides [1]
(A1) a metallocene compound component of a transition metal of Group IV or V of the periodic table containing at least one hydrogen and / or hydrocarbyl group as a ligand, and (B) a cyclopentadienyl anion or a substituted cyclopentadienyl anion. An olefin polymerization catalyst comprising an ionic compound component containing
[2] (A2) Group IV or V transition metal metallocene compound component, (B) cyclopentadienyl anion or substituted cyclopentadienyl anion compound component, and (C) Periodic table The present invention relates to an olefin polymerization catalyst comprising an organometallic compound component of a group I to III main element metal.

The metallocene compound which is the component (A2) in the present invention is a transition metal compound containing at least one ligand having a cyclopentadienyl skeleton. Examples of the transition metal include titanium, zirconium, hafnium and other periodic group IV transition metals, or vanadium and other group V metals.
Group transition metal etc. are mentioned. As the ligand having a cyclopentadienyl skeleton, a cyclopentadienyl group,
An indenyl group, a fluorenyl group, or an alkyl-substituted cyclopentadienyl group having a substituent such as methyl, dimethyl, or pentamethyl, a substituted indenyl group,
Examples thereof include a substituted fluorenyl group. Alternatively, these cyclopentadienyl skeletons are alkylene groups, hydrocarbyl groups such as substituted alkylene groups, silanylene groups, substituted silanylene groups, silaalkylene groups, hydrocarbyl silicon such as substituted silaalkylenes, oxasilanylene groups, substituted oxasilanylene groups, oxasilaalkylene groups. It is also possible to use those crosslinked with an oxygen-, nitrogen-, or phosphorus-containing substituent such as a substituted oxasilaalkylene group, an aminosilyl group, a mono-substituted aminosilyl group, a phosphinosilyl group, or a mono-substituted phosphinosilyl group.

Specific examples thereof include the following patent publications, JP-A-58-19309, JP-A-60-35006 and JP-A-60-35007.
61-130314, 61-264010, 61-296008,
63-222177, 63-222178, 63-222179, 63
-251405, JP-A-1-66214, 1-74202, 1-27
5609, 1-301704, 1-319489, 2-41303,
2-131488, 3--12406, 3-139504, 3-1630
No. 88, No. 3-179006, No. 3-185005, No. 3-188092, No.
3-197514, 3-207703, 4-253771, 5-209013
No. 1-501950, No. 1-502036, No. 5-505593
Those listed in No. can be mentioned. For example, M
For example, e ₂ Si (2,4-Me ₂ Cp) (3 ′, 5′-Me ₂ Cp) ZrCl ₂ and ethylenebisindenylzirconium dichloride can be used.

Specific examples of the metallocene compound of Group IV or V transition metal of the periodic table containing at least one hydrogen and / or hydrocarbyl group as a ligand, which is the component (A1) in the present invention, are mentioned above. The metallocene compound described in 1) can be mentioned. Among the metallocene compounds described in the above publications, metallocene compounds containing at least one hydrogen and / or hydrocarbyl group as a ligand are represented by the general formula MH _a R _b X _c (M is I to III of the periodic table). Group main element metal, R is a hydrocarbon group having 1 to 16 carbon atoms, X is a halogen atom, a + b + c is the maximum valence of the metal, and a + b is a hydrogen represented by a value greater than 0) The component (A1) of the present invention can be obtained by reacting with a metal halide compound, an organometallic compound, an organometallic halogen compound, a hydrogenated organometallic compound, or the like. For example, Me ₂ S
i (2,4-Me ₂ Cp) (3 ′, 5′-Me ₂ Cp) ZrMe _{2 and the} like can be used.

Examples of the metal hydride compound include NaH
, LiH, CaH ₂ , LiAlH ₄ , NaBH _{4 and the} like.

Examples of the organometallic compound include methyl lithium, butyl lithium, phenyl lithium, dibutyl magnesium, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, and isoprenyl aluminum. .

Examples of the organometallic halogen compound include methyl magnesium chloride, ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride, diethyl aluminum chloride, sesquimethyl aluminum chloride, sesquiethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, Examples thereof include diisobutylaluminum chloride and isobutylaluminum chloride.

As the hydrogenated organometallic compound, for example,
Examples thereof include dimethyl aluminum hydride, diethyl aluminum hydride, sesquimethyl aluminum hydride, and sesquiethyl aluminum hydride. As the above-mentioned organometallic compound, organometallic halogen compound, and hydrogenated organometallic compound, those having a methyl metal bond are preferable.

The organometallic compound of Group I to Group III main element metal, which is the component (C) in the present invention, is
The above-mentioned organometallic compounds, organometallic halogen compounds and hydrogenated organometallic compounds are also mentioned. Among them, preferred compounds are organoaluminum, organoaluminum hydride, and organoaluminum halide, and particularly preferred are those having a sterically bulky hydrocarbyl group such as triisobutylaluminum, or organoaluminum thereof. It includes a part. In the present invention, the general formula (-Al (R ')-O is used.
-) It is a linear or cyclic polymer represented by _n (R 'is a hydrocarbyl group having 1 to 10 carbon atoms and includes those partially substituted with a halogen atom and / or an R'O group. n is a degree of polymerization and is 5 or more, preferably 10 or more) An organoaluminum oxy compound can be used as the organometallic compound instead of the organoaluminum.

The component (B) in the present invention is an ionic compound component containing a cyclopentadienyl anion or a substituted cyclopentadienyl anion. Substituted cyclopentadienyl anion of the general _{formula, R m C 5 H 5-} m - · A
⁺ (In the formula, R represents a hydrocarbyl group having 1 to 20 carbon atoms, halogen, a halogen-substituted hydrocarbyl group, or a hydrocarbylsilyl group, or a plurality of R may form a cyclic substituent, and m is An integer from 0 to 5, A ⁺
Represents a cation. ) Is represented.

Specific examples of the substituted cyclopentadienyl anion include cyclopentadienyl anion, 1,2-dimethylcyclopentadienyl anion, 1,2,4-trimethylcyclopentadienyl anion and pentamethylcyclopentadienyl anion. Enyl anion, methylphenylcyclopentadienyl anion, 1,2-diphenylcyclopentadienyl anion, indenyl anion, 1,2,3-trimethylindenyl anion, 1,2-dimethylindenyl anion, 2-
Methylindenyl anion, 1,2-diphenylindenyl anion, 1,2,3-triphenylindenyl anion, fluorenyl anion, 1-phenylfluorenyl anion, 1-methylfluorenyl anion, tetrahydroindenyl anion Anion, 1,2,3-trimethyltetrahydroindenyl anion, 1,2-dimethyltetrahydroindenyl anion, octahydrofluorenyl anion, 1-phenyloctahydrofluorenyl anion, 1-methyloctahydrofluorenyl anion Is mentioned.

The cyclopentadienyl anion or substituted cyclopentadienyl anion has the general formula R
^{_{1 (R 2 q C 6 H}} 5-q) 4 C 5 - (. Wherein, q is an integer of from 1 to 5) substituted tetraphenyl cyclopentadienyl anion represented by is preferably used. Examples of the substituents R ¹ and R ² of the substituted tetraphenylcyclopentadienyl anion include hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a halogen-substituted hydrocarbyl group, a hydrocarbylsilyl group and the like. Specific examples of halogen include fluorine, chlorine, bromine and the like. Specific examples of the hydrocarbyl group having 1 to 20 carbon atoms include an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl and octyl, an aryl group such as phenyl and toluyl, and a cycloalkyl group such as cyclohexyl. Can be mentioned. Specific examples of the halogen-substituted hydrocarbyl group include pentafluorophenyl and trifluoromethyl groups. Specific examples of the hydrocarbylsilyl group include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, dimethylhydrosilyl, methyldihydrosilyl and triphenylsilyl, alkylhydrosilyl groups and triarylsilyl groups. R ¹ and R ² may be the same as or different from each other, or may be two or more kinds. A particularly preferred anion is a pentaphenylcyclopentadienyl anion.

The cation A ⁺ is carbonium cation, oxonium cation, ammonium cation,
Examples thereof include phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenyl carbonium cation and tri-substituted phenyl carbonium cation. Specific examples of the tri-substituted phenyl carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation. Specific examples of the ammonium cation include trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, trialkylammonium cation such as tri (n-butyl) ammonium cation, N, N-diethylanilinium cation, N , N-2,4,6-pentamethylanilinium cation and other N, N-dialkylanilinium cations, di (i-propyl) ammonium cation, dicyclohexylammonium cation and other dialkylammonium cations.

Specific examples of the phosphonium cation include:
Examples include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As the cation A ⁺ , a carbonium cation, an ammonium cation and the like are preferable, and particularly,
Triphenylcarbonium cation and N, N-diethylanilinium cation are preferred.

The ionic compound of the present invention reacts with anionic ligands other than the cyclopentadienyl or substituted cyclopentadiene ligands of the metallocene compound to give a cationic metallocene compound and (substituted) cyclopentadienyl. Form a compound consisting of anions.

That is, the reaction is performed according to the following reaction formula. _{(C P) l MQ r +} R m C 5 H 5-m - · A + → [(C P) l MQ r-1] + [R m C 5 H 5-m] - + QA ( wherein, C _P represents a ligand having a cyclopentadienyl skeleton, M represents a transition metal of Group IV or V of the periodic table,
Q represents an anionic ligand. )

In the present invention, the metallocene compound and / or the ionic compound can be used by supporting them on an inorganic compound or an organic polymer compound. As the inorganic compound as a carrier, inorganic oxides, inorganic chlorides and inorganic hydroxides are preferable, and those containing a small amount of carbonates and sulfates can also be adopted. Particularly preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia, and calcia. These inorganic oxides have an average particle size of 5 to 150 μ and a specific surface area of 2 to 800 m ² / g.
The above porous fine particles are preferable, and they can be used after being heat-treated at 100 to 800 ° C., for example. The organic polymer compound is preferably one having an aromatic ring, a substituted aromatic ring or a functional group such as a hydroxy group, a carboxyl group, an ester group or a halogen atom in its side chain. Specific examples include ethylene, propylene, α-olefin homopolymer having the functional group by chemical modification such as polybutene, α-olefin copolymer, acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, homopolymers such as divinylbenzene, Mention may be made of copolymers, as well as their chemical modifications. As these organic polymer compounds, spherical fine particles having an average particle diameter of 5 to 250 µ are used. By loading the metallocene compound and / or the ionic compound, it is possible to prevent the catalyst from being contaminated due to adhesion to the polymerization reactor.

In the present invention, although not particularly limited,
Olefin can be polymerized by the following method with the above-mentioned catalyst system for olefin polymerization. However, in the present invention, olefin polymerization also includes olefin polymerization and copolymerization between different olefins. (1) A solution or slurry [M] of a hydrocarbon or a halogenated hydrocarbon of a metallocene compound and a solution or a slurry [I] of a hydrocarbon or a halogenated hydrocarbon of an ionic compound are contacted with each other in advance, and then an olefin is polymerized. . (2) After contacting [M] and the olefin in advance, [I] is contacted to carry out polymerization. (3) After contacting [I] with an olefin in advance, contacting with [M] to carry out polymerization. (4) After making contact with [M], [I] and the organometallic compound in advance, the olefin is polymerized. (5) After contacting [M] with the organometallic compound in advance, [I]
And olefin are contacted to carry out polymerization. (6) After contacting [I] and the organometallic compound in advance, [M]
And olefin are contacted to carry out polymerization. (7) A solution of a hydrocarbon or halogenated hydrocarbon of a metallocene compound [N] and a solution of a hydrocarbon of an ionic compound or a halogenated hydrocarbon [P] are mixed and then contacted with a carrier, and the carrier is separated to obtain an olefin. Polymerize by contact. (8) After contacting [N] with the carrier, contacting with [P] to separate the carrier and polymerize the olefin. (9) After contacting [P] with the carrier, contacting with [N] to separate the carrier and polymerize the olefin. (10) After contacting [N] and the carrier, the organometallic compound and [P] are further contacted, and the carrier is separated to polymerize the olefin. Further, when an organoaluminum oxy compound is used, it can be added, for example, at the time of preparation of the catalyst system before polymerization, or at the time of polymerization.

As the hydrocarbon solvent for dissolving and slurrying each component, for example, an inert hydrocarbon such as hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene, or a halogenated hydrocarbon solvent. Examples thereof include chloroform, methylene chloride, dichloroethane, chlorobenzene and the like.

In the above, the contact of each component is usually 0 to
Perform at 100 ℃ for 10 to 180 minutes. The amount of each component used is such that the metallocene compound / ionic compound molar ratio is usually 0.01 to 100,
It is preferably 0.1 to 10. Further, when the organometallic compound is shared, the molar ratio of organometallic compound / metallocene compound is usually 0.1 to 10000, preferably 1 to 1000.

The olefin polymerization in the present invention is usually a fluidized or stirred gas phase method using a supported catalyst, a slurry method in an inert hydrocarbon solvent, a solution method in an inert hydrocarbon solvent at high temperature, It can be used in both high temperature and high pressure polymerization methods. The polymerization conditions are, for example, in the gas phase method or the slurry method, a temperature of −110 to 110 ° C. and a time of 10 to 360.
Min, pressure is normal pressure ~ 100 kg / cm ² , in solution method, temperature is 100 ~
250 ° C., time 1 to 60 minutes, the pressure is 10~300kg / cm ² below, in the high-temperature high-pressure polymerization processes, a temperature 120 to 300 ° C., 5 to 600 seconds, the pressure is carried out at 400 kg / cm ² or more.

Further, the polymerization activity is improved, the shape of the solid catalyst of the produced polymer is maintained, the catalyst is easily introduced into the main polymerization reaction vessel, the catalyst is prevented from adhering to the polymerization reaction vessel, and the fluidity in the gas phase reaction vessel is improved. For the purpose of, for example, preliminarily polymerized olefins according to the above-mentioned various polymerization methods can be used as a catalyst in the main polymerization. Preliminary polymerization should be performed, for example, in a slurry method in an inert hydrocarbon solvent, usually at 5 to 80 ° C for 5 to 60 minutes under the condition that 1 to 100 g of olefin polymer is obtained per 1 mg of metallocene transition metal. You can

Specific examples of the olefin in the present invention include:
Ethylene, propylene, butene-1,4-methylpentene-
1, acyclic monoolefins such as hexene-1 and octene-1, and cyclic monoolefins such as cyclopentene, cyclohexene and norbornene. Also,
In the above-mentioned olefin polymerization and copolymerization, a small amount of dicyclopentadiene, 5-ethylidene-2 norbornene,
Alternatively, non-conjugated diolefins such as 1,5 hexadiene can be copolymerized.

[0029]

When an olefin polymer is produced by using the relatively inexpensive catalyst system of the present invention, the activity of the catalyst is high, and the transition metal and aluminum components in the produced polymer are small, so that deashing is not required, There are few problems with equipment corrosion. In addition, since it is a homogeneous catalyst, the molecular weight distribution of the produced polymer is narrow, a polymer with high stereoregularity can be obtained in the polymerization of α-olefins, and the composition distribution is narrow in the copolymerization of olefins. Coalescence can be produced.

[0030]

EXAMPLES In the examples, "polymerization activity" is the polymer yield (kg) per 1 mmol of transition metal of the metallocene catalyst used in the polymerization reaction. The molecular weight distribution is the weight average molecular weight obtained from GPC using polystyrene as a standard substance.
It was evaluated by the ratio Mw / Mn of Mw and number average molecular weight Mn. The comonomer content in the copolymer was measured by 1 H-NMR.

Example 1 (Trityl pentaphenyl cyclopentadienyl complex)
^{_{[Ph 3 C + · Ph 5}} C p -] Synthesis) after a flask equipped with a stirrer was replaced with nitrogen, pentaphenyl cyclopentadienyl lithium salt (Journal of Organometallic Chemis
try, 229 (1982) 109-112 was used) 0.48 g (1.06 mmol), triphenylmethyl chloride 0.3 g (1.08 mmol) and heptane 50 ml were added and stirred for 2 days at room temperature. This gave a reddish purple solid with a purple solution. After distilling off the solvent under reduced pressure, add 30 ml of methylene chloride to remove the lithium salt, and add a few ml of the resulting reddish purple solution.
It was distilled off under reduced pressure. After charging 30 ml of heptane and leaving it overnight, it was separated and purified by filtration to obtain 0.24 g (yield 33%) of blackish brown crystals.

Example 2 (Ethylene Polymerization) 200 ml of purified toluene was charged into a 500 ml flask which had been sufficiently purged with nitrogen, and converted into aluminum atoms.
Triisobutylaluminum equivalent to 0.2mg atom 10μ
Charged mol. After heating to 40 ℃, add 1 ethylene gas.
It was introduced at a rate of 000 ml / min. After that, trityl pentaphenyl cyclopentadienyl complex (toluene solution) was added.
10 μmol, and Me ₂ Si (2,4-Me ₂ Cp) (3 ', 5'-Me ₂ Cp) ZrCl
Polymerization was initiated by charging 10 μmol of ₂ (synthesized by the method of Chemistry letters, 1853, (1989)). After reacting for 1 hour, ethanol was added to terminate the polymerization. The polymer slurry solution was added to a large amount of ethanol solution to precipitate the polymer. After filtration and separation, overnight
After drying under reduced pressure at 70 ° C., 15.2 g of polymer was obtained. Table 1 shows the polymerization results.

Example 3 (Ethylene / Propylene Copolymerization) Fully nitrogen-substituted 5
After charging 200 ml of purified toluene into a 00 ml flask, triisobutylaluminum corresponding to 0.2 mg atom in terms of aluminum atom was charged. After the temperature was raised to 40 ° C., a monomer gas (ethylene / propylene = 1/3) was introduced at a rate of 1000 ml / min. Then, 10 μmol of trityl pentaphenyl cyclopentadienyl complex and Me ₂ Si (2,4-Me ₂ Cp) were added.
Polymerization was initiated by charging 10 μmol of (3 ′, 5′-Me ₂ Cp) ZrCl ₂ . After reacting for 1 hour, ethanol was added to terminate the polymerization. The polymer slurry solution was added to a large amount of ethanol solution to precipitate the polymer. After separation by filtration, the product was dried overnight at 70 ° C. under reduced pressure to obtain 18.1 g of a polymer. Table 1 shows the polymerization results.

Example 4 The same procedure as in Example 3 was carried out except that triisobutylaluminum was inserted in an amount corresponding to 0.3 mg atom in terms of aluminum atom. The polymer yield after drying is
It was 21.2 g. Table 1 shows the polymerization results.

Example 5 The same procedure as in Example 3 was carried out except that triisobutylaluminum was inserted in an amount corresponding to 0.3 mg atom in terms of aluminum atom and the polymerization temperature was 30 ° C. The polymer yield after drying was 24 g. Table 1 shows the polymerization results.

Example 6 The procedure of Example 3 was repeated except that triisobutylaluminum was replaced with triethylaluminum in an amount corresponding to 0.2 mg atom in terms of aluminum atom. The polymer yield after drying was 12 g. Table 1 shows the polymerization results.

Comparative Example 1 The procedure of Example 3 was repeated except that the tritylpentaphenylcyclopentadienyl complex was not used.
The polymer yield after drying was 4 g. Table 1 shows the polymerization results.

Example 7 Me₂Si (2,4-Me₂Cp) (3 ', 5'-Me₂Cp) ZrMe₂ After replacing the flask equipped with a stirrer with nitrogen,₂Si
(2,4-Me₂Cp) (3 ', 5'-Me ₂Cp) ZrCl₂4.0 g (0.01 mol) and
70 ml of ruene was charged and cooled to -70 ° C. And
Add chilled lithium 0.02 mol dropwise within 30 minutes and then
The temperature was gradually raised to warm. Remove the resulting white precipitate
Then, the mixture was concentrated under reduced pressure and 30 ml of heptane was charged. Tea that deposits in small amounts
After removing the brown powder by filtration, the solvent was concentrated and removed by half, and the temperature was raised to room temperature.
And leave it overnight to give dimethyl as white crystals.
1.7 g (Y = 46.7%) of the body was obtained. Elemental analysis results of the obtained crystals
Is the theoretical value C: 59.44, H: 7.76; measured value C: 59.04, H:
It was 7.96.

Example 8 In the method of Example 3, Me ₂ Si (2,4-Me ₂ Cp) (3 ', 5'-Me
₂ Cp) ZrCl ₂ instead of Me ₂ Si (2,4-Me ₂ Cp) (3 ', 5'-Me ₂ Cp) Zr
Me ₂ was charged in an amount of 10 μmol, and the same procedure was performed except that triisobutylaluminum was not added. The polymer yield after drying was 10.1 g. Table 1 shows the polymerization results.

Example 9 Synthesis of N, N-diethylanilinium pentaphenylcyclopentadienyl complex After replacing a flask equipped with a stirrer with nitrogen, pentaphenylcyclopentadienyl lithium salt (Journal of
Organometallic Chemistry, 229 (1982) 109-112) was used to prepare 0.48 g (1.06 mmol) of N, N-
0.2 g (1.08 mmol) of diethyl aanilinium chloride and 50 ml of heptane were added, and the mixture was stirred at room temperature for 2 days to obtain a slurry solution containing a purple solid. After distilling off the solvent under reduced pressure, 60 ml of methylene chloride was charged, the lithium salt was removed, and the resulting purple solution was distilled off under reduced pressure to several ml. Toluene 3
Charge 0 ml and let stand overnight, then isolate and purify by filtration to give 0.31 g.
Red-brown crystals (yield 49%) were obtained. The elemental analysis result of the obtained crystal is theoretical value C: 90.72, H: 6.93; measured value C: 90.1.
It was 4, H: 6.70.

Example 10 In the method of Example 3, instead of the trityl pentaphenylcyclopentadienyl complex, the N, synthesized in Example 9 was used.
The same procedure was performed except that 10 μmol of N-diethylanilinium pentaphenylcyclopentadienyl complex was charged.
The polymer yield after drying was 15.2 g. Table 1 shows the polymerization results.

Example 11 In the method of Example 3, instead of the tritylpentaphenylcyclopentadienyl complex, the N, synthesized in Example 9 was used.
The same procedure was performed except that 10 μmol of N-diethylanilinium pentaphenylcyclopentadienyl complex was charged and triisobutylaluminum was charged in an amount corresponding to 0.3 mg atom in terms of aluminum atom. The polymer yield after drying was 18.3 g. Table 1 shows the polymerization results.

Example 12 In the method of Example 3, Me ₂ Si (2,4-Me ₂ Cp) (3 ', 5'-Me
_{The same} procedure was carried out except that 5 μmol of ethylenebisindenyl zirconium dichloride and 5 μmol of tritylpentaphenylcyclopentadienyl complex were charged instead of ₂ Cp) ZrCl ₂ . The polymer yield after drying was 25.2 g. Table 1 shows the polymerization results.

Example 13 In the method of Example 3, Me ₂ Si (2,4-Me ₂ Cp) (3 ', 5'-Me
5 μmol of ethylenebisindenyl zirconium dichloride instead of ₂ Cp) ZrCl ₂ and N, N-diethylanilinium pentaphenylcyclopentadienyl synthesized in Example 9 instead of the trityl pentaphenylcyclopentadienyl complex. The same procedure was performed except that 5 μmol of the complex was charged. The polymer yield after drying was 26.3 g. Table 1
The results of the polymerization are shown in.

Example 14 In the method of Example 3, Me ₂ Si (2,4-Me ₂ Cp) (3 ', 5'-Me
₆ μmol of ethylenebisindenylzirconium dichloride instead of ₂ Cp) ZrCl ₂ and N, N-diethylanilinium pentaphenylcyclopentadienyl synthesized in Example 9 instead of the tritylpentaphenylcyclopentadienyl complex. The same procedure was performed except that 5 μmol of the complex was charged. The polymer yield after drying was 29.5 g. Table 1
The results of the polymerization are shown in.

[0046]

[Table 1]

[Brief description of drawings]

FIG. 1 is a flow chart showing steps for preparing a solid catalyst for olefin polymerization of the present invention.

Front page continuation (72) Inventor Eiko Ogawa 8-1 Goi Minami Kaigan, Ichihara, Chiba Ube Industries Ltd. Chiba Research Institute (72) Inventor Nobuhiro Mitani 8-1 Goi Minami Kaigan, Ichihara-shi, Chiba Ube Ko Sanba Co., Ltd. Chiba Research Center

Claims (2)

[Claims] 1. A metallocene compound component of a transition metal of Group IV or V of the periodic table containing (A1) at least one hydrogen and / or hydrocarbyl group as a ligand, and (B) a cyclopentadienyl anion or a substituted cycloalkyl group. An olefin polymerization catalyst comprising an ionic compound component containing a pentadienyl anion. 2. (A2) a metallocene compound component of a transition metal of Group IV or V of the periodic table, (B) an ionic compound component containing a cyclopentadienyl anion or a substituted cyclopentadienyl anion, and (C) a periodic table Table 1 Olefin polymerization catalyst comprising an organometallic compound component of Group I to III main element metals.