JP3117257B2 - Solid catalyst for producing polyolefin and method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyolefin. Specifically, the present invention relates to a method for producing a polyolefin having good particle properties by using a solid catalyst supported on a carrier.

[0002]

PRIOR ART Cyclopentadienyl group, indenyl group,
It is known that a transition metal compound having a fluorenyl group or a derivative thereof as a ligand, a so-called metallocene compound, can produce a poly-α-olefin by polymerizing an α-olefin using a co-catalyst such as an aluminoxane. ing.

JP-A-58-19309 and JP-A-6-19
JP-A-0-35008 describes a method of polymerizing or copolymerizing an olefin in the presence of a catalyst comprising a metallocene compound and an aluminoxane.

JP-A-61-130314 and JP-A-64-66124 disclose poly-α having a high isotacticity by using a catalyst comprising a metallocene compound having a crosslinking ligand and an aluminoxane. It states that olefins can be produced.

JP-A-2-41303, JP-A-2-41303
274703 and JP-A-2-274704 disclose that syndiotactic poly-α-olefins are produced by using a metallocene compound having a crosslinkable ligand comprising asymmetrical ligands and a catalyst comprising aluminoxane. It states that it can.

On the other hand, the active species of the so-called Kaminsky type catalyst is [Cp ' ₂ MR] ⁺ (where Cp' = cyclopentadienyl derivative, M = Ti, Zr, Hf, R
= Alkyl), several catalyst systems not using aluminoxanes as cocatalysts have been reported.

Taube et al., J. Organometall. Chem., 34
7 , C9 (1988) shows [Cp ₂ TiMe (THF)] ⁺ [B
Ph _4] ^- (Me = methyl, Ph = phenyl group) with a compound represented by have successfully ethylene polymerization. Jo
rdan et al. in J. Am. Chem. Soc., 109 , 4111 (1987)
It shows that a zirconium complex such as [Cp ₂ ZrR (L)] ⁺ (R = methyl group, benzyl group, L = Lewis base) polymerizes ethylene.

Japanese Patent Publication No. 1-501950, Japanese Patent Publication No.
JP-A-502036 describes a method of polymerizing an olefin using a catalyst comprising a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation.

Zambelli et al., Macromolecules, 22 , 2186.
(1989) reported that isotactic polypropylene can be produced using a catalyst obtained by combining trimethylaluminum and fluorodimethylaluminum with a zirconium compound having a cyclopentadiene derivative as a ligand.

JP-A-3-179005 discloses a)
Neutral metallocene compounds, b) aluminum alkyls,
c) An olefin polymerization catalyst comprising a Lewis acid is disclosed.

Since the above-mentioned Kaminski type catalyst is generally a system which is soluble in a solvent, when the solvent polymerization or the gas phase polymerization is carried out, the bulk specific gravity of the produced polymer is low and the powder property is low. Problems such as poor adhesion and adhesion of a wall to a polymerization machine.

To solve these problems, Japanese Patent Application Laid-Open No.
JP-A-108610, JP-A-63-66206, and JP-A-2-173104 describe a method of polymerizing an olefin using a solid catalyst in which a metallocene compound and an aluminoxane are supported on a fine particle carrier. I have. However, the solid catalysts obtained using these aluminoxanes have a drawback of low activity per solid catalyst. Therefore, development of a solid catalyst that does not use aluminoxane is desired.

JP-A-3-234709 discloses that
(A) A solid catalyst for olefin polymerization comprising a particulate carrier and (B) a transition metal compound containing a ligand having a cycloalkadienyl skeleton and containing an anion containing a boron element is disclosed. . However, a solid catalyst in which a transition metal compound and an anion containing a boron element are supported on the same carrier as described in the same publication has poor storage stability of the catalyst, and further, has been applied to solvent polymerization and the like. In this case, the powder properties such as the bulk specific gravity of the produced polymer and the problems such as adhesion to the wall of the polymerization machine were insufficient.

[0014]

The so-called Kaminsky type catalyst comprising a metallocene compound / aluminoxane as described above requires the use of a large amount of aluminoxane in order to obtain high activity. Therefore, the solid catalyst obtained from this has a problem that the activity per solid catalyst is low. Further, a solid catalyst obtained without using an aluminoxane as described in JP-A-3-234709 is inferior in powder properties such as a bulk specific gravity of a produced polymer or adheres to a polymerization machine by a wall. Was causing.
Further, in the solid catalyst in which the metallocene is supported on the fine particle carrier as described above, the low activity of the metallocene is generally caused by low activity, and the improvement of the activity is a problem.

[0015]

Means for Solving the Problems The present inventors have solved the above-mentioned problems, and have been aimed at producing a polyolefin having a high metallocene content and excellent in powder properties even when applied to solvent polymerization with high activity. As a result of intensive studies on the development of solid catalysts, we found that the above-mentioned object was achieved by the solid catalyst obtained by a special supporting method, and that the polymer did not adhere to the wall of the polymerization machine even when continuous polymerization was performed.
The present invention has been completed.

That is, the present invention relates to (A) (a) a tetravalent zirconia having a crosslinkable or non-crosslinkable ligand comprising at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof;
Um, a compound containing a transition metal compound selected from compounds of titanium and hafnium (b) a solid catalyst component aluminoxane treated is formed from particulate inorganic oxide support which has been subjected, and (B) (c) anion and From Lewis acidic compounds
It is an object of the present invention to provide a solid catalyst for producing a polyolefin, comprising a solid cocatalyst component formed from a compound capable of stabilizing a cation of a selected transition metal compound of the component (a) .

Further, the present invention is a method for producing a polyolefin, comprising polymerizing an olefin in the presence of the catalyst comprising the above (A) and (B). In the present invention, among the component (A), tetravalent having a cross-linkable or non-cross-linkable ligand comprising at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof used as the component (a) Of zirconium, titanium and
Transition metal compound selected from compounds of hafnium, Ri compound der so-called metallocene compound, preferably the following general formula (Formula 1)

[0018]

Embedded image (Wherein, A ^1, A ² is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof,, A ^1, A ² good be different be the same as each other .A ^3, A ⁴ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, an aryl halide group, or a hydrocarbon group containing a hetero atom such as oxygen, nitrogen, sulfur, or silicon. Q is a carbon atom linking A ¹ and A ²
To 10 or a hydrocarbon group containing silicon, germanium, and tin. A ³ and A ⁴ may be connected to each other to form a ring structure among A ³ , A ⁴ and Q. R ¹ and R ² represent a halogen atom, a hydrogen atom, and a carbon number of 1 to
10 alkyl groups, silicon-containing alkyl groups, 6 to 2 carbon atoms
0 represents an aryl group, an alkylaryl group, or an arylalkyl group, wherein at least one of R ¹ and R ² is a hydrogen atom,
An alkyl group having 1 to 10 carbon atoms, a silicon-containing alkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, and an arylalkyl group. M is titanium, zirconium, hafnium. ) Is used.

In the formula, A ¹ and A ² represent a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof. Specific examples of A ¹ and A ² include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an indenyl group, a 3-methylindenyl group,
Fluorenyl group, 1-methylfluorenyl group, 2,7-
And a di-t-butylfluorenyl group. A ³ and A ⁴ are an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogenated aryl group or oxygen, nitrogen,
It is a hydrocarbon group containing a hetero atom such as sulfur or silicon or a hydrogen atom. Specific examples of A ³ and A ⁴ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a phenyl group, a toluyl group, a fluorophenyl group, a methoxyphenyl group,
A benzyl group and the like can be mentioned. Q is A ¹ , A ²
Is a hydrocarbon group having 1 to 10 carbon atoms or a hydrocarbon group containing silicon, germanium, and tin, and is preferably a hydrocarbon group or a silicon atom. A ³ and A ⁴ may be linked to each other to form a ring structure between A ³ , A ⁴ and Q. In such a case, A ³ , A ⁴ and Q may form a group. Examples thereof include a cyclopentylidene group, a cyclohexylidene group, and a tetrahydropyran-4-ylidene group. R ^1, R ² represents a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, silicon-containing alkyl group, an aryl group having up to 20 carbon atoms, an alkylaryl group, an arylalkyl group, R ^1, R ^At least one of ² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a silicon-containing alkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. R ¹ , R
Preferred specific examples of ² include a chlorine atom, a methyl group, a phenyl group, and a trimethylsilylmethyl group.

In the present invention, a transition metal compound in which at least one of R ¹ and R ² is a hydrogen atom, a methyl group, a phenyl group or a trimethylsilylmethyl group is preferably used. Such transition metal compounds are described, for example, in J. Or.
ganometal.Chem., 34 , 155 (1972), Macromolecules, 2
0, 1015 (1987) and the like, it can be obtained by reacting a corresponding dihalogen compound with an organometallic compound having Li or Mg.

Preferred examples of the transition metal compound represented by the above general formula (Formula 1) include bis (cyclopentadienyl) zirconium dimethyl and bis (cyclopentadienyl) transition metal compounds having a non-bridging ligand. ) Zirconium diphenyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, (cyclopentadienyl)
(Pentamethylcyclopentadienyl) zirconium dimethyl, and transition metal compounds having a bridging ligand include ethylene bis (1-indenyl) zirconium dimethyl;
Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, dimethylsilylenebis (methylcyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentane In addition to zirconium compounds such as dienyl) (9-fluorenyl) zirconium dimethyl and diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dimethyl, similar hafnium compounds and the like, for example, JP-A-3-9913, Kaihei 2-13
Transition metal compounds such as those described in JP-A-1488, JP-A-3-21607, JP-A-3-106907 and the like can be mentioned. In addition, the transition metal compounds discovered by the present inventors, isopropylidene (cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dimethyl, 1,4-
And cyclohexanediylidenebis [(cyclopentadienyl) (9-fluorenyl) zirconium dimethyl].

In the present invention, the aluminoxane used in the treatment of the finely divided inorganic oxide carrier with the component (b) in the component (A) is represented by the general formula (3).

[0023]

Embedded image Wherein R is a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, and n is an integer of 2 or more. In particular, R is an alkylaluminoxane having an alkyl group, and n is 5 or more, preferably 10 or more. Is used. More preferred are methylaluminoxane, ethylaluminoxane and isobutylaluminoxane. The aluminoxane may contain some alkylaluminum compounds. In addition, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, JP-A-3-103407 and the like can also be suitably used.

The fine inorganic oxide carrier has an average particle diameter of 0.01 to 500 μm, preferably 1 to 200 μm.
m, more specifically, for example, SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , Mg
O or a complex thereof can be mentioned.

As a method of treating these particulate inorganic oxide carriers with the aluminoxane, a method of contacting the particulate inorganic oxide carrier and the aluminoxane in an organic solvent or in the absence of a solvent is preferably used. The contacting temperature is -50 ° C to 300 ° C, preferably 0 ° C to
It is in the range of 200 ° C. The organic solvent used when contacting in an organic solvent is not particularly limited as long as it is inert to aluminoxane, and specifically, benzene, toluene, xylene, pentane, hexane, heptane, decane And cyclohexane and other aromatic and aliphatic hydrocarbons. The use ratio of aluminoxane to the particulate inorganic oxide carrier is 0.01
It is 100 times by weight, preferably 0.1 to 10 times by weight.

The solid catalyst component (A) in the present invention can be obtained by bringing the transition metal compound component (a) into contact with the particulate inorganic oxide carrier component (b) treated with aluminoxane. As a method for contacting, benzene, toluene, xylene, pentane, hexane, heptane, decane, aromatic and aliphatic hydrocarbon solvents such as cyclohexane, a method of contacting both components,
Alternatively, a co-pulverization method using a pulverizer or the like with substantially no solvent may be used. The contact temperature is -10
The temperature ranges from 0 ° C to 200 ° C, preferably from -50 ° C to 100 ° C.

In the present invention, the step of contacting the particulate inorganic oxide carrier with aluminoxane, or the step of bringing the transition metal compound component (a) and the particulate inorganic oxide carrier component (b) treated with aluminoxane into contact with each other. It is desirable to wash with an organic solvent in at least one of the steps. Otherwise, problems may occur in powder properties such as bulk specific gravity of the produced polymer. Examples of the organic solvent used in the washing include aromatic and aliphatic hydrocarbons such as benzene, toluene, xylene, pentane, hexane, heptane, decane, and cyclohexane. The solid catalyst component (A) of the present invention thus obtained has a transition metal atom of 0.01 to 70% by weight, preferably 0.1 to 30% by weight, and an Al atom of 0.1 to 90% by weight. , Preferably 1
８０80% by weight.

In the component (B) of the present invention, the compound capable of stabilizing the cation of the transition metal compound of the component (a) used as the component (c) includes the transition metal compound. And a compound containing an anion capable of stabilizing the cation, and a Lewis acidic compound.

Examples of the anion capable of stabilizing the cation of the transition metal compound include an organic boron compound anion, an organic arsenic compound anion, an organic phosphorus compound anion, an organic aluminum compound anion, and an organic gallium compound anion. Among them, those which are relatively bulky and do not bind to the formed transition metal cation compound or strongly coordinate to inactivate the polymerization active species are preferably used. Examples of such suitable anions include, for example, the above-mentioned tetraphenylboron anion by Taube, Jordan, et al.
Examples thereof include tetrakis (pentafluorophenyl) boron anions and similar aluminum compound anions and gallium compound anions described in JP-A-502020, JP-A-3-179006 and JP-A-3-207703. A compound containing an aluminum compound anion or a gallium compound anion can be produced by a method similar to a compound containing a boron compound anion described in, for example, JP-A-3-207703.

The cation for forming an ionic compound by forming a pair with these anions is not particularly limited as long as it does not inactivate the polymerization active species. Cations can be mentioned. Examples of such a cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, and an ammonium cation. Specifically, silver cation, dicyclopentadienyl iron cation,
Triphenylcarbenium cation, triphenylphosphonium cation, tributylammonium cation and the like.

The Lewis acidic compound can be used without particular limitation as long as it is a known compound exhibiting Lewis acidity and does not inactivate the polymerization active species. Preferable examples include tris (pentafluorophenyl) boron described in JP-A-3-179005.

The fine particle carrier used as the component (d) has an average particle diameter of 0.01 to 500 μm, preferably 1 to 500 μm.
Particulate inorganic or organic carrier in the range of 200 μm. Examples of the fine inorganic carrier include metal oxides and metal chlorides. Specifically, SiO ₂ , Al ₂ O ₃ , T
iO ₂ , ZrO ₂ , MgO or a composite thereof, Mg
Cl ₂ , AlCl _{3 and the} like. Examples of the fine organic carrier include organic polymers such as polyethylene, polypropylene, polystyrene, and polynorbornene.

The solid co-catalyst component (B) in the present invention can be obtained by bringing the components (c) and (d) into contact with each other. As a method of contacting, in an organic solvent,-
A method in which the components (c) and (d) are brought into contact at a temperature in the range of 100 ° C to 300 ° C, preferably -50 ° C to 200 ° C, is preferably used. As the organic solvent used at that time,
Although not particularly limited, specifically, benzene, toluene, xylene, pentane, hexane, heptane, decane, aromatic and aliphatic hydrocarbons such as cyclohexane, chloroform, halogenated hydrocarbons such as dichloromethane, diethyl ether, tetrahydrofuran, In addition to ethers such as dimethoxyethane, alcohols such as methanol, ethanol, isopropanol and butanol can be exemplified. The use ratio of the component (c) to the component (d) is 0.001 to 100 times by weight, preferably 0.01 to 50 times by weight. The solid catalyst component (B) of the present invention thus obtained includes the component (a)
0.1 to 99% by weight, preferably 5 to 90% by weight of a compound capable of stabilizing the cation of the transition metal compound .

By bringing the above components (A) and (B) into contact, it can be used as the solid catalyst for producing a polyolefin of the present invention. The method for bringing the component (A) and the component (B) into contact is not particularly limited, and the method can be used in the polymerization of an olefin by bringing the component into contact with or without a solvent in the presence or absence of an olefin. In the polymerization of the olefin, the use ratio of the component (B) to the component (A) is 0.01 to 50 times by weight, preferably 0.1 to 10 times by weight.

In the present invention, a polyolefin can be produced by using a solid catalyst comprising the above components (A) and (B) in the presence of an organoaluminum compound. As the organoaluminum compound of the general formula _{^{R 1 j Al (OR 2)}} k H l X m ( wherein R ^1, R ² represents a hydrocarbon group having up to 20 carbon atoms, R ^1, R ² are each X is a halogen atom, O is an oxygen atom, H is a hydrogen atom, j is an integer of 1 to 3, and k, l, and m are integers of 0 to 2. And j + k + 1 + m = 3). Specific examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum hydride and the like. Among them, triethylaluminum and triisobutylaluminum are preferably used.

The polymerization method and polymerization conditions carried out by the method of the present invention are not particularly limited, and known methods carried out in the polymerization of olefins are used, and a solvent polymerization method using an inert hydrocarbon medium or a substantially insoluble solvent is used. A bulk polymerization method or a gas phase polymerization method in which no active hydrocarbon medium is present can be used, and the polymerization is generally performed at a polymerization temperature of -100 to 200 ° C and a polymerization pressure of normal pressure to 100 kg / cm ² . Preferably, it is -50 to 100 ° C and normal pressure to 50 kg / cm ² .

In the present invention, examples of the hydrocarbon medium used in the polymerization include butane, pentane, hexane, and the like.
In addition to saturated hydrocarbons such as heptane, octane, nonane, decane, cyclopentane, and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene can be used. Examples of the olefin used in the polymerization include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, And olefins having 2 to 25 carbon atoms such as octadecene.

In the present invention, the present invention can be used not only for homopolymerization of olefins but also for producing copolymers of olefins having about 2 to 25 carbon atoms such as propylene and ethylene and propylene and 1-butene.

[0039]

The present invention will be specifically described below with reference to examples.

[0040] Example 1 Ethyl aluminoxane synthetic thoroughly nitrogen-purged glass flask copper pentahydrate 23.6g sulfate 300 cm ³ was suspended in toluene 100 cm ^3. To this suspension, 33.4 g of triethylaluminum diluted with 50 cm ³ of toluene was added dropwise at -50 ° C.
After slowly raising the temperature to room temperature and stirring at room temperature for 10 hours, the reaction was further performed at 50 ° C. for 5 hours. The reaction slurry was filtered to obtain a toluene solution of ethylaluminoxane. The molecular weight of this ethylaluminoxane determined by the freezing point depression method was 1,130. Preparation of Solid Catalyst Component (A1) In a 100 cm ³ glass flask, put silica (manufactured by Fuji Devison Co., surface area 300 m ² / g, average particle diameter 57).
μm) of 2.0 g, 25 mmol of toluene solution of ethylaluminoxane synthesized above as Al atom and 20 cm ³ of toluene were added, and the mixture was stirred at 50 ° C. for 3 hours. The supernatant was removed by decantation, and the residue was washed three times with 50 cm ³ of heptane to complete the treatment of silica with ethylaluminoxane.

Isopropylidene (cyclopentadienyl) synthesized by the method described in JP-A-2-41303
0.39 g of isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dimethyl obtained by further reacting (9-fluorenyl) zirconium dichloride with methyllithium was added to ethylaluminoxane-treated silica and heptane prepared above. At room temperature for 2 hours. The supernatant was removed by decantation and further washed three times with 50 cm ³ of heptane to obtain a solid catalyst component (A1). As a result of analyzing this solid catalyst, 1.8 wt% as Zr atom,
The content was 12.7% by weight as Al atoms. Preparation of Solid Cocatalyst Component (B1) In a 100 cm ³ glass flask, put silica (manufactured by Fuji Devison, surface area 300 m ² / g, average particle diameter 57).
4.2 μm) were suspended in 70 cm ³ of toluene. 1.3 g of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to the suspension, followed by stirring at room temperature overnight. The supernatant was removed by decantation and further washed three times with 70 cm ³ of heptane to obtain a solid promoter component (B1). As a result of analyzing this solid cocatalyst, it was found to contain 10.8 wt% as carbon atoms.

Example 2 Polymerization In a 1.5 dm ³ autoclave sufficiently purged with nitrogen, 0.2 g of the solid catalyst component (A1) and 0.2 g of the solid cocatalyst component (B1) prepared in Example 1 were charged. 0.75 dm ³ of propylene was added, and polymerization was carried out at 40 ° C. for 1 hour. After terminating the polymerization by adding a small amount of methanol into the system, unreacted propylene was purged and dried to obtain 158.3 g of syndiotactic polypropylene powder. Intrinsic viscosity (hereinafter abbreviated as [η]) measured with a tetralin solution of powder at 135 ° C.
Was 0.92 dl / g, the syndiotactic pentad fraction (rrrr) measured by ¹³ C-NMR was 0.83, and the bulk specific gravity was 0.35 g / cm ³ . Also, little adhesion of the polymer to the walls of the autoclave.

Example 3 As a polymerization catalyst, the solid catalyst component (A1) prepared in Example 1
Polymerization was carried out in the same manner as in Example 1 except that 0.1 g, 0.1 g of the solid cocatalyst component (B1) and 0.06 g of triethylaluminum were used. As a result, 131.7 g of syndiotactic polypropylene powder was obtained. [Η] of the powder was 0.90 dl / g, rrrr was 0.83, bulk specific gravity was 0.26 g / cm ³ , and the polymer hardly adhered to the autoclave wall.

Example 4 Synthesis of transition metal compound [isopropylidene (cyclopentadiene) (2,7-
Di-t-butyl-9-fluorene)] into a 300 cm ³ glass flask sufficiently purged with nitrogen.
12.0 g of 7-di-t-butyl-9-fluorene (Synth
sis, 335 (synthesized by the method described in 1984) was dissolved in 100 cm ³ of tetrahydrofuran. To this solution, 44 mmol of a methyllithium ether solution was added dropwise at -78 ° C. After dropping, raise the reaction solution to room temperature,
Stir at the same temperature for 3 hours. To this reaction solution, 4.6 g of 6,6-dimethylfulvene diluted with 50 cm ³ of tetrahydrofuran was added dropwise at -78 ° C. After dropping,
The reaction temperature was raised to room temperature and stirring was continued for another 10 hours. The reaction was stopped by adding 100 cm ^{3 of} 3.6% hydrochloric acid, and the ether layer was washed with water and evaporated to dryness to obtain a reddish brown viscous liquid. The viscous liquid was recrystallized from hot acetone to give a white powder of isopropylidene (cyclopentadiene) (2,7-di-t-butyl-9-
Fluorene) was obtained.

The physical properties of this compound are shown below. [Isopropylidene (cyclopentadienyl) (2,7
-Di-tert-butyl-9-fluorenyl) zirconium dimethyl] First, the isopropylidene (cyclopentadiene) (2,7-di-tert-butyl-9-fluorene) 1 synthesized above
By lithiating 0.0 g with n-butyllithium, isopropylidene (cyclopentadiene) (2,
A dilithium salt of 7-di-t-butyl-9-fluorene) was prepared.

Next, 6.1 g of zirconium tetrachloride was suspended in 100 cm ³ of methylene chloride in a 500 cm ³ glass flask sufficiently purged with nitrogen. -78 ° C
A solution of isopropylidene (cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) dilithium in 300 m ³ of methylene chloride was added at −78 ° C. After stirring at −78 ° C. for 4 hours, the temperature was slowly raised to room temperature, and the reaction was continued at that temperature for another 15 hours.
The reddish-brown solution containing a white precipitate of lithium chloride was filtered off, and the filtrate was concentrated and then cooled at −30 ° C. for 24 hours to give isopropylidene (cyclopentadienyl) (2,7-di-t- Butyl-9-fluorenyl)
4.3 g of zirconium dichloride were obtained.

Further, this isopropylidene (cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride was dissolved in diethyl ether.
It was reacted with 2 equivalents of methyllithium and recrystallized from hexane to obtain isopropylidene (cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dimethyl. The physical properties of this compound are shown below. Preparation of Solid Catalyst Component (A2) Instead of isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dimethyl, the isopropylidene (cyclopentadienyl) (2,7
-Di-tert-butyl-9-fluorenyl) zirconium dimethyl, except that the solid catalyst component (A
The solid catalyst component (A2) was prepared in the same manner as in the preparation of 1) . In the obtained solid catalyst, 1.5 wt% of Zr was contained.
Atoms and 15.9 wt% Al atoms.

Example 5 Polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component (A2) obtained in Example 4 and the solid promoter component (B1) obtained in Example 1 were used as the polymerization catalyst. went. As a result, 224.7 g of syndiotactic polypropylene powder was obtained. [Η] of the powder is 0.63 dl /
g and rrrr are 0.87 and bulk specific gravity is 0.33 g / cm ^3.
And there was little adhesion of the polymer to the walls of the autoclave.

Example 6 [Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate] In a 500 cm ³ flask purged with nitrogen, 19.6 g of bromopentafluorobenzene was dissolved in 150 cm ³ of toluene, and n-butyl was added to this solution. 80 mmol of lithium was added dropwise at -78 ° C over 2 hours. After stirring at −78 ° C. for 30 minutes, 50 cm ³ of a toluene solution containing 5.3 g of aluminum bromide was added dropwise, and the mixture was reacted at room temperature overnight. After evaporating the solvent from the reaction slurry containing the white precipitate under reduced pressure, 150 cm ^{3 of} methylene chloride and 2.3 g of triphenylchloromethane were added, and the mixture was reacted at room temperature for 1 hour. The obtained reaction solution was filtered, and the filtrate was dried under reduced pressure to obtain 2.9 g.
Of triphenylcarbenium tetrakis (pentafluorophenyl) aluminate was obtained as a brown powder. The physical properties of this compound are shown below. Elemental analysis _{C 43 H 15 F 20 Al C} H F calc (%) 55.01 1.60 40.5 Found (%) 56.19 1.58 39.7 solid catalyst prepared tri component (B2) Instead of phenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) synthesized above
Example 1 except that 2.0 g of aluminate was used.
Solid co-catalyst component (B2) was prepared in the same manner as preparation of solid co-catalyst component (B1) . As a result of analyzing this solid cocatalyst, it was found to contain 13.5 wt% as carbon atoms.

Example 8 The polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component (A1) obtained in Example 1 and the solid cocatalyst component (B2) obtained in Example 7 were used as the polymerization catalyst. went. As a result, 121.1 g of syndiotactic polypropylene powder was obtained. [Η] of the powder is 0.99 dl /
g and rrrr are 0.86 and bulk specific gravity is 0.32 g / cm ^3.
And there was little adhesion of the polymer to the walls of the autoclave.

[0051]

By using the solid catalyst of the present invention and carrying out the method of the present invention, a polyolefin having good powder properties can be produced with high activity, and the adhesion of the polymer to the wall of the polymerization machine. Is extremely valuable industrially.

Continuation of the front page (56) References JP-A-5-125112 (JP, A) JP-A-5-148316 (JP, A) JP-A-5-247128 (JP, A) JP-A-4-142306 (JP) , A) JP-A-3-74412 (JP, A) JP-A-3-709 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (5)

(57) [Claims] (A) (a) a tetravalent zirconium having a cross-linkable or non-cross-linkable ligand comprising at least one cyclopentadienyl group, indenyl group, fluorenyl group, or a derivative thereof;
Um, a compound containing a transition metal compound selected from compounds of titanium and hafnium (b) a solid catalyst component aluminoxane treated is formed from particulate inorganic oxide support which has been subjected, and (B) (c) anion and From Lewis acidic compounds
A solid catalyst for producing a polyolefin comprising a solid co-catalyst component formed from a selected compound capable of stabilizing the cation of the transition metal compound as the component (a) . 2. A method for producing a polyolefin, comprising polymerizing an olefin in the presence of the solid catalyst of claim 1 or in the presence of a catalyst comprising the solid catalyst of claim 1 and an organoaluminum compound. 3. The transition metal compound used as the component (a) is represented by the following general formula (1). (Wherein, A ^1, A ² is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof,, A ^1, A ² good be different be the same as each other .A ^3, A ⁴ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, an aryl halide group, or a hydrocarbon group containing a hetero atom such as oxygen, nitrogen, sulfur, or silicon. Q is a carbon atom linking A ¹ and A ²
To 10 or a hydrocarbon group containing silicon, germanium, and tin. A ³ and A ⁴ may be connected to each other to form a ring structure among A ³ , A ⁴ and Q. R ¹ and R ² represent a halogen atom, a hydrogen atom, and a carbon number of 1 to
10 alkyl groups, silicon-containing alkyl groups, 6 to 2 carbon atoms
0 represents an aryl group, an alkylaryl group, or an arylalkyl group, wherein at least one of R ¹ and R ² is a hydrogen atom,
An alkyl group having 1 to 10 carbon atoms, a silicon-containing alkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, and an arylalkyl group. M is titanium, zirconium, hafnium. 2. The solid catalyst for producing a polyolefin according to claim 1, which is a transition metal compound represented by the formula: 4. The compound which can stabilize the cation of the transition metal compound of component (a) used as component (c) is a compound containing boron. Item 7. A solid catalyst for producing a polyolefin according to Item 1. 5. The compound capable of stabilizing the cation of the transition metal compound of the component (a) used as the component (c) is a compound containing aluminum or gallium. The solid catalyst for producing a polyolefin according to claim 1.