JP3405784B2 - Method for producing polyolefin - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing olefins using a metallocene catalyst.

[0002]

2. Description of the Related Art Recently, it has been known that stereospecific polymerization is possible in the polymerization of .alpha.-olefins (mainly propylene) with a metallocene catalyst system. For example, atactic polypropylene (Makromol.Chem., Rapid Commu
n.4, 417-421 (1983), JP-A-58-19309, isotactic polypropylene (Angew. Chem. Int. Ed. En.
gl., 24,507-508 (1983), J.Am.Chem.Soc., 106,6355 (198
4), J. Am. Chem. Scc., 109, 6544 (1987), Chem. Lett., 1853-1.
856 (1989), JP-A-2-76887), Syndiotactic polypropylene (J. Am. Chem. Soc., 110, 6255, (1988))
It is known that the above can be produced. The ligand structure and the three-dimensional structure of the zirconium complex are the key to the development of these stereospecificities. However, the type and performance of metallocene compounds capable of producing industrially important isotactic polypropylene are very limited.

For example, ethylene bis (indenyl) zirconium dichloride and ethylene bis (tetrahydroindenyl) zirconium dichloride disclosed in JP-A-63-295607 (Cosden) can produce isotactic polypropylene in the presence of methylaluminoxane. However, its stereoregularity is relatively low at about 95% in mm%, and the melting point of the polymer is 135 ° C to 146 ° C.
And there is a low drawback. Even isotactic polypropylene obtained from dimethylsilylenebis (indenyl) zirconium dichloride (USP 5,017,714) in which the cross-linking portion is changed to silicon has a low melting point of 149 ° C to 153 ° C.
In addition, these C ₂ symmetric complexes have two structural isomers, a racemic body and a meso body, and only one racemic body can produce isotactic polypropylene. The meso body generated in the process is
It produces an atactic polymer which is industrially undesirable. Therefore, a complicated purification process for body separation of meso is required, and there is a drawback that the cost for producing the complex increases.

Further, JP-A-1-301704, JP-A-1-319489, JP-A-2-76887, and Chem. Let.
Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride disclosed in t., 1853 (1989) is a high isotactic polypropylene of 99% or more in mm% in the presence of methylaluminoxane. Although it can be produced, this complex also has two structural isomers structurally, a racemic body and a meso body, and one isomer (racemic body) capable of producing isotactic polypropylene is the other. A very complicated purification process is required to purify and separate from the (meso form).

Others Bis (t-butylcyclopentadienyl) zirconium dichloride (Organometallics, 10,
2061 (1991)), dimethylsilylene bis (3-t-butyl-5-methylcyclopentadienyl) zirconium dichloride (USP 5,132,262) and the like also obtain highly isotactic polypropylene in the presence of methylaluminoxane. In that case, it is necessary to separate the racemate and the meso form, and the separation and purification of the isomers are very complicated. The above is
An example of the prior art for the production of isotactic polypropylene by a C ₂ symmetric complex that requires isomer separation, but recently a C ₁ symmetric complex that does not require isomer separation has been disclosed.

Dimethylsilylene (indenyl) (fluorenyl) zirconium dichloride (EP 052828)
7) is based on this idea, but in the polymerization of propylene, only atactic polypropylene is given and stereoregular polymerization does not occur. C with a similar idea
_One- symmetric complex, Tobin J. Marks et al. (J. Am. Chem. So.
c., 115, 3326 (1993)) gave isotactic polypropylene with methylaluminoxane as a cocatalyst. However, the reported complexes are expensive complexes with chiral substituents introduced and do not give polypropylene of sufficient stereoregularity and molecular weight unless lowered to temperatures as low as -45 ° C.

According to Chien et al., Ethylidene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride gives a thermoplastic elastomer having a melting point of about 60 ° C. when propylene polymerization is carried out in combination with methylaluminoxane ( J. Am. Chem. Soc., 112, 2030 (19
90) J. Am. Chem. Soc., 113,8569 (1991) Macromol., 2
4, 850 (1991) Macromol., 25, 1242 (1992) J. Poly.
Sci. Part A: Poly. Chem., 30, 2601 (1992)), does not give highly isotactic polymers. In addition, dimethylsilylene (fluorenyl) disclosed by Canich
(T-Butylamino) zirconium dichloride (WO 92 /
05204) is also an example of giving an asymmetric isotactic polypropylene, but has the drawback that the melting point is as low as 145 ° C. and the activity per complex is extremely low.

Further, conventionally, isopropylidene (methylcyclopentadienyl) (fluorenyl) zirconium dichloride (Makromol. Chem., Macromol. Symp., 48/49,
253 (1991), JP-A-3-9913) is known. However, this complex gives a syndio-isoblock polymer in propylene polymerization (32% in mm%), not the industrially more important isotactic polypropylene.

These catalyst systems are characterized by a significantly higher activity per transition metal. Biscyclopentadienyl zirconium dichloride is a metallocene compound that has been widely known and classically used. A technique for polymerizing olefins using a catalyst composed of this compound and aluminoxane is disclosed by Kaminsky et al. (JP-A-58-19309). However, in this biscyclopentadienylzirconium dichloride catalyst system, it is necessary to use a large amount of very expensive methylaluminoxane as a co-catalyst, and it is industrially difficult to obtain sufficient activity with relatively inexpensive ethylaluminoxane. It is a big barrier when using it. Regarding the degree of polymerization of methylaluminoxane,-(O-Al (M
e)) It is disclosed that n is preferably 2 to 16 when described as n-, and in JP-A-61-211307, n is 4
It is disclosed that 0 or more is suitable. However, the activity is extremely low when the alkyl group is changed to a group other than the methyl group.

Further, a method has been proposed in which methylaluminoxane is generated in-situ by directly reacting trimethylaluminum with hydrous silica without using methylaluminoxane (Japanese Patent Laid-Open No. 20720/1988).
3). The essential reason why methylaluminoxane is expensive is that trimethylaluminum, which is a raw material, is more expensive than other organoaluminum compounds, and cannot be an essential solution as long as trimethylaluminum is used.

Further, a method of mixing and using methylaluminoxane and triisobutylaluminum for the purpose of reducing the amount of methylaluminoxane used (JP-A-60-13060).
4) and an attempt to use an aluminoxane obtained from a mixture of trimethylaluminum and another trialkylaluminum are disclosed (EP0482453), but sufficient activity is not obtained. It is also known that organoaluminum sulfate obtained by reacting organoaluminum with sulfuric acid is used as a co-catalyst (IUPAC 32nd Internati
onal Symposium on Macromolecules, E.Chiellini)
Polymerization activity for metallocene catalyst is not sufficient. Also,
It has been disclosed that a dimer of isobutylaluminoxane is effective for olefin polymerization (JP-A-3-1975).
04). However, the polymerization activity is low.

Further, as a method without using methylaluminoxane, a catalyst in which a metallocene cation species is stabilized with a special boron compound has been proposed. For example RF Jordan
Et al. Have reported that ethylene polymerizes with tetraphenylboron as a counter anion in a THF complex of zirconocene cation (Organometallics, 8,2892,198).
9). Further, JAEwen et al. Disclose that isotactic polypropylene polymerizes with high activity in a combination of a C ₂ symmetric ethylenebisindenyl zirconium dimethyl complex and a tetrakispentafluorophenylborate / triphenylcarbonium salt (special feature: Kaihei 3-207
703, 207704). Also, Turner et al. Report that ethylene and propylene can be polymerized with a combination of bis (cyclopentadienyl) zirconium dimethyl and tetrakispentafluoroborate ammonium salt. However, the boron compound is as expensive as methylaluminoxane, and the active species are unstable, so that it has not been industrially used (JP-A-64-5).
01950, JP-A-64-502036). Further, with respect to the polymerization of isotactic polypropylene, the stereoregularity and melting point of the produced polypropylene are low, which is not practical.

Further, as the polypropylene obtained by the metallocene catalyst, the one having a specific structure is isoblock PP,
Although known as hemi-iso PP, they all have low melting points according to the facts described, which are different from the properties of the polypropylene obtained in the present invention. Furthermore, the polypropylene obtained by the conventional Ziegler type catalyst has insufficient stereoregularity, and the atactic component is present in the resin.
The xylene insoluble matter ratio by the xylene insoluble matter measuring method described in O / DIS 1873-1 is not sufficiently high.

[0014]

DISCLOSURE OF THE INVENTION The present invention provides a catalyst system which is inexpensive in view of the above-mentioned conventional techniques and which sufficiently exhibits the activity of a metallocene catalyst and does not use aluminoxane as a cocatalyst. This also provides a high melting point polypropylene having a high xylene insoluble content.

[0015]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a combination of a specific metallocene compound and a non-coordinating ionic compound
The present invention has been achieved by finding that the above problems can be solved.

The main catalyst component [A] of the present invention has a C ₁ symmetric structure and is represented by the formula [1].

[Chemical 5] [In the formula, M ¹ is Ti, Zr or Hf, and R ¹ ,
R ² and R ³ are hydrocarbon groups having 1 to 20 carbon atoms or alkylsilyl groups and may be the same or different, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are hydrogen atoms. , Carbon number 1
To 20 hydrocarbon groups, or alkylsilyl groups, which may be the same or different from each other, and adjacent R ^{1 to} R ⁷ on the cyclopentadienyl ring are cyclic to each other via a hydrocarbon group. May be formed, Y is an alkylene group, a silylene group, or a germylene group, and n is 1
To 3 and R ⁸ and R ⁹ are hydrogen atoms and 1 to 2 carbon atoms.
A hydrocarbon group of 0 or an alkylsilyl group, which may be the same or different from each other, and may form a ring via a hydrocarbon group, and X ¹ and X ² are hydrogen. An atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen, an alkylsilyl group, or a silylalkyl group. ]

Specific examples of the transition metal compound [A] in which M ¹ is zirconium are shown below. (C ₁ symmetry) dimethylsilylene (tetramethylcyclopentadienyl) (3-t-butylcyclopentadienylzirconium) dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-neomenthylcyclopentadienylzirconium) Dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-
Menthylcyclopentadienylzirconium) dichloride, methylmethylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride, preferably R ⁴ and R ⁷ in the formula [1] are hydrogen atoms.

For example, dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilylene (3-cyclohexylcyclopentyl). Pentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dichloride,
Dimethylsilylene (3-((1,1-diethyl) butyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-phenylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-mesityl) Cyclopentadienyl) (fluorenyl) zirconium dichloride,
Dimethylsilylene (3- (o-tolyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3- (2,6-xylyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-benzyl) Cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-tritylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, dimethylsilylene (3-trimethylsilylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, methylphenylsilylene (3-t-butylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, methylphenylsilylene (3-t-butylcyclopentadienyl)
(Fluorenyl) hafnium dichloride, methylphenylsilylene (3-cyclohexylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-(( 1,1-diethyl) butyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-phenylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylsilylene (3-mesitylcyclopentadienyl) (Fluorenyl) zirconium dichloride, methylphenylsilylene (3- (o-tolyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, Preferably, in the formula [1] R
⁴ , R ⁵ and R ⁷ are hydrogen atoms.

For example, ethylene (4-methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, ethylene (4-tbutyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, ethylene ( 4-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, ethylene (4-methyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, ethylene (4-methyl-cyclo) Pentadienyl)
(3-Trimethylsilyl-indenyl) zirconium dichloride, isopropylidene (4-methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, isopropylidene (4-tbutyl-cyclopentadienyl) (3-methyl- Indenyl) zirconium dichloride, isopropylidene (4-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, dimethylsilylene (4-methyl-cyclopentadienyl) (3-methyl-indenyl)
Zirconium dichloride, dimethyl silylene (4-tbutyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, dimethyl silylene (4-
t-Butyl-cyclopentadienyl) (3-t-butyl-indenyl) zirconium dichloride, isopropylidene (4-methyl-cyclopentadienyl) (1,2,3-
Trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (4-tbutylcyclopentadienyl) (1,2,3-trimethylcyclopentadienyl) zirconium dichloride, isopropylidene (4-tbutylcyclopentadienyl) ( 1,2,3-t
Butylcyclopentadienyl) zirconium dichloride, isopropylidene (4-methyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dimethyl, isopropylidene (4-tbutyl-cyclopentadienyl) (3-methyl-indenyl) ) Zirconium dimethyl, isopropylidene (4-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dimethyl, ethylene (4-methyl-cyclopentadienyl) (3-methyl-indenyl) hafnium dichloride. In the above zirconium compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can be exemplified.

The component [B] according to the present invention is a non-coordinating ionic compound represented by the formula [2] [2].

Embedded image (M ² X ¹ X ² X ³ X ⁴ ) ^(pq)- · C ^{(pq) +} ··· [2] (In the formula, M ² is selected from 5 to 15 groups in the periodic table. Metal, X ¹ , X ² , X ³ and X ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group. An aryl group, an arylalkyl group, a substituted alkyl group, a halogen-substituted aryl group, an organic metalloid group or a halogen atom, C represents a counter cation such as carbonium or ammonium, and q represents M.
² valences at 1-7 integer, p is an integer of 2-8. )

Specific examples of these compounds include tetra (phenyl) borate / triethylammonium salt, tetra (phenyl) borate / tripropylammonium salt, tetra (phenyl) borate / tributylammonium salt, tetra (p-tolyl). Borate / trimethylammonium salt, tetra (pentafluorophenyl) borate / tributylammonium salt, tetra (pentafluorophenyl) borate / dimethylanilinium salt, tetra (3,5trifluoromethylphenyl) borate / tripropylammonium salt, tetra ( Examples thereof include o-tolyl) borate / tributylammonium salt and tetra (pentafluorophenyl) borate / tritylcarbonium salt. Preferred is a dimethylanilinium salt of tetra (pentafluorophenyl) boron or a trityl carbonium salt.

Further, in the present invention, if necessary,
It can also be used in combination with [C] an organoaluminum compound component. For example, trialkylaluminum, halogen-containing organoaluminum compounds, or aluminoxanes. Preferably, triethyl aluminum, triisobutyl aluminum, trimethyl aluminum,
Trihexyl aluminum and trioctyl aluminum compounds. Preferred are ethyl aluminum dichloride, diethyl aluminum monochloride, and ethyl aluminum sesquichloride. The amount used is 0.001 to 1 mmol / l in terms of aluminum concentration in the reaction system. The organoaluminum component at this time may be used by premixing with the components [A] and [B] immediately before the polymerization.

In the process of the present invention, the olefins to be polymerized are mainly propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-.
Decene, 4-methyl-1-pentene, cyclopentene,
Examples thereof include olefins such as cyclopentadiene, butadiene, 1,5-hexadiene, 1,4-hexadiene and 1,4-pentadiene, cyclic olefins, and dienes. Copolymerization can also be carried out by mixing two or more kinds of these comonomers. There is no limitation on the number or ratio of the monomers used in the copolymerization. For example, the fraction of ethylene and the α-olefin comonomer in the polymer is not particularly limited, but preferably ethylene / comonomer = 10.
000 to 0.5, and more preferably 1000 to 1
It is 0. Further, the lower limit of the density range that can be achieved by these copolymers can be up to 0.80, and preferably 0.
Used in the range 89 to 0.94.

The polymerization method used in the present invention can be any of liquid phase polymerization, slurry polymerization and gas phase polymerization.
Preferred is isobutane slurry polymerization or solution polymerization. Further, multistage polymerization is also possible. Alternatively, the particle size can be controlled by prepolymerizing the olefin.

The olefin pressure in the reaction system is not particularly limited, but is preferably in the range of normal pressure to 50 kg / cm ² G, and the polymerization temperature is not limited, but preferably -30.
It is in the range of ℃ to 200 ℃. Particularly preferably 0 ° C
To 120 ° C. More preferably, 50-
It is 70 ° C. Also, multistage polymerization is possible. The molecular weight at the time of polymerization can be adjusted by known means, for example, selection of temperature or introduction of hydrogen.

The polypropylene obtainable according to the present invention contains xylene-insoluble matter as compared with conventional polypropylene.
It is a completely new polymer whose physical properties such as melting point and HDT are remarkably improved, and its properties can be defined as follows. 1) It is a homopolymer of propylene,
CH ₂ -CH (CH ₃₎ - consists of repeating units of.
2) The molecular weight is 0.01 to 50 at MFR (230 ° C).
0 g / 10 min, preferably MFR (230
0.5 to 100 g / min. 3) DSC
There is a peak at a melting point of 160 ° C. or higher estimated by.
4) The xylene insoluble content evaluated by the xylene insoluble content measurement method described in ISO / DIS1873-1 is 99.8%.
What is above. The polypropylene thus limited has greatly improved properties and is extremely valuable industrially.

If desired, well-known additives and compounding agents may be used in the polymer obtained in the present invention. As examples of additives and compounding agents, antioxidants (heat resistance stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), Inorganic and organic fillers, reinforcements, colorants (dyes,
Pigments), foaming agents, cross-linking agents, fragrances and the like.

Examples of heat-resistant stabilizers include phenol-based stabilizers, sulfur-based stabilizers, and phosphorus-based stabilizers, and specifically, 2,6-di-t-butyl-4. −
Methylphenol, stearyl-β- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate and other phenolic stabilizers, dilaurylthiodipropionate and other sulfur stabilizers, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite and other phosphorus stabilizers Can be shown. Examples of the light stabilizer include salicylic acid type, benzophenone type, and benzotriazole type. Antistatic agents, antifogging agents such as esters, sulfates, phosphorus oxides, quaternary ammonium salts,
Examples thereof include betaines and polyethylene glycol type nonionic antistatic agents. Examples of the flame retardant include halogen-based flame retardants, phosphorus-based flame retardants, antimony oxide, magnesium hydroxide, and other flame retardants. Examples of lubricants (including slip agents and anti-blocking agents in a broad sense) include hydrocarbon-based, fatty acid-based, fatty acid amide-based, ester-based, alcohol-based and metal soaps.

As the filler, for example, carbon black,
White carbon, calcium carbonate, hydrous basic magnesium carbonate, clay, silicate minerals, natural silicic acid, alumina hydrate, barium sulfate, calcium sulfate, metal powder, organic fillers (for example, wood powder, fruit shell powder, Examples of the reinforcing material include asbestos, glass fiber, carbon fiber, stainless fiber, aluminum fiber, potassium titanate fiber, aramid fiber, glass beads, aluminum flakes, and the like. Colorants (dye, pigment) include titanium oxide, zinc oxide, barium sulfate,
Carbon black, aniline black, lead white, cadmium yellow, yellow lead, zinc chromate, ocher, Hansa yellow, red iron oxide, resole red, alizarin lake,
Cadmium red, Rouge, Quinacridone red, Cobalt violet, Ultramarine, Cobalt blue, Phthalocyanine blue, Phthalocyanine green, Chrome green,
Examples thereof include aluminum powder and bronze powder. Examples of the foaming agents include inorganic foaming agents such as ammonia carbonate, sodium bicarbonate, sodium nitrite, etc., nitroso-based foaming agents such as dinitrosopentamethylenetetramine, dimethyldinitrosoterephthalamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p- Examples thereof include p-oxybis (benzenesulfonyl hydrazide), disulfone hydrazide diphenyl sulfone and other sulfohydrazide foaming agents, azobisisobutyronitrile, azodicarbonamide, and other azo foaming agents. As the fragrance, there can be used natural fragrances such as musk, civet, catrium, ambergris, various synthetic fragrances, masking agents and the like.

The additives may be added at the time of pelletizing, but the pellets and the additives may be kneaded by using a Banbury mixer, rolls and various extruders as is conventionally done. It is normal to do. In some cases, it is also possible to dry-blend the pellets and the additive without melt-mixing them and then directly form them in a molding machine.

The polypropylene resin obtained in the present invention may be used as a composition by mixing it with a polyolefin resin other than the above. For example, polyethylene, EP
It can also be used as HIPP by mixing with R. In addition, general-purpose resins such as polyolefin and polystyrene, polyethylene terephthalate, nylon, EV
It can be used for melt lamination with resins such as OH, and can be applied to both in-die lamination and outside die lamination.

[0032]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, in the synthesis, unless otherwise stated, it was carried out under an argon atmosphere, and the solvent used was Na-
What was subjected to reflux dry degassing with K alloy was used. Regarding physical properties measurement, HDT was performed according to JIS-K-7207. The Tm and Tcp are measured by Perkin Elme
r DSC-7, and the measurement conditions at that time are
The value of Tcp when the temperature is raised from 20 ° C. to 230 ° C. at 20 ° C./min, held for 5 minutes, and then lowered to 20 ° C. at 20 ° C./min, and further from 20 ° C. to 20 ° C./m
The value of Tm obtained when the secondary temperature was raised to 230 ° C. in was adopted. The flexural modulus was determined according to JIS-K-6758. The xylene insoluble content Xi of the polymer is ISO
/ DIS 1873-1.
In measuring mechanical properties, BHT / Irg1010
/CA-ST=0.08/0.05/0.1 phr, and kneaded with a Labo Plastomill.

Example 1 [Synthesis of isopropylidene (4-tbutyl-cyclopentadienyl) (3-tbutylindenyl) zirconium dichloride] All reactions were carried out under an inert gas atmosphere. The reaction vessel used was previously dried. Dry THF 10 in a 300 ml glass reaction vessel
0 ml was added thereto, and 3 g of dimethyl (4-tbutylcyclopentadienyl) (3-tBuindenyl) methane was added thereto.
Was dissolved, and 15 ml of a 1.6 mol / l n-BuLi hexane solution was added under ice cooling. After reacting for 1 hour at room temperature, THF was distilled off under reduced pressure. While cooling, 50 ml of methylene chloride was added. A separately prepared flask was charged with 2.63 g of zirconium tetrachloride, and 50 ml of methylene chloride was added and suspended. This is cooled and dimethyl (4-t butylcyclopentadienyl) (3-t
A suspension of the butylindenyl) methane lithium salt was added via cannula while cooling. After reacting at room temperature for 2 hours, the produced lithium chloride was removed and the solution was concentrated to give orange crystals. (Result of X-ray crystal analysis was threo body) Yield 0.3 g The elemental analysis value of this compound is shown below. Elemental _{analysis: (C 25 H 32 ZrCl 2} ) Calculated (%): C; 60.78, H; 6.53 Found (%): C; 60.81, H; 6.48

[Synthesis of isopropylidene (4-tbutyl-cyclopentadienyl) (3-tbutylindenyl) zirconium dimethyl] isopropylidene (4-tbutyl-cyclopentadienyl) (3-tbutylindenyl) ) 200 mmol of zirconium dichloride was dissolved in 50 ml of anhydrous ether, and 400 mmol of methyl magnesium iodide (methyl grignard) was added. The precipitated salt was removed by centrifugation, and the solution was concentrated under reduced pressure. This was extracted with toluene and recrystallized from toluene to obtain a dimethyl compound. Yield 70% Purity was confirmed by NMR and Mass.

[Catalyst Preparation] Isopropylidene (4-t butyl-cyclopentadienyl) (3-t
7 ml of a toluene solution of butylindenyl) zirconium dimethyl (0.001 mol / l) was charged into a well-dried, 50-ml two-necked flask which had been purged with argon. Solution (0.001mo
7 ml of 1 / l) was added and stirred at room temperature for 20 minutes. This is designated as the main catalyst solution A.

[Polymerization] 1.5 L of dehydrated toluene was charged into a stainless autoclave having a volume of 6 L and dried and purged with nitrogen. To this, 5 ml of a toluene solution of triisobutylaluminum (1 mol / l) was added, and the mixture was stirred at room temperature for 30 minutes. Then, after the entire amount of the main catalyst solution A was charged into this autoclave, the temperature was adjusted to a predetermined temperature (in this case, 5 ° C.), and the propylene monomer was added to 10
mol was slowly introduced to carry out polymerization. The polymerization reaction was carried out for 1 hour, and the reaction was stopped by adding ethanol as a killer to the reactor. The obtained polymer was poured into a large amount of methanol and filtered to obtain a polymer. The polymer was rinsed with an acetone solution of BHT (0.1%) and then dried under reduced pressure. The yield was 108 g.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the organic aluminum used in the polymerization in Example 1 was triethylaluminum.

Example 3 Polymerization was carried out in the same manner as in Example 1 except that hydrogen was charged in a 20 ml micro cylinder at 1 kg / cm ² and 7 ml of the main catalyst component A was charged at the time of polymerization.

Example 4 Polymerization was carried out in the same manner as in Example 1 except that 2 kg / cm ² of hydrogen was charged with a 20 ml micro cylinder at the time of polymerization and 4 ml of the main catalyst component A was charged at the time of polymerization.

Example 5 The same polymerization as in Example 1 was carried out except that the metallocene complex of Example 1 was changed to the complex shown in Table 1.

Example 6 The same polymerization as in Example 1 was carried out except that the metallocene complex of Example 1 was changed to the complex shown in Table 1.

Comparative Example 1 In Example 1, MAO was added to Al / Zr = when preparing the catalyst.
The same procedure was performed, except that the toluene solution of tetra (pentafluorophenyl) borate / triphenylcarbonium salt was used instead of the toluene solution so that the concentration became 2000.

Comparative Example 2 In Example 1, MAO was added to Al / Zr = when preparing the catalyst.
Used instead of a toluene solution of tetra (pentafluorophenyl) borate · triphenyl carbonium salt to be 2000, the metallocene complex is a C ₂ symmetry r
Example 1 was repeated except that ac-ethylenebis (tetrahydroindenyl) zirconium dimethyl (Et (THIND) ₂ ZrMe ₂ ) was used.

Comparative Example 3 In Example 1, MAO was added to Al / Zr = when preparing the catalyst.
Used instead of a toluene solution of tetra (pentafluorophenyl) borate · triphenyl carbonium salt to be 2000, the metallocene complex is a C ₂ symmetry ra
Example 1 was repeated except that c-Et (Ind) ₂ ZrMe ₂ was used.

Table 1 shows a comparison of the polymerization activities of the above Examples and Comparative Examples.

[0046]

[Table 1]

Example 7 [Copolymerization] A 1.5-liter stainless steel autoclave was charged with 800 ml of dehydrated toluene, 1 ml of a toluene solution of triisobutylaluminum (1 mol / l) was added thereto, and the mixture was stirred for 20 minutes. 14 ml of the main catalyst component A described in 1 was added, 3 g of 1-hexene and 3 mol of propylene were added while maintaining the temperature of the reactor at 5 ° C. to initiate polymerization, and the temperature during polymerization was maintained at 5 ° C. 1 hour after the initiation of the polymerization, the polymerization is stopped by a small amount of alcohol,
The polymer was added to a methanol-hydrochloric acid solution together with a solvent, filtered, and dried to obtain 20 g of a propylene-hexene copolymer.

Comparative Example 4 As a comparative example of the obtained polypropylene, Ziegler
Showa Denko Show Allomer (SA
710).

Table 2 shows a comparison of the physical properties of the polypropylenes obtained in the above Examples and Comparative Examples.

[0050]

[Table 2]

[0051]

According to the present invention, the activity is remarkably improved as compared with the conventional cocatalyst methylaluminoxane, and
It is possible to provide an excellent polymer exhibiting a high melting point, a high rigidity, a high heat distortion temperature, and a high xylene insoluble content that cannot be achieved by conventional metallocene catalysts.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-287212 (JP, A) JP-A-4-275293 (JP, A) JP-A-4-85310 (JP, A) JP-A-1- 266116 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (2)

(57) [Claims] 1. An [A] C ₁ symmetric structure having the formula [1] [In the formula, M ¹ is Ti, Zr or Hf, and R ¹ , R ² and R ³ are hydrocarbon groups having 1 to 20 carbon atoms or alkylsilyl groups, which may be the same or different. R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkylsilyl group, and they may be the same or different from each other. Adjacent R ^{1 to} R ⁷ on the dienyl ring may form a ring with each other via a hydrocarbon group, Y is an alkylene group, a silylene group, or a germylene group, and n is 1 to 3 And R ⁸ and R ⁹ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkylsilyl group, and they may be the same or different from each other, and these are bonded via a hydrocarbon group. To form a ring, X ¹ and X ² are each a hydrogen atom, It is a hydrocarbon group having 1 to 20 carbon atoms, a halogen, an alkylsilyl group, or a silylalkyl group. ] And a metallocene compound represented by the formula: [B] Formula [2] (M ² X ¹ X ² X ³ X ⁴ ) ^(pq)- · C ^{(pq) +} [2] [wherein M ² is a metal selected from Groups 5 to 15 in the periodic table, and X ¹ , X ² , X ³ , and X ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, or a carbon number of 1.
To an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, a halogen-substituted aryl group, an organic metalloid group, or a halogen atom, and C is a counter cation, q is an integer of 1 to 7 in the valence of M ² , and p is an integer of 2 to 8. ] The manufacturing method of the polyolefin characterized by using the catalyst component which consists of a non-coordinating ionic compound represented by these. 2. An [A] C ₁ symmetric structure having the formula [1] [In the formula, M ¹ is Ti, Zr or Hf, and R ¹ , R ² and R ³ are hydrocarbon groups having 1 to 20 carbon atoms or alkylsilyl groups, which may be the same or different. R ⁴ , R ⁵ , R ⁶ , and R ⁷ are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkylsilyl group, and they may be the same or different from each other. Adjacent R ^{1 to} R ⁷ on the dienyl ring may form a ring with each other via a hydrocarbon group, Y is an alkylene group, a silylene group, or a germylene group, and n is 1 to 3 And R ⁸ and R ⁹ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkylsilyl group, and they may be the same or different from each other, and these are bonded via a hydrocarbon group. To form a ring, X ¹ and X ² are each a hydrogen atom, It is a hydrocarbon group having 1 to 20 carbon atoms, a halogen, an alkylsilyl group, or a silylalkyl group. ] And a metallocene compound represented by the following formula: [B] Formula [2] (M ² X ¹ X ² X ³ X ⁴ ) ^(pq)-. C ^{(pq) +} [2] [wherein M ² is a metal selected from Groups 5 to 15 in the periodic table, and X ¹ , X ² , X ³ , and X ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, or a carbon number of 1.
To an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, a halogen-substituted aryl group, an organic metalloid group, or a halogen atom, and C is a counter cation, q is an integer of 1 to 7 in the valence of M ² , and p is an integer of 2 to 8. ] The manufacturing method of high melting point polypropylene with a high xylene insoluble content characterized by using the catalyst component which consists of a non-coordinating ionic compound represented by these.