JPH111511A - Olefin polymerization method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin polymerization method excellent in cost and capable of controlling the molecular weight distribution even in polymerization in a single tank. SOLUTION: An olefin polymerization method characterized by polymerizing an olefin in the presence of a catalyst comprising the following components (A) and (B). Component (A): a solid component obtained by contacting the following components (A ₁ ), (A ₂ ) and (A ₃ ) Component (A ₁ ): a solid component containing titanium, magnesium and halogen as essential components Solid component component (A ₂ ) obtained by prepolymerization of an ethylenically unsaturated compound in the presence of an aluminum compound: transition metal compound component (A ₃ ) of the Periodic Table Group IVB to VIB having at least one conjugated five-membered ring ): Alumoxane compound component (B): Organoaluminum compound

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin polymerization method. More specifically, the present invention relates to a method for polymerizing an olefin, which enables control of the molecular weight distribution by a combination of specific catalyst components.

[0002]

2. Description of the Related Art It is generally known that the molecular weight distribution of an α-olefin polymer affects the moldability of a polymer. In addition, since the molecular weight distribution also affects the strength and appearance of the molded product, it is preferable that the molecular weight distribution of the produced polymer can be freely controlled according to the intended use.

[0003] Titanium-based catalysts are widely known as catalysts for polymerizing α-olefins, but such catalysts have a relatively narrow molecular weight distribution. Therefore, in order to obtain an α-olefin polymer having a broad molecular weight distribution, it is usual to use a multi-stage polymerization method in the presence of such a catalyst. However, in such a method,
Since a plurality of reactors are required, the cost is high and the operation is complicated.

On the other hand, in recent years, transition metal metallocene catalysts excellent in copolymerization have been developed. This catalyst generally has a very narrow molecular weight distribution and is inferior in moldability. However, recently, an attempt has been made to obtain a polymer having a wide molecular weight distribution by combining two types of catalyst components, utilizing the fact that the two types of catalysts having a narrow molecular weight distribution have greatly different molecular weight responsiveness to hydrogen. (JP-A-60-35006, JP-A-5-205)
186523, each gazette etc.).

However, in such a method, two kinds of
The polymer formed by the catalyst component separates and has
Dispersion is poor, and the expected effect of improving formability cannot be obtained.
No. Therefore, a catalyst in which two types of catalyst components are supported in the catalyst particles is used.
A medium system has been devised (Japanese Patent Laid-Open No. 3-203903,
Kaihei 3-203905, JP-A-5-105718,
Publications). However, in such a method, the catalyst
The amount of the catalyst is too large and the particle properties of the catalyst are poor.
But difficult. Also, the particle properties of the resulting polymer
bad. On the other hand, SiO_TwoIn the method using a carrier, catalyst particles are used.
Despite good physical properties, SiO _TwoFisheye caused by
There was a problem with the appearance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymerization method capable of controlling the molecular weight distribution in polymerization using a single tank which is excellent in cost.

[0007]

SUMMARY OF THE INVENTION The present invention has been made as a result of studies for solving the above problems. That is,
The olefin polymerization method of the present invention is characterized by polymerizing an olefin in the presence of a catalyst comprising the following components (A) and (B). Component (A): a solid component obtained by bringing the following components (A ₁ ), (A ₂ ) and (A ₃ ) into contact Component (A ₁ ): a solid component containing titanium, magnesium and halogen as essential components Solid component obtained by prepolymerizing an ethylenically unsaturated compound in the presence of an aluminum compound Component (A ₂ ): transition metal compound of Groups IVB to VIB of the Periodic Table having at least one conjugated 5-membered ring Component (A ₃ ): Alumoxane compound Component (B): organoaluminum compound

[0008]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, an olefin is polymerized in the presence of a catalyst comprising the following components (A) and (B).
Here, the term "consisting of" includes, in addition to the combination of the components (A) and (B), the combination of auxiliary components which is suitable for the purpose.

<Component (A)> Component (A) comprises the following component (A)
₁ ) A solid component obtained by contacting (A ₂ ) and (A ₃ ). (Component (A ₁ )) The component (A ₁ ) is a solid component obtained by prepolymerizing an ethylenically unsaturated compound in the presence of an organoaluminum compound with a solid component containing titanium, magnesium and halogen as essential components. .

Here, "containing as an essential component" means that besides the listed three components, other suitable elements may be contained, and each of these elements is a suitable optional element. It indicates that they may be present as compounds and that these elements may be present as bonded to each other. In a solid component containing titanium, magnesium and halogen as essential components, a titanium compound serving as a titanium source has a general formula of Ti (OR ¹ )
_{4-n Xn} (where R ¹ is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, X represents a halogen, and n represents a number of 0 ≦ n ≦ 4) The compound represented by these is mentioned. Specific examples include TiCl ₄ , TiBr
₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) _{2
Cl 2, Ti (OC 2 H} 5) 3 Cl, Ti (O-iC 3
_{H 7) Cl 3, Ti (} O-nC 4 H 9) Cl 3, Ti
_{(O-nC 4 H 9)} 2 Cl 2, Ti (OC 2 H 5) Br
_{3, Ti (OC 2 H 5} ) (OC 4 H 9) 2 Cl, Ti
_{(O-nC 4 H 9)} 3 Cl, Ti (O-C 6 H 5) Cl
_{3, Ti (O-iC 4} H 9) 2 Cl 2, Ti (OC 5 H
₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti (OC _{2
H 5) 4, Ti (O} -nC 3 H 7) 4, Ti (O-nC
_{4 H 9) 4, Ti (} O-iC 4 H 9) 4, Ti (O-n
_{C 6 H 13) 4, Ti} (O-nC 8 H 17) 4, Ti [OC
H ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] ₄ , and the like.

Further, TiX '_Four(Where X 'is a halogen
), Which is reacted with an electron donor as described below.
Compounds can also be used. Tools for such molecular compounds
For example, TiCl_Four・ CH_ThreeCOC_TwoH_Five, Ti
Cl_Four・ CH_ThreeCO_TwoC_TwoH _Five, TiCl_Four・ C₆H_Five
NO_Two, TiCl_Four・ CH_ThreeCOCl, TiCl_Four・ C
₆H_FiveCOCl, TiCl_Four・ C₆H_FiveCO_TwoC
_TwoH_Five, TiCl_Four・ ClCOC_TwoH_Five, TiCl_Four・
C_FourH_FourO, and the like. Of these titanium compounds
Among them, preferred is TiCl_Four, Ti (OC
_TwoH _Five)_Four, Ti (OC_FourH₉)_Four, Ti (OC
_FourH₉) Cl_ThreeAnd so on.

The general formula Ti (OR^Two)_3-pX_p(This
Where R^TwoIs a hydrocarbon residue, preferably having 1 carbon atom
X is a halogen, and p is 0
<P ≦ 3. ) Is also used.
Is available. As a specific example of such a titanium compound,
Is TiCl_Three, TiBr_Three, Ti (OCH_Three) C
l _Two, Ti (OC_TwoH_Five) Cl_TwoEtc. In addition,
Cyclopentadienyl dichlorotitanium, dicyclope
Nthadenyldimethyltitanium, bisindenyldic
It is also possible to use titanocene compounds such as lolotitanium.
You.

Examples of the magnesium compound serving as a magnesium source include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylate. Among these magnesium compounds, magnesium halide, dialkoxymagnesium, and alkoxymagnesium halide are preferred. The halogen of the halide is typically chlorine and bromine, and the alkoxy is typically lower alkoxy.

The halogen source is usually supplied from the above-mentioned magnesium and / or titanium halide compounds, but other halogen sources such as aluminum halides, silicon halides and phosphorus halides It can also be supplied from a known halogenating agent. It is also possible to use an ester as an electron donor (described later in detail) in the form of its acyl halide (for example, phthalic acid chloride) and use its halogen as a halogen source. The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

Optional Components As described above, the solid component used in the present invention may further contain various optional components in addition to the above essential components. Thus, for example, when producing this solid component, it can be produced using an electron donor as an internal donor. Examples of electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acids. Examples include oxygen-containing electron donors such as anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

The following are further used as optional components:
can do. That is, the solid component is SiC
l_Four, CH_ThreeSiCl_ThreeEtc., silicon compounds, methyl high
Polymeric silicon compounds such as drogen polysiloxane,
Al (OiC_ThreeH₇)_Three, AlCl_Three, AlBr_Three, A
l (OC_TwoH_Five)_Three, Al (OCH_Three)_TwoAl such as Cl
Minium compounds and B (OCH_Three)_Three, B (OC_TwoH
_Five)_Three, B (OC₆H _Five)_ThreeBoron compounds such as WCl
₆, WCl_Five, Wl_FiveTungsten compounds such as MoC
l_Five, MoBr_FiveOther components such as molybdenum compounds
For silicon, aluminum, ho
Solid as a component such as silicon, tungsten and molybdenum
It may be left in the components.

Examples of the silicon compound include, in addition to the above, an organic silicon compound represented by the following general formula.

[0018]

Embedded image R ⁴ R ⁵ _3-r Si (OR ⁶ ) _r

(Where R ⁴ is a branched hydrocarbon residue, R ⁵ is the same or different hydrocarbon residue as R ⁴ , R ⁶ is a hydrocarbon group, and r is 1 ≦ r ≦ 3) The silicon compounds are represented by the following numbers: Where R
Preferably, ⁴ is branched from a carbon atom adjacent to a silicon atom. In this case, the branching group is preferably an alkyl group, a cycloalkyl group, or an aryl group (for example, a phenyl group or a methyl-substituted phenyl group).
More preferred R ⁴ is one in which the carbon atom adjacent to the silicon atom, ie, the carbon atom at the α-position, is a secondary or tertiary carbon atom. In particular, those having a tertiary carbon atom bonded to a silicon atom are preferred. The carbon number of R ⁴ is usually 3 to 20, preferably 4 to 10. R
⁵ is usually a branched or linear aliphatic hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms. R ⁶ is an aliphatic hydrocarbon group, preferably having 1 to 4 carbon atoms.
Is usually a linear aliphatic hydrocarbon group.

Further, a vinylsilane compound can be used as the silicon compound. Furthermore, in the present invention, in the production of the component (A1), if necessary, the periodic table I-
Organometallic compounds of Group III metals can also be used.
As an organometallic compound, this compound has at least one organic group-metal bond. In this case, the organic group is typically a hydrocarbyl group having about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms. Representative metals in this compound are lithium, magnesium, aluminum and zinc, especially aluminum. The remaining valences (if any) of the metal of the organometallic compound in which at least one of the valences is satisfied by an organic group are hydrogen, halogen, hydrocarbyloxy (hydrocarbyl has 1 carbon atom). About 10 to 10, preferably about 1 to 6) or the metal via an oxygen atom (specifically, -O-Al (CH ₃ ) in the case of methylalumoxane)
−), Others are satisfied.

Preparation Method In order to obtain a solid component containing titanium, magnesium and halogen as essential components, the above-mentioned titanium source, magnesium source and halogen source, and, if necessary, other components described above or below such as an electron donor are used. It is produced, for example, by the following production method.

(A) A method of contacting a magnesium halide with a titanium-containing compound and, if necessary, an electron donor. (B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and is contacted with a magnesium halide, an electron donor, and a titanium halide-containing compound. (C) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound. As the polymer silicon compound, a compound represented by the following formula is suitable.

[0023]

Embedded image

(Where R ³ is a hydrocarbon residue having about 1 to 10 carbon atoms, and q is a polymer silicon compound having a viscosity of 1
It shows a degree of polymerization of about 100 centistokes. Among them, methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 7,9-
Pentamethylcyclopentasiloxane is preferred.

(D) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the solid component precipitated with a halogenating agent or a titanium halide compound is brought into contact with the titanium compound. (E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, and the like, and then, if necessary, contacted with an electron donor and a titanium compound. (F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor. (G) A method in which any one of the above-mentioned components is present.

The contact temperature is about -50 to 200 ° C, preferably about 0 to 100 ° C. As a contact method,
Examples thereof include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, and a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes and the like. Upon such contact, other components other than the above components, such as methyl hydrogen polysiloxane, ethyl borate, aluminum triisopropoxide, aluminum trichloride, aluminum trichloride, silicon tetrachloride, as long as the effects of the present invention are not impaired, Tetravalent titanium compound,
It is also possible to coexist a trivalent titanium compound or the like.

In this manner, a solid component for a Ziegler catalyst containing titanium, magnesium and halogen as essential components is obtained. Such solid components themselves containing titanium, magnesium and halogen are known.
In the present invention, known solid components can be used. For example, JP-A-53-45688, 5
Nos. 4-3894, 54-31092 and 54-39
No. 483, No. 54-94591, No. 54-11848
No. 4, No. 54-131589, No. 55-75411
Nos. 55-90510, 55-90511, 55-127405, 55-147507, and 5
Nos. 5-155003, 56-18609, 56-
Nos. 70005, 56-72001, 56-869
No. 05, No. 56-90807, No. 56-155206
Nos. 57-3803, 57-34103, 5
Nos. 7-92007, 57-121003 and 58-
Nos. 5309, 58-5310, 58-5311
No. 58-8706, No. 58-27732, No. 5
8-32604, 58-32605, 58-6
No.7703, No.58-117206, No.58-127
Nos. 708, 58-183708, 58-1837
No. 09, No. 59-149905, No. 59-14990
Nos. 6 and 6 are used. Further, those obtained by treating these with tungsten or a molybdenum compound may also be used.

The amount of each of the above components may be any as long as the effects of the present invention are recognized.
The following range is preferred. The amount of the titanium compound used is 1 × in molar ratio with respect to the amount of the magnesium compound used.
It is good to be in the range of 10 ^{-4 to} 1000, preferably 0.01.
It is in the range of -10. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 5 in molar ratio with respect to the amount of magnesium used irrespective of whether the titanium compound and / or the magnesium compound contains halogen or not. ^{-2 to} 1000, preferably 0.
1 to 100. When the electron donating compound is used, the amount of the electron donating compound used is 1 × 10 ⁻³ to 10 and preferably 0.1 to 10 in terms of a molar ratio with respect to the amount of the magnesium compound.
01 to 5.

Silicon, aluminum as an optional component,
When the boron, tungsten and molybdenum compounds are used, the amount used is 1 × 10 ^{−3 to} 100, preferably 0.1% by mol, relative to the above-mentioned magnesium compound.
01 to 10. Component (A ₁ ) of the present invention
Is a solid component obtained by prepolymerizing an ethylenically unsaturated compound in the presence of an organoaluminum compound with the solid component containing titanium, magnesium and halogen as essential components.

Here, as the organoaluminum compound to be used, specifically, the component (B) described later can be used.
Further, the ethylenically unsaturated compound is, specifically, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1- Butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3
-Methyl-1-pentene, 4-methyl-1-pentene,
2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 3,3-dimethyl-1- Butene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 2-octene, 3-octene,
4-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecane, 1-tridecane, 1-tetradecane, 1-pentadecane, 1-hexadecane, 1-heptadecane, 1-octadecane, 1-nonadecane, and the like α-
Olefins, also styrene, α-methylstyrene,
Styrenes such as divinylbenzene, ethyl and vinylbenzene, butadiene, isoprene, hexadiene, 1,4
-Hexadiene, 1,5-hexadiene, 1,3-pentadiene, 1,4-pentadiene, 2,3-pentadiene, 2,6-octadiene, cis-2, trans4
-Hexadiene, trans2, trans4-hexadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene,
2,4-heptadiene, dicyclopentadiene, 1,3
-Cyclohexadiene, 1,4-cyclohexadiene,
Dienes such as 1,9-decadiene, 7-methyl and 1,7-octadiene; and cyclic olefins such as cyclopentene, cycloheptene and norbornene. These may be used in combination of a plurality of types. Of these, α
-Olefins include ethylene, propylene, 1-butene, and styrenes include styrene and divinylbenzene.

The amount of prepolymerization is 1 to 500 times, preferably 3 to 100 times, more preferably 5 to 50 times the weight of the solid component containing titanium, magnesium and halogen as essential components. Here, if the amount of prepolymerization is low, the properties of the catalyst particles deteriorate, and if the amount is high, the catalyst productivity decreases. The prepolymerization is carried out in the presence of organoaluminum, and the organoaluminum compound is used usually in an Al / Ti ratio of about 0.1 to 50, preferably about 0.5 to 10, based on the titanium atom in the solid component.

The prepolymerization is preferably carried out by a slurry method using an inert hydrocarbon as a medium or using the monomer itself as a medium. Here, as the inert hydrocarbon medium, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane and paraffin; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; benzene; toluene And aromatic hydrocarbons such as xylene.

The prepolymerization temperature is usually from -20 ° C to 110 ° C.
And preferably 0 to 90 ° C. It is preferable that the average particle size of the component (A ₁ ) is 20 to 300 μm, preferably 35 to 200 μ by such prepolymerization in order to maintain the particle properties of the catalyst.

[0034] (component (A ₂₎₎ components of the present invention (A ₂₎
Is a periodic table having at least one conjugated five-membered ring.
It is a Group VIB transition metal compound. Specifically, it is a transition metal compound represented by the following general formula (I) or (II).

[0035] _{Q a (C 5 H 5-} ab R 3 b) (C 5 H 5-ac R 4 c) MeXY ... (I) S a (C 5 H 5-ad R 5 d) ZMeXY ... (II)

Here, Q represents a bonding group bridging between the two conjugated five-membered ring ligands, and S represents a bonding group bridging the conjugated five-membered ring ligand with the Z group. Specific examples of Q and S are
(A) a C ₁ -C ₄ alkylene group such as a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group or a cyclohexylene group, or a lower-chain side chain alkyl or phenyl-substituted product thereof; (B) A silylene group such as a silylene group, a dimethylsilylene group, a phenylmethylsilylene group, a diphenylsilylene group, a disilylene group, a tetramethyldisilylene group or an oligosilylene group or a lower alkyl or phenyl-substituted side chain thereof; A hydrocarbon group containing phosphorus, nitrogen, boron or aluminum, that is, a hydrocarbon group excluding the divalent valence of these elements required as a crosslinking group, preferably a lower alkyl group or a phenyl group, or a hydrocarbyloxy group, preferably Is a low alco Shi groups, in particular (CH _{3) 2} G
e group, (C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C ₆
H ₅₎ P group, (C ₄ H ₉₎ N group, (C ₆ H ₅₎ N group,
(CH ₃ ) B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B
Group, (C ₆ H ₅ ) Al group, (CH ₃ O) Al group and the like. Preferred are an alkylene group and a silylene group.
a is 0 or 1; The length of the crosslinking group of Q and S is preferably relatively short, and specifically, for example, 1 to 3 atoms, preferably 1 to 2 atoms is appropriate.
In this case, the cycloalkylene group and the phenylene group are counted as one atom. Therefore, preferable Q and S are, for example, a methylene group (1 atom), an isopropylene group (1 atom), an ethylene group (2 atoms), a silylene group (1 atom), a dimethylsilylene group (1 atom), and a disilylene group (2 atoms). ).

In the above general formula, (C ₅ H _5-ab R ³
_{b), (C 5 H 5} -ac R 4 c) and (C ₅ H _5-ad R
^{Although the} conjugated five-membered ring ligand represented by ⁵ _d ) is independently defined, the definitions of b, c and d, and R ³ , R ⁴ and R ⁵ are the same (details described later). It goes without saying that these three conjugated five-membered ring groups may be the same or different.

One specific example of this conjugated five-membered ring group is b =
0 (or c = 0, d = 0) is a cyclopentadienyl group (no substituent other than the crosslinking group Q or S).
This conjugated five-membered ring group has b ≠ 0 (or c ≠ 0, d ≠ 0)
In the case of having a substituent, one specific example of R ³ (or R ⁴ and R ⁵ ) is a hydrocarbon group (C ₁ to
C ₂₀ , preferably C ₁ -C ₁₂ ), even if this hydrocarbon group is bonded to a cyclopentadienyl group as a monovalent group, May be bonded at the other end to form a ring together with a part of the cyclopentadienyl group. A typical example of the latter is that in which R ³ (or R ⁴ , R ⁵ ) shares a double bond of the cyclopentadienyl group to form a fused 6-membered ring, that is, the conjugated 5-membered ring group is It is an indenyl group or a fluorenyl group. That is, typical examples of the conjugated five-membered ring group are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group.

R^Three, R^FourAnd R^FiveAre respectively
C₁~ C₂₀, Preferably C₁~ C ₁₂Of the hydrocarbon radical
In addition, halogen groups (eg, fluorine, chlorine, bromine),
An alkoxy group (eg, C₁~ C₁₂), Silicon
Containing hydrocarbon group (for example, a silicon atom is -Si (R)
(R ') (R ") containing 1 to 24 carbon atoms
Group), a phosphorus-containing hydrocarbon group (e.g.,
(R) a group having about 1 to 18 carbon atoms in the form of (R ′)),
Nitrogen-containing hydrocarbon group (for example, when a nitrogen atom is -N (R)
(A group having about 1 to 18 carbon atoms contained in the form of (R ')) or
Boron-containing hydrocarbon group (for example, when a boron atom is -B
(R) a group having about 1 to 18 carbon atoms in the form of (R '))
is there. b (or c, d) is 2 or more and R^Three(Ah
Or R^Four, R ^Five) When there is more than one
They may be the same or different.

B, c and d are such that when a is 0, 0 ≦ b
≦ 5, 0 ≦ c ≦ 5, 0 ≦ d ≦ 5, and when a is 1, 0 ≦
It is an integer satisfying b ≦ 4, 0 ≦ c ≦ 4, and 0 ≦ d ≦ 4. Me is a transition metal of Groups IVB to VIB of the Periodic Table, preferably titanium, zirconium and hafnium. Particularly, zirconium is preferable. Z is oxygen (-O-), sulfur (-S-), an alkoxy group having 1 to 20, preferably 1 to 10 carbon atoms, 1 to 20, preferably 1 to 12 carbon atoms;
Thioalkoxy group, having 1 to 40 carbon atoms, preferably 1 to
18, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 nitrogen-containing hydrocarbon groups, having 1 to 4 carbon atoms
0, preferably 1 to 18 phosphorus-containing hydrocarbon groups.

X and Y each independently represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, Group, having 1 to 20 carbon atoms, preferably 1 to 1
2, a phosphorus-containing hydrocarbon group (specifically, for example, diphenylphosphine group) or a silicon-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms (specifically, for example, trimethylsilyl group) is there. X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferred.

Specific examples of the transition metal compound when Me is zirconium are as follows. (A) Transition metal compounds having no bridging linking group and having two conjugated five-membered ring ligands, such as (1) bis (cyclopentadienyl) zirconium dichloride and (2) bis (methylcyclopentadienyl) ) Zirconium dichloride, (3)
Bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadienyl) zirconium dichloride, (5) bis (tetramethylcyclopentadienyl) zirconium dichloride, (6)
Bis (pentamethylcyclopentadienyl) zirconium dichloride, (7) bis (n-butylcyclopentadienyl) zirconium dichloride, (8) bis (t-butylcyclopentadienyl) zirconium dichloride, (9)
Bis (indenyl) zirconium dichloride, (10) bis (fluorenyl) zirconium dichloride, (11) bis (cyclopentadienyl) zirconium monochloride monohydride, (12) bis (cyclopentadienyl) methyl zirconium monochloride, (13) ) Bis (cyclopentadienyl) ethyl zirconium monochloride, (14) bis (cyclopentadienyl) phenyl zirconium monochloride, (15) bis (cyclopentadienyl) zirconium dimethyl, (16) bis (cyclopentadienyl) ) Zirconium diphenyl, (17) bis (cyclopentadienyl) zirconium dineopentyl, (18) bis (cyclopentadienyl) zirconium dihydride, (19) (cyclopentadienyl) (indenyl) zirconium dichloride, (20) ) (Cyclopentadienyl (Fluorenyl) zirconium dichloride and the like.

(B) Transition metal compounds having two five-membered ring ligands bridged by an alkylene group, such as (1) methylenebis (indenyl) zirconium dichloride, (2) ethylenebis (indenyl) zirconium dichloride, (3) Ethylene bis (indenyl) zirconium monohydride monochloride, (4) ethylene bis (indenyl) methyl zirconium monochloride, (5) ethylene bis (indenyl) zirconium monomethoxy monochloride, (6)
Ethylene bis (indenyl) zirconium diethoxide, (7) ethylene bis (indenyl) zirconium dimethyl, (8) ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, (9) ethylene bis (2- Methylindenyl) zirconium dichloride, (10) ethylenebis (2-ethylindenyl) zirconium dichloride, (11) ethylenebis (2,4-dimethylindenyl) zirconium dichloride, (12) ethylenebis (2-methyl-4 -Trimethylsilylindenyl)
Zirconium dichloride, (13) ethylenebis (2,4-
Dimethyl-5,6,7-trihydroindenyl) zirconium dichloride, (14) ethylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (15) Ethylene (2-methyl-4-tertbutylcyclopentadienyl) (3'-tertbutyl-5'-methylcyclopentadienyl) zirconium dichloride, (16) ethylene (2,3,5-trimethylcyclopentadienyl) )
(2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (17) isopropylidenebis (2-methylindenyl) zirconium dichloride,
(18) isopropylidenebis (indenyl) zirconium dichloride, (19) isopropylidenebis (2,4-dimethylindenyl) zirconium dichloride, (20) isopropylidene (2,4-dimethylcyclopentadienyl)
(3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (21) isopropylidene (2-methyl-4-tertbutylcyclopentadienyl) (3'-
tertbutyl-5'-methylcyclopentadienyl)
Zirconium dichloride, (22) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, (23) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl)
Zirconium chloride hydride, (24) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl, (25) methylene (cyclopentadienyl) (3, 4-dimethylcyclopentadienyl) zirconium Diphenyl, (26) methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (27) methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (28) isopropylidene (cyclo (Pentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (29) isopropylidene (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride,
(30) isopropylidene (cyclopentadienyl) (3-
Methylindenyl) zirconium dichloride, (31) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (32) isopropylidene (2-methylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, (33) isopropylidene (3-
t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, (34) isopropylidene (2.5
-Dimethylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (35)
Isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (36)
Ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (37)
Ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (38) ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (39) ethylene (2,5-diethylcyclopentadienyl) ( (Fluorenyl) zirconium dichloride, (40) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (41) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadiyl) (Enyl) zirconium dichloride, (42) cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (43) cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethyldimethylcyclo Pentadienyl Zirconium dichloride and the like.

(C) Transition metal compounds having a five-membered ring ligand of a silylene group, such as (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis (4,5,6,7-tetrahydro (Indenyl) zirconium dichloride, (3) dimethylsilylenebis (2-methyl-4,4-dimethyl-4,5,6,7-
Tetrahydro-4-silinedenyl) zirconium dichloride, (4) dimethylsilylenebis (2-methylindenyl) zirconium dichloride, (5) dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, (6) Dimethylsilylene bis (2,4
-Dimethylindenyl) zirconium dichloride, (7)
Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, (8) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′,
5'-dimethylcyclopentadienyl) zirconium dichloride, (9) phenylmethylsilylenebis (indenyl) zirconium dichloride, (10) phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl)
Zirconium dichloride, (11) phenylmethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, (12) phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadiyl (Enyl) zirconium dichloride, (13) phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (14) phenylmethylsilylenebis (Tetramethylcyclopentadienyl) zirconium dichloride, (15) diphenylsilylene bis (2,4-dimethylindenyl) zirconium dichloride, (16) diphenylsilylene bis (indenyl)
Zirconium dichloride, (17) diphenylsilylene bis (2-methylindenyl) zirconium dichloride, (1
8) diphenylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, (19) tetramethyldisilylenebis (indenyl) zirconium dichloride, (20) tetramethyldisilylenebis (cyclopentadienyl) zirconium dichloride, (21) tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, (22) dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (23) Dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (24) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (25) dimethylsilylene (cyclopen Dienyl) (3,4-diethyl-cyclopentadienyl) zirconium dichloride, (26) dimethylsilylene (cyclopentadienyl)
(Triethylcyclopentadienyl) zirconium dichloride, (27) dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (28) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (2
9) Dimethylsilylene (cyclopentadienyl) (2.7
-Di-t-butylfluorenyl) zirconium dichloride, (30) dimethylsilylene (cyclopentadienyl)
(Octahydrofluorenyl) zirconium dichloride, (31) dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (3
2) dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (3
3) dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, (34)
Dimethylsilylene (2-ethylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, (35) dimethylsilylene (2,5-diethylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, (36) dimethylsilylene (2-methylcyclopentadienyl) (2,
7-di-t-butylfluorenyl) zirconium dichloride, (37) dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (38) Dimethylsilylene (2-ethylcyclopentadienyl) (2,7-di-t
-Butylfluorenyl) zirconium dichloride, (39)
Dimethylsilylene (diethylcyclopentadienyl)
(2,7-di-t-butylfluorenyl) zirconium dichloride, (40) dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (41) dimethylsilylene (dimethylcyclopentadienyl) ) (Octahydrofluorenyl) zirconium dichloride, (42) dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (43) dimethylsilylene (diethylcyclopentadienyl) (octahydrofluoride Nil)
Zirconium dichloride and the like.

(D) Transition metal compounds having a five-membered ring ligand bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, such as (1) dimethylgermanium bis (indenyl) zirconium dichloride, 2) Dimethylgermanium (cyclopentadienyl) (fluorenyl) zirconium dichloride, (3) methylaluminum bis (indenyl) zirconium dichloride, (4) phenylaluminum bis (indenyl)
Zirconium dichloride, (5) phenylphosphinobis (indenyl) zirconium dichloride, (6) ethylboranobis (indenyl) zirconium dichloride, (7)
Phenylaminobis (indenyl) zirconium dichloride, (8) phenylamino (cyclopentadienyl)
(Fluorenyl) zirconium dichloride and the like.

(E) Transition metal compounds having one five-membered ring ligand, such as (1) pentamethylcyclopentadienyl-bis (phenyl) amidozirconium dichloride,
(2) indenyl-bis (phenyl) amido zirconium dichloride, (3) pentamethylcyclopentadienyl-
Bis (trimethylsilyl) amide zirconium dichloride, (4) pentamethylcyclopentadienylphenoxyzirconium dichloride, (5) dimethylsilylene (tetramethylcyclopentadienyl) (t-butylamide)
Zirconium dichloride, (6) dimethylsilylene (tetramethylcyclopentadienyl) phenylamido zirconium dichloride, (7) dimethylsilylene (tetrahydroindenyl) decylamido zirconium dichloride,
(8) Dimethylsilylene (tetrahydroindenyl) (bis (trimethylsilyl) amide) zirconium dichloride, (9) Dimethylgermane (tetramethylcyclopentadienyl) phenylamido zirconium dichloride, and the like.

(F) Further, compounds obtained by replacing chlorine in the compounds (a) to (e) with bromine, iodine, hydride, methyl, phenyl and the like can also be used. Further, in the present invention, the above-mentioned (A) to (A) are used as the transition metal component and the component (A ₂ ).
Compounds in which the center metal of the zirconium compound exemplified in (f) is changed from zirconium to titanium, hafnium, niobium, molybdenum, tungsten or the like can also be used.

Preferred among these are zirconium compounds, hafnium compounds and titanium compounds. More preferred are titanium compounds, zirconium compounds, and hafnium compounds cross-linked with an alkylene group or a silylene group.

Component (A ₃ ) is an alumoxane compound. The alumoxane compound is specifically a compound represented by the following general formula (III) or (IV).

[0050]

Embedded image

(Wherein p is 0 to 40, preferably 2 to 3
And each of R ⁵ , R ⁶ and R ⁷ is a hydrogen atom or preferably 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
The compounds of the general formulas (III) and (IV) are products obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water. Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane obtained from one kind of trialkylaluminum and water, (b) two kinds of trialkylaluminum and water Methylethylalumoxane obtained from
Examples thereof include methylbutylalumoxane and methylisobutylalumoxane. Among them, particularly preferred is methylalumoxane or methylisobutylalumoxane.

These alumoxanes may be used in combination of two or more in each group or between groups, and may be used in combination with other alkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum and dimethylaluminum chloride. It is also possible. These alumoxanes can be prepared by various known methods, and specific examples include the following methods.

(A) a method in which a trialkylaluminum is directly reacted with water using a suitable organic solvent such as toluene, benzene, or ether; (b) a salt hydrate containing a trialkylaluminum and water of crystallization, for example, copper sulfate; (C) a method of reacting trialkylaluminum with water impregnated in silica gel or the like, (d) mixing trimethylaluminum and triisobutylaluminum, and adding toluene, benzene,
A method of directly reacting with water using an appropriate organic solvent such as ether; (e) mixing trimethylaluminum and triisobutylaluminum to form a salt hydrate having water of crystallization, for example, a hydrate such as copper sulfate or aluminum sulfate; A method of performing a heating reaction, (f) a method of impregnating moisture into silica gel or the like, treating with triisobutylaluminum, and then performing an additional treatment with trimethylaluminum, (g) synthesizing methylalumoxane and isobutylalumoxane by a known method,
A method of mixing a predetermined amount of these two components and causing a heat reaction,
(H) A salt having water of crystallization, such as copper sulfate pentahydrate, is added to an aromatic hydrocarbon solvent such as benzene or toluene.
A method of reacting with trimethylaluminum under a temperature of about 0 ° C. In this case, the amount of water used is usually 0.5 to 1.5 in molar ratio with respect to trimethylaluminum.
The methylalumoxane thus obtained is a linear or cyclic organoaluminum polymer.

(Contact Method) The component (A) of the present invention can be obtained by contacting the components (A ₁ ), (A ₂ ) and (A ₃ ). Examples of the contact method include a rotary ball mill, a vibration mill, Examples thereof include a mechanical method using a jet mill and a medium stirring / pulverizing machine, a method of bringing into contact by stirring in the presence of an inert diluent, and a method of mixing and drying in the presence of an inert diluent. As the inert diluent used at this time, there may be mentioned, for example, aliphatic or aromatic hydrocarbons and halohydrocarbons which are used for preparing known catalyst components for olefin polymerization. When making these contacts,
As long as the effects of the present invention are not impaired, other components other than those described above, for example, siloxanes, aluminum alkoxides, silicon halides, organic alkoxysilanes, tetravalent titanium compounds, trivalent titanium compounds, and the like may be allowed to coexist. It is possible. The order of contact may be such that (A ₁ ), (A ₂ ) and (A ₃ ) are mixed at the same time, or any two components may be mixed in advance and then another component may be mixed. Preferably, after (A ₂ ) and (A ₃ ) have been brought into contact,
Preferably, ₁ ) is contacted. Contact temperature is -50 ° C
The temperature is about 200C to about 200C, preferably about 0C to 100C.

In contacting the above components, the amount of each component used is arbitrary as long as the effects of the present invention are recognized, but generally the following range is preferred. The transition metal compound (A ₂ ) has a molar ratio to the titanium atom in the component (A ₁ ) of from 0.01 to 20, preferably from 0.5 to 10.
The weight ratio of the alumoxane (A ₃ ) to the solid component (A ₁ ) is 0.005 to 1, preferably 0.01 to 0.5. Further, the molar ratio of the aluminum atom of the alumoxane (A ₃ ) to the transition metal compound of (A ₂ ) is 5 to 500,
Preferably it is 10-200.

<Component (B)> The component (B) is an organoaluminum compound. Specific examples of the organic aluminum compound used in the present invention, _R ⁹ _3-r AlX _r or R
¹⁰ _3-s Al (OR ¹¹ ) _s (where R ⁹ and R ¹⁰ are a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, R ¹¹ is a hydrocarbon group, X is halogen, r And s represent 0 ≦ r <3 and 0 <s <3, respectively.) Specifically, (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum Alkyl aluminum halides such as sesquichloride and ethyl aluminum dichloride,
(C) Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; and (d) alkyl aluminum alkoxides such as diethyl aluminum ethoxide and diethyl aluminum phenoxide.

These organoaluminum compounds (a) to (d) may be replaced with another organometallic compound such as R ¹² _3-t Al (O
R ¹³ ) _t (where R ¹² and R ¹³ are the same or different and are a hydrocarbon group having 1 to 20 carbon atoms, and t is 0 <
t ≦ 3. )) Can also be used in combination. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum and diethylaluminum ethoxide and diethylaluminum monochloride And the like. The ratio of the organoaluminum compound to the titanium component in the solid catalyst is Al / Ti = 1 to 1000
Mol / mol is common, and preferably, Al / Ti =
It is used at a rate of 10 to 500 mol / mol.

<Polymerization of Olefin> (Polymerization Mode) The production method of the polymer according to the present invention is a batch type,
It can be carried out by any of a continuous method and a semi-batch method. At this time, a method of performing polymerization using the monomer itself as a medium, a method of performing polymerization using a hydrocarbon such as propane, butane, pentane, hexane, heptane, toluene, or cyclohexane as a medium, without using a medium In addition, there is a method of performing polymerization in a gaseous monomer, and a method of performing polymerization by combining these methods. A preferred polymerization mode is a method in which polymerization is performed in a gaseous monomer without using a medium, for example, a method in which produced polymer particles are caused to flow by a monomer stream to form a fluidized bed, or the produced polymer particles are reacted with a stirrer in a reaction tank. In which stirring is performed.

(Olefin monomer and formed polymer) The olefin polymerized by the catalyst system of the present invention is represented by the general formula R ^14-
CH = CH ₂ (where R ¹⁴ is a hydrogen atom or a carbon atom having 1 to
Ten hydrocarbon residues, which may have a branched group. )
It is represented by Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
-Olefins such as -methylpentene-1, 1-octene, cyclopentene, cycloheptene, norbornene and styrene. Preferred are ethylene and propylene. In the case of these polymerizations, 5
Up to 0 weight percent, preferably up to 20 weight percent, of the olefin and ethylene can be copolymerized, and up to 30 weight percent of the olefin, especially ethylene, with propylene, to propylene. be able to. Copolymerization with other copolymerizable monomers (eg, vinyl acetate, diolefin, etc.) can also be performed.

Typical examples of the polymer obtained according to the present invention include:
(A) homopolymers such as ethylene and propylene, (b)
Random copolymers of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, propylene and 1-hexene, and (c) propylene and ethylene, or propylene and ethylene / propylene. , Block copolymers and the like.

Polymerization conditions The polymerization temperature is 30 ° C. to 150 ° C., preferably 50 ° C. to 10 ° C.
0 ° C., and the polymerization pressure is usually 1 to 50 kg / cm.
² G. In the polymerization, the MFR can be controlled by using a molecular weight modifier such as hydrogen, if necessary.

[0062]

【Example】

<Example -1> (component (A ₁₎ of the preparation) sufficiently introducing dehydration and deoxygenated n- heptane 100ml purged with nitrogen flask, then MgCl ₂ 0.1 mol, Ti (O-nC ₄ H
₉ ) 0.2 mol of ₄ was introduced and reacted at 95 ° C. for 2 hours. After the completion of the reaction, the temperature was lowered to 40 ° C., and then 12 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane. Then, the solid component synthesized above was placed in a flask sufficiently purged with nitrogen,
60 mmol in terms of atoms were introduced, and n-heptane was further added to 200 cc. Then, 22 mmol of SiCl _{4 was} added dropwise at 25 ° C. in 15 minutes. Further, TiCl ₄
85 mmol was added dropwise at 25 ° C. in 30 minutes, and the temperature was increased.
The reaction was performed at 50 ° C. for 3 hours. After the reaction is completed, the product is
-Washed thoroughly with heptane and dried under reduced pressure. This had a Ti loading of 10.8 wt%.

In a 1.5-liter stainless steel autoclave with stirring blades sufficiently purged with nitrogen, n was sufficiently purified.
-500 ml of heptane and 3 g of the solid component obtained above were introduced, furthermore 0.45 g of triethylaluminum and 0.45 g of diethylaluminum chloride were introduced. Next, after introducing hydrogen up to 1.2 kg / cm ² G, ethylene was introduced at 40 ° C. at a rate of 0.4 liter / min for 4 hours. The product was thoroughly washed with heptane and dried under reduced pressure to obtain a component (A ₁ ). The polymerization amount of ethylene was 36.5 g / g catalyst component, and the average particle size was 57 microns.

(Production of Component (A)) Into a flask sufficiently purged with nitrogen, 27.2 g of the above catalyst component (A ₁ ) was introduced, and then 50 ml of dehydrated and deoxygenated toluene was introduced. To this, 3.0 mmol of biscyclopentadienyl zirconium dichloride and P
MAO (methylalumoxane 85 grams / liter) 1
A solution in which 50 mmol was reacted at room temperature for 1 hour was added in total. This was reacted at room temperature for 1 hour. After completion of the reaction, the mixture was dried under reduced pressure with stirring to obtain a fluid powder.

(Polymerization) 0.8 l of sufficiently dehydrated and deoxygenated n-heptane was introduced into a 1.5-liter stainless steel autoclave having a stirring and temperature control device. Then trimethyl aluminum 100
Milligram, 4 ml of 1-hexene, the catalyst component (A)
Was introduced in 750 milligrams. Then, 100cc of hydrogen
, And ethylene was further introduced up to a total pressure of 2.6 kg / cm ² G, and reacted at 90 ° C. for 1 hour. As a result, 34
g of polymer were obtained. The MI of this polymer is 0.12
6, FR was 15.6, showing a bimodal molecular weight distribution from GPC, with Mn 6020 and Mw 217,700.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the organoaluminum used in the polymerization was changed to 200 mg of triisobutylaluminum. As a result, 71.4 g of a polymer was obtained. The MI of the polymer is 0.016 and the FR is 21.3.
Indicates a bimodal molecular weight distribution from GPC, and Mn1
5500, Mw 459500.

<Example 3> In Example 1, at least one conjugated 5-membered ring used in the production of the catalyst component (A) was used.
Example 1 was carried out except that bis (n-butylcyclopentadienyl) zirconium chloride was used as the transition metal compound. As a result, the obtained polymer was 93.2 g, and its MI was 8.88, FR
Was 11.1. This also shows a bimodal molecular weight distribution by GPC, Mn 10200, Mw 83500
Met.

Example 4 Polymerization was carried out in the same manner as in Example 3, except that 20 ml of 1-hexene was used. As a result, 87.0 g of a polymer was obtained.
This polymer showed a bimodal molecular weight distribution from GPC, with Mn 9160 and Mw 166100.

Comparative Example 1 The component (A) was prepared in the same manner as in Example 1 except that 725 mg of a solid catalyst containing no titanium, magnesium and chloro, which was not subjected to prepolymerization, was used. However, the powder properties of the catalyst were not favorable. This was used as a solid catalyst in an amount of 20 mg.
Polymerized in the same manner as in No. 1. As a result, 24.9 g of a polymer was obtained. This shows unimodal by GPC and Mn
54400, Mw 277,500.

<Comparative Example 2> In the same manner as in Comparative Example 1,
The component (A) was produced from a solid catalyst containing no titanium, magnesium, and chloro which was not subjected to prepolymerization, and was used for prepolymerization. That is, 500 ml of sufficiently purified n-heptane and 3 g of the component (A) produced from a solid catalyst containing titanium, magnesium, and chloro which are not subjected to prepolymerization were introduced into a 1.5-liter autoclave with stirring blades sufficiently purged with nitrogen. Then, 0.6 g of triisobutylaluminum was further introduced. Then, at 40 ° C., ethylene was introduced at a rate of 0.4 liter / min for 4 hours. After the completion of the reaction, the recovered partial product was sufficiently washed with heptane and dried under reduced pressure. Using this as a solid catalyst, 750
The polymerization was carried out in the same manner as in Example 1 using mg. As a result, 1
8.6 g of polymer were obtained. MI could not be measured because the molecular weight of the polymer was too high. This polymer shows unimodal by GPC, Mn 52300, Mw 28740
It was 0.

Comparative Example 3 In a flask sufficiently purged with nitrogen, 40 g of the solid catalyst component (A ₁ ) obtained in Example 1 after the prepolymerization was added to 200 ml of n-heptane.
Using 400 ml of n-butanol, the reaction was carried out at 80 ° C. with stirring for 6 hours to remove the catalyst. This was washed with n-heptane and dried under reduced pressure to obtain a white polymer. In the production of the catalyst component (A), a solid catalyst component was obtained in the same manner as in Example 1, except that the above decatalyzed polymer was used instead of (A ₁ ). Polymerization was carried out in the same manner as in Example 1;
7.2 g of polymer were obtained. This was unimodal by GPC and had Mn of 4,200 and Mw of 27,800.

<Comparative Example 4> In Example 1, the component (A) was used.
Was carried out in the same manner as in Example 1, except that the solid catalyst component (A ₁ ) was used in place of the component (A). As a result, 38.1 g of a polymer was obtained. This was 0.42 g / 10 min at MI of 20 kg load. It is unimodal by GPC, and Mn4130
0, Mw 232,400.

<Example-5> [Production of component (A ₁ )] 100 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then 0.1 mol of MgCl ₂ and Ti (O— nC ₄ H
₉ ) 0.2 mol of ₄ was introduced and reacted at 95 ° C. for 2 hours. After the completion of the reaction, the temperature was lowered to 40 ° C., and then 12 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane. Then, in a flask sufficiently purged with nitrogen, the solid component synthesized above was Mg,
0.06 mol in terms of atoms was introduced, and n-heptane was further added to 200 cc. Then, at 25 ° C., 6.5 mmol of ethyl aluminum dichloride was added dropwise in 20 minutes.
Further, 0.2 mol of SiCl _{4 was} added dropwise for 20 minutes and reacted for 3 hours. Then, the temperature was raised to 90 ° C. and the reaction was further performed for 3 hours. The reaction product was sufficiently washed with n-heptane. Then, 0.033 mol of ethyl aluminum dichloride (1
(5 wt% heptane solution) was added dropwise, and the mixture was reacted at 35 ° C. for 2 hours. The reaction product was sufficiently washed with n-heptane and dried under reduced pressure. This had a Ti loading of 4.76 wt%. 500 ml of sufficiently purified n-heptane and 4 g of the solid catalyst component obtained above were introduced into a 1.5 liter stainless steel autoclave with stirring blades sufficiently purged with nitrogen, and further 0.8 g of triisobutylaluminum was introduced. did. Next, 0.5 kg / cm ² G of hydrogen was added.
After that, ethylene was introduced at 80 ° C. for 0.4 hour at a rate of 0.4 liter / min. The product was sufficiently washed with n-heptane and dried under reduced pressure to obtain a component (A ₁ ). In addition,
The polymerization amount of ethylene was 14.7 g / g solid component. The average particle size of the catalyst component (A ₁ ) was 60 microns.

(Production of Component (A)) 5.52 g of the above-mentioned catalyst component (A ₁ ) was introduced into a flask sufficiently purged with nitrogen, and 50 ml of dehydrated and deoxygenated toluene was introduced therein. To this, a total amount of a yellow solution prepared by previously reacting 0.71 mmol of dimethylsilylbis (tetrahydroindenyl) zirconium dichloride and 35.5 mmol of MAO (88 g / l of methylalumoxane) manufactured by Schering at room temperature for 1 hour was added. . And it was made to react at room temperature for 1 hour. After the completion of the reaction, the reaction mixture was dried under reduced pressure to obtain a fluid powder.

(Polymerization) In the same manner as in Example 1, polymerization was carried out using 300 mg of the catalyst component. As a result, 102.2 g of a polymer was obtained. MI of this thing
Was 0.04 and FR was 11.2. GPC indicates a bimodal structure, and Mn32400, Mw3699
00.

<Example-6> [Production of component (A ₁ )] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then 0.4 mol of MgCl ₂ and Ti (O ₂₎ were added. -nC ₄
0.8 mol of H ₉ ) ₄ was introduced and reacted at 95 ° C. for 2 hours. After the completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane. Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Then, 0.4 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane.
Next, 0.024 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. Next, 10 ml of SiCl ₄ was introduced and reacted at 80 ° C. for 6 hours. After the completion of the reaction, the resultant was sufficiently washed with n-heptane. Its titanium content was 1.24% by weight.

Next, 50 ml of dehydrated and deoxygenated n-heptane and 5 g of the solid component synthesized above were introduced into a flask which had been sufficiently purged with nitrogen. Then (t-C ₄ H ₉₎
5 mmol of (CH ₃ ) Si (OCH ₃ ) ₂ and 15 mmol of triethylaluminum were added and reacted at 30 ° C. for 2 hours. After completion of the reaction, the resultant was sufficiently washed with n-heptane and dried under reduced pressure. The titanium content was 1.04 wt%. 500 ml of sufficiently purified n-heptane and 3.15 g of the solid component obtained above were introduced into a 1.5-liter stainless steel autoclave with stirring blades sufficiently purged with nitrogen, and further 0.47 g of triethylaluminum was introduced. . At 15 ° C., propylene was introduced at a rate of 0.33 l / min for 2 hours. The product was thoroughly washed with n- heptane to obtain a component (A ₁₎ and dried under reduced pressure.
The polymerization amount of propylene was 20.0 g / g catalyst component, and the average particle size was 50 microns.

[Production of Component (A)] Into a flask sufficiently purged with nitrogen, 14.5 g of the above catalyst component (A ₁ ) was introduced, and then 50 ml of dehydrated and deoxygenated toluene was introduced. A red-brown solution prepared by reacting 1.0 mmol of bis (n-butylcyclopentadienyl) zirconium dichloride and 100 mmol of MAO manufactured by Schering Co. in advance for 1 hour at room temperature was added thereto. This was reacted at room temperature for 1 hour, and the reaction mixture was dried under reduced pressure to obtain a fluid powder.

(Polymerization) In the same manner as in Example 1, polymerization was carried out using 420 mg of the catalyst component. As a result, 81.8 g of a polymer was obtained. Its MI was 1.57, FR was 11.4, and bulk density was 0.494. Its GPC was Mn32400, Mw3699
00.

[0080]

According to the present invention, it is possible to provide a polymerization method capable of arbitrarily controlling the molecular weight distribution which is important in material design. Further, according to this method, a solid catalyst having good powder properties can be obtained, which is advantageous in producing a solid catalyst. Further, it is possible to provide a polymerization method having good properties of the produced polymer particles.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention.

Claims (1)

[Claims] 1. A method for polymerizing an olefin, comprising polymerizing the olefin in the presence of a catalyst comprising the following components (A) and (B). Component (A): a solid component obtained by bringing the following components (A ₁ ), (A ₂ ) and (A ₃ ) into contact Component (A ₁ ): a solid component containing titanium, magnesium and halogen as essential components Solid component obtained by prepolymerizing an ethylenically unsaturated compound in the presence of an aluminum compound Component (A ₂ ): transition metal compound of Group IVB to VIB in the Periodic Table having at least one conjugated five-membered ring Component (A ₃ ): Alumoxane compound Component (B): Organoaluminum compound