JP3529941B2 - Solid titanium catalyst component, production method thereof, olefin polymerization catalyst containing solid titanium catalyst component, and olefin polymerization method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid titanium catalyst component capable of producing a polyolefin, a method for producing the same, an olefin polymerization catalyst containing the solid titanium catalyst component, and an olefin polymerization method.

[0002]

BACKGROUND OF THE INVENTION Ziegler-Natta catalysts composed of a titanium catalyst component and an organoaluminum compound have been widely used as a catalyst for producing polyolefins. Particularly, a carrier-supported solid titanium catalyst component is used as the titanium catalyst component. The catalyst used is known to exhibit high polymerization activity.

Among such solid titanium catalyst components, the catalyst using the magnesium chloride-supported titanium catalyst component exhibits high polymerization activity and exhibits stereoregularity when olefins such as propylene and butene are polymerized. It is known that high polyolefins can be produced.

Various catalysts have been proposed which can produce polyolefins having higher stereoregularity. For example, a solid titanium catalyst component supporting magnesium chloride and an organoaluminum compound are used as a third component together with an electron donating compound (electron donating compound). A catalyst using the body has been proposed.

However, when olefins are polymerized by using the catalyst containing the solid titanium catalyst component, there is a problem that a highly stereoregular polyolefin and a low stereoregular polyolefin are by-produced. Even with the catalyst for producing highly stereoregular polyolefin using the electron donor as the third component as described above, there is a limit in reducing the production amount of low stereoregular polyolefin.

The solid titanium catalyst component as described above is prepared by bringing a titanium compound, a magnesium compound and an electron donor into contact with each other. Among the solid titanium catalyst components thus prepared, It also contains a residual titanium compound that causes low stereoregular polyolefin by-products. In order to produce a highly stereoregular polyolefin, it is preferable that the solid titanium catalyst component does not contain this excess titanium compound.

It is known that a part of the surplus titanium compound is desorbed even when the solid titanium catalyst component is washed with hexane at room temperature, but titanium compound, magnesium compound, electron donor and the like are removed. A method of preparing a solid titanium catalyst component by removing excess titanium compound from a solid obtained by contact with a solvent has been proposed. For example, JP-A-59-124909 discloses aromatic compounds such as toluene. It has been proposed that cleaning the excess titanium compound with hydrocarbons is effective.

However, when the solid titanium catalyst component is washed with the aromatic hydrocarbon as described above, the electron donor is removed together with the excess titanium compound, so that the resulting solid titanium catalyst component results in low stereoregularity. The effect of reducing the amount of polyolefin cannot be sufficiently expressed.

Therefore, it has been desired to develop a solid titanium catalyst component and a catalyst capable of producing a highly stereoregular polyolefin with a high activity by producing a small amount of a low stereoregular polyolefin by-product.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is capable of producing a highly stereoregular polyolefin with a high activity, in which the amount of a low stereoregular polyolefin produced as a by-product is small. Provided are a method for producing a solid titanium catalyst component, a solid titanium catalyst component, a prepolymerization catalyst containing the solid titanium catalyst component, an olefin polymerization catalyst, and an olefin polymerization method using the olefin polymerization catalyst. It is an object.

[0011]

SUMMARY OF THE INVENTION The solid titanium catalyst component according to the present invention comprises (i) magnesium, titanium, halogen and an electron donor.
And contains titanium by washing with hexane at room temperature.
Contact solid titanium that does not desorb with (ii) a halogen-containing aromatic hydrocarbon at 40 ° C or higher.
And the titanium content in the solid titanium (i) is 25% by weight.
Obtained by reducing or, (1) a titanium content of 2.5 wt% or less, (2) a total content of magnesium and halogen is less than 65 wt% or more 92 wt%, (3) Electronic The donor content is 8 to 30% by weight, (4) the electron donor / titanium (weight ratio) is 7 or more , and (5) titanium is substantially desorbed by washing with hexane at room temperature. And the reduction rate of the titanium content when washed with o-dichlorobenzene at 90 ° C. is less than 15% by weight.

The method for producing a solid titanium catalyst component according to the present invention comprises (i) a solid titanium catalyst which contains magnesium, titanium, a halogen and an electron donor and which does not release titanium by hexane washing at room temperature. Titanium and (ii) a halogen-containing aromatic hydrocarbon are contacted at 40 ° C or higher to reduce the titanium content in the solid titanium (i) by 25% by weight or more, and (1) the titanium content is 2 . it is 5 wt% or less, (2) total content of magnesium and halogen 65 weight
% And less than 92 wt%, (3) an electron donor content of from 8 to 30% by weight, (4) an electron donor / titanium (weight ratio) Ri der least 7, (5) at room temperature Titanium is substantially removed by washing with hexane.
90 ° C o- dichlorobenzene that is not separated
The reduction rate of titanium content when washed with
It is characterized by producing a solid titanium catalyst component.

[0013]

In the solid titanium (i) used for contact with the halogen-containing aromatic hydrocarbon as described above, the electron donor / titanium (weight ratio) is preferably 6 or less.

The solid titanium (i) is specifically (a)
A solid compound (1) obtained by contacting a liquid-state magnesium compound, (b) a liquid-state titanium compound, and (c) an electron donor is preferable. This solid product (1)
Further, it may be a solid substance (2) obtained by further contacting (b) a titanium compound in a liquid state.

The olefin polymerization catalyst according to the present invention comprises (A) a solid titanium catalyst component as described above, (B) an organometallic compound, and (C) an organosilane compound having at least one alkoxy group. It is characterized by consisting of.

The prepolymerization catalyst according to the present invention is an organic compound having the above-mentioned (A) solid titanium catalyst component, (B) organometallic compound, and (C) at least one alkoxy group if necessary. It is characterized in that an olefin is prepolymerized or prepolymerized with a silane compound.

In the present invention, a catalyst for olefin polymerization is prepared from the above-mentioned prepolymerization catalyst and, if necessary, (B) an organometallic compound and / or (C) an organosilane compound having at least one alkoxy group. May be formed.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized in the presence of the above-described olefin polymerization catalyst. It is possible to produce a highly stereoregular polyolefin with a small amount of regular polyolefin produced.

[0020]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for producing a solid titanium catalyst component, a solid titanium catalyst component, a prepolymerization catalyst containing the solid titanium catalyst component, an olefin polymerization catalyst, and an olefin polymerization method according to the present invention will be described. explain.

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used not only as a homopolymer but also as a copolymer. It may be used in a meaning that also includes.

FIG. 1 shows an example of a process for preparing a solid titanium catalyst component and a process for preparing an olefin polymerization catalyst containing this solid titanium catalyst component.

(A) Method for Producing Solid Titanium Catalyst Component In the method for producing a solid titanium catalyst component according to the present invention, titanium is contained by magnesium, titanium, halogen and an electron donor and washed with hexane at room temperature. The solid titanium (i) that does not desorb and the polar compound (ii) having a dipole moment of 0.50 to 4.00 Debye are used.
The solid titanium (i) is contacted at a temperature of ℃ or more to reduce the titanium content in the solid titanium (i) by 25% by weight or more to produce a solid titanium catalyst component having an electron donor / titanium (weight ratio) of 7 or more. There is.

The above solid titanium (i) can be prepared by contacting a magnesium compound, a titanium compound, an electron donor and the like by various methods, and the preparation method is not limited, but in the present invention, It is preferable to contact (a) the magnesium compound in the liquid state, (b) the titanium compound in the liquid state, and (c) the electron donor to produce a solid material as solid titanium (i).

[0025] The following first specifically illustrated with the KakuNaru fraction used for preparing the solid titanium (i).

(A) Magnesium Compound In the present invention, when preparing solid titanium (i), the magnesium compound is preferably used in a liquid state. The magnesium compound in a liquid state may be one magnesium compound itself is a liquid state, or a solid magnesium compound, even those to which the compound is formed in the magnesium compound solution with a solvent Good.

As such a magnesium compound,
Examples thereof include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability. Examples of the magnesium compound having a reducing ability include organomagnesium compounds represented by the following formula.

In the formula X _n MgR _2-n , n is 0 ≦ n <2, R is hydrogen or carbon number 1
Is an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 21 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms, and when n is 0, two Rs may be the same or different. X is halogen.

Specific examples of the organomagnesium compound having such a reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
Dialkyl magnesium compounds such as dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium and ethyl butyl magnesium, alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride and amyl magnesium chloride Examples thereof include alkyl magnesium alkoxides such as halides, butyl ethoxy magnesium, ethyl butoxy magnesium, and octyl butoxy magnesium, and butyl magnesium hydride.

Specific examples of the magnesium compound having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, magnesium methoxy chloride, magnesium ethoxy chloride, and isopropoxy magnesium chloride. , Butoxy magnesium chloride, alkoxy magnesium chloride such as octoxy magnesium chloride, phenoxy magnesium chloride, allyloxy magnesium halide such as methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy Alkoxy magnesium, such as magnesium,
Examples thereof include allyloxy magnesium such as phenoxy magnesium and dimethylphenoxy magnesium, and magnesium carboxylates such as magnesium laurate and magnesium stearate. In addition, magnesium metal and magnesium hydride can also be used.

The magnesium compound having no reducing ability may be a compound derived from the above-mentioned magnesium compound having reducing ability or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is used as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, It may be brought into contact with a halogen-containing compound or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compound having the reducing ability and the magnesium compound having no reducing ability are the organic metal compounds described later, such as aluminum and zinc,
It may form a complex compound or a double compound with another metal such as boron, beryllium, sodium or potassium, or may be a mixture with another metal compound. Furthermore, the magnesium compound may be a single compound, or two or more of the above compounds may be combined.

As the magnesium compound used for preparing the solid titanium (i), magnesium compounds other than those mentioned above can be used, but the solid titanium finally obtained.
In (i), it is preferably present in the form of a halogen-containing magnesium compound, and therefore, when a halogen-free magnesium compound is used, it is preferable to react with the halogen-containing compound during the preparation.

Of these, a magnesium compound having no reducing ability is preferable, a halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferable.

Among the above magnesium compounds,
If the magnesium compound is a solid, an electron donor
Liquid state can be obtained by using (ci). As the electron donor (ci), alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and the like which will be described later as the electron donor (c) can be used.

Further, metal acid esters such as tetraethoxy titanium, tetra-n-propoxy titanium, tetra-i-propoxy titanium, tetrabutoxy titanium, tetrahexoxy titanium, tetrabutoxy zirconium and tetraethoxy zirconium can be used. .

Of these, alcohols and metal acid esters are particularly preferably used.

An electron donor (c
The solubilization reaction by -i) is generally carried out by bringing the solid magnesium compound and the electron donor (ci) into contact with each other and heating them as necessary. This contact is usually 0 to 200 ° C, preferably 20 to 180 ° C, more preferably 50 to 150 ° C.
Done at temperature.

In the above solubilization reaction, a hydrocarbon solvent is used.
(d) and the like may coexist. Specific examples of such a hydrocarbon solvent include pentane, hexane, heptane, octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, Alicyclic hydrocarbons such as cyclohexene,
Halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene and chlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene are used.

(B) Titanium Compound In the present invention, a tetravalent titanium compound is particularly preferably used as the liquid titanium compound (b). Examples of such a tetravalent titanium compound include compounds represented by the following formula.

In the formula Ti (OR) _g X _4-g , R is a hydrocarbon group having 1 to 15 carbon atoms, X is a halogen atom, and 0≤g≤4.

Specific examples of such a compound include:
Tetrahalogenated titanium such as TiCl ₄ , TiBr ₄ , TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On
-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C
₄ H ₉ ) Br ₃ and other trihalogenated alkoxy titanium, Ti
(OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C
₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ and other dihalogenated dialkoxy titanium, Ti (OCH ₃ ) ₃ Cl, Ti (OC
₂ H ₅ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ).
Monohalogenated trialkoxy titanium such as ₃ Br, T
i (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ ,
Examples thereof include tetraalkoxy titanium such as Ti (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used in combination of two or more. The titanium compound may be diluted with a hydrocarbon, a halogenated hydrocarbon or an aromatic hydrocarbon before use.

(C) Electron Donor An electron donor (c) used in the preparation of solid titanium (i)
As, alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, Examples thereof include oxygen-containing cyclic compounds. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl. C1-C18 alcohols such as alcohols, C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol , Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as naphthol, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone and other ketones having 3 to 15 carbon atoms, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and the like having 2 to 15 carbon atoms
Aldehydes, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, crotonic acid Ethyl, cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate,
Amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-
Butyrolactone, δ-valerolactone, coumarin, phthalide, dimethyl carbonate, ethyl carbonate and the like having 2 to 30 carbon atoms
C2-15 acid halides such as organic acid esters, acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether,
C2-C20 ethers such as amyl ether, anisole, diphenyl ether, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide and other acid amides, methylamine, Amines such as ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine, nitriles such as acetonitrile, benzonitrile, tolunitrile, acetic anhydride, phthalic anhydride, benzoic anhydride Acid anhydrides such as acids, pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole, pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethyl Pyridines such as pyridine, trimethylpyridine, phenylpyridine, benzylpyridine, and pyridine chloride, nitrogen-containing cyclic compounds such as piperidines, quinolines, and isoquinolines, tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, Examples thereof include cyclic oxygen-containing compounds such as methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumarane, phthalane, tetrahydropyran, pyran and dihydropyran.

As the electron donor (c), polyhydric hydroxy compound ethers such as 1-methoxyethanol, 2-methoxyethanol, 4-methoxybutanol and 2-butoxyethanol can be mentioned as particularly preferable examples.

As the above organic acid ester, a polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferable example.

[0047]

[Chemical 1]

In the above formula, R¹Is substituted or unsubstituted carbonization
Hydrogen radical, R², R^Five, R⁶Is hydrogen or a substitution or
Unsubstituted hydrocarbon group, R³, R^FourIs hydrogen or substitution
Or an unsubstituted hydrocarbon group, preferably a small amount thereof
At least one is a substituted or unsubstituted hydrocarbon group. Well
R³And R^FourAnd are connected to each other to form a ring structure
You may stay. Hydrocarbon group R¹~ R⁶Is generally 1 to 15
Substitutions with carbon atoms of and if they are substituted
The group includes heteroatoms such as N, O and S, and is, for example, C-
OC, COOR, COOH, OH, SO₃H, -C-
N-C-, NH₂ Have groups such as.

Specific examples of such polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate and isopropylmalon. Acid diethyl, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, diethyl butylmaleate, β-methylglutar Acid diisopropyl, ethyl allyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarboxylic acid esters such as diethyl itaconate, dioctyl citraconic acid, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Ester, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate , Di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate,
Aromatic polycarboxylic acid esters such as diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate, 3,4-furandicarboxylic acid and ethanol, n-butanol, i-butanol , Heterocyclic polycarboxylic acid esters such as esters with 2-ethylhexanol and the like.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate,
Mention may also be made of long-chain dicarboxylic acid esters such as diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate and di-2-ethylhexyl sebacate.

In the present invention, as the electron donor (c),
It is also possible to use a polyether compound having two or more ether bonds existing via a plurality of atoms. Examples of the polyether include carbon, silicon, oxygen, nitrogen, phosphorus, boron, sulfur, or compounds in which two or more kinds of atoms are present between ether bonds. Of these, a compound in which a relatively bulky substituent is bonded to an atom between ether bonds and a plurality of carbon atoms are contained in atoms existing between two or more ether bonds is preferable, for example, represented by the following formula. Polyethers are preferred.

[0052]

[Chemical 2]

(Where n is an integer of 2 ≦ n ≦ 10,
R ^{1 to} R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any R ^{1 to} R ²⁶ ,
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ) Of these, 1,3-diethers are preferably used,
In particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-
Isopropyl-2-isobutyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2 , 2-Diphenyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane and the like are preferably used.

Further, as the electron donor (c), an organic silane compound (C) having at least one alkoxy group as will be described later, water, or an anionic, cationic or nonionic surfactant is used. It can also be used.

In the present invention, it is preferable to use a carboxylic acid ester among the above as the electron donor (c), and in particular, polyvalent carboxylic acid esters, polyvalent hydroxy compound esters, especially phthalic acid esters, and aliphatic compounds. It is preferable to use a polyhydric hydroxy compound ether and an acid anhydride.

Two or more of these electron donors (c) can be used in combination.

Preparation of Solid Titanium (i) In the present invention, the liquid state magnesium compound (a), the liquid state titanium compound (b), and the electron donor are used.
Solid titanium (i) can be prepared by contact with (c). When these components are brought into contact with each other, the liquid titanium compound (b) may be used once to produce a solid (1), and the solid titanium (b) is further added to the liquid (1). May be contacted with each other to form a solid (2).

When the solids are prepared by bringing the components (a) to (c) into contact with each other, a hydrocarbon solvent (d) as shown in the liquid magnesium compound (a) preparation may be added, if necessary. Can be used.

In the present invention, the solid compound (1) or (2) obtained by contacting these (a) to (c) with the polar compound (ii) having a dipole moment of 0.50 to 4.00 Debye. The solid titanium (i) can be directly used as the solid titanium (i) to be contacted with, but the solid titanium (i) can be prepared by washing the solid (1) or (2) with a hydrocarbon solvent, if necessary. preferable.

When preparing the solid titanium (i),
In addition to these compounds, organic compounds or inorganic compounds containing silicon, phosphorus, aluminum, etc. used as carriers and reaction aids may be used.

Examples of such a carrier include Al ₂ O ₃ and Si.
O ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, Sn
Examples thereof include resins such as O ₂ , BaO, ThO, and styrene-divinylbenzene copolymer. Among these,
_{TiO 2, Al 2 O 3,} SiO 2, a styrene - divinylbenzene copolymer are preferably used.

Examples of the method for preparing the solid (1) or (2) (or the direct solid titanium (i)) from the above components include the following methods. The method for preparing a solid material shown below also includes a step of preparing a magnesium compound (a) in a liquid state. Further, in the following method, as the organoaluminum compound, an organoaluminum compound as described below as the organometallic compound (B) is used.

(1) After the magnesium compound (a) in the liquid state consisting of the magnesium compound, the electron donor (ci) and the hydrocarbon solvent is reacted with the organoaluminum compound to precipitate a solid, or after the precipitation. While reacting, the titanium compound (b) in the liquid state is contact-reacted.

In this process, the electron donor (c) is contacted with the contact product at least once.

(2) The titanium compound (b) and the electron donor (c) in the liquid state are contact-reacted with the contact product of the inorganic carrier and the liquid organomagnesium compound (a). At this time, the contact product of the inorganic carrier and the liquid organomagnesium compound (a) may be previously contact-reacted with the halogen-containing compound and / or the organoaluminum compound.

(3) Magnesium compound, electron donor (c-
i), a magnesium compound-supported inorganic or organic carrier is prepared from a mixture of a magnesium compound (a) in a liquid state optionally comprising a hydrocarbon solvent and an inorganic carrier or an organic carrier. The titanium compound (b) in a liquid state is contacted.

In this process, the electron donor (c) is contacted with the contact product at least once.

(4) Magnesium compound, titanium compound (b) in a liquid state, electron donor (ci) and / or
Alternatively, a solution containing a hydrocarbon solvent, an inorganic carrier or an organic carrier, and the electron donor (c) are brought into contact with each other.

(5) Liquid state organomagnesium compound
After contacting (a) and the titanium compound (b) in a liquid state,
Contact with electron donor (c). (6) The organomagnesium compound (a) in the liquid state is contact-reacted with the halogen-containing compound, and then the titanium compound (b) in the liquid state is brought into contact.

In this process, the electron donor (c) is used at least once.

(7) Alkoxy-containing magnesium compound
(a) is a liquid titanium compound (b) and an electron donor
Contact with (c).

(8) Magnesium compound and electron donor (c-
i) a hydrocarbon solution of a complex consisting of (a magnesium compound (a) in a liquid state), a titanium compound (b) in a liquid state,
Catalytically reacts with electron donor (c).

(9) Magnesium compound and electron donor (c-
A liquid complex (i) and (a magnesium compound (a) in a liquid state) is brought into contact with an organoaluminum compound, and then contacted with a titanium compound (b) in a liquid state.

In this process, the electron donor (c) is contacted with the contact product at least once.

(10) A liquid magnesium compound (a) having no reducing ability and a liquid titanium compound (b) are brought into contact with each other in the presence or absence of the electron donor (c). In this process, the electron donor (c) is contacted with the contact product at least once.

(11) The reaction product (solid (1)) obtained in (1) to (10) is further mixed with a titanium compound in a liquid state.
Contact (b). (12) The electron donor (c) and the liquid titanium compound (b) are brought into contact with the reaction product (solid (1)) obtained in (1) to (10).

The contact of each component as described above is usually -70.
C. to + 200.degree. C., preferably -50.degree. C. to + 150.degree. C., more preferably -30 to + 130.degree. The amount of each component used when preparing solid titanium (i) varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of electron donor is 0.01 per mol of magnesium compound.
The amount of the titanium compound is 0.01 to 1000 mol, preferably 0.1 to 200 mol.
It can be used in molar amounts.

In the present invention, among the above, the solid (1) is produced by the contact method (8), or the solid (2) is obtained by the contact method (11) or (12) including the contact method (8). Is preferably generated, and it is particularly preferable to generate the solid (1) by the contacting method (8).

Since the olefin polymerization catalyst containing the solid (1) exhibits high activity in propylene homopolymerization and gives a propylene random copolymer having a low decane-soluble content, the solid (1) Is preferred.

Further, in such a method, the liquid state magnesium compound (a) prepared from the magnesium compound and the electron donor (ci) is brought into contact with the liquid state titanium compound (b), and then the electron donating is carried out. It is preferable to use polyvalent carboxylic acid esters and / or polyvalent hydroxy compound ethers as the electron donor (c) when the body (c) is contacted.

In the present invention, the solid substance (1) or (2) thus obtained can be used as it is as the solid titanium (i). The solid substance is used as a hydrocarbon solvent at 0 to 150 ° C. It is preferable to wash with.

Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane and cetane, non-halogenated aromatic hydrocarbon solvents such as toluene, xylene and benzene, which will be described later. A halogen-containing aromatic hydrocarbon solvent or the like is used. Of these, an aliphatic hydrocarbon solvent or a halogen-free aromatic hydrocarbon solvent is preferably used.

When washing the solid matter, the hydrocarbon solvent is usually used in an amount of 10 to 500 ml, preferably 20 to 100 ml, per 1 g of the solid matter. Solid titanium (i) thus obtained is magnesium, titanium,
It contains halogens and electron donors. In this solid titanium (i), the electron donor / titanium (weight ratio) is preferably 6 or less.

This solid titanium (i) is not desorbed by washing with hexane at room temperature.

Contact Treatment with Polar Compound (ii) In the present invention, the above-mentioned solid titanium (i) and the polar compound (i) having a dipole moment of 0.50 to 4.00 Debye are used.
The solid titanium catalyst component (A) is prepared by contacting with i).

Specific examples of the polar compound (ii) (also simply referred to as polar compound) having a dipole moment of 0.50 to 4.00 Debye used for contact with solid titanium (i) include chlorobenzene and o. -Halogen-containing aromatic hydrocarbons such as dichlorobenzene, m-dichlorobenzene, trichlorobenzene, α, α, α-trichlorotoluene, o-chlorotoluene, benzyl chloride and 2-chlorobenzyl chloride, 1,2-
Dichloroethane, 1,1,2,2-tetrachloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, 2-chloro-2 Examples thereof include halogen-containing aliphatic hydrocarbons such as -methylpropane and 1-chloropentane, and halogen-containing Si compounds such as diphenyldichlorosilane and methyltrichlorosilane. Of these, halogen-containing aromatic hydrocarbons are preferable.

The contact between the solid titanium (i) and the polar compound (ii) is usually 40 to 200 ° C., preferably 50 to 180 ° C., more preferably 60 to 160 ° C., for 1 minute to 10 hours, preferably 10 minutes. Minutes to 5 hours.

In this contact, the polar compound (ii) is usually 1 to 10000 ml, preferably 5 to 5000 ml, more preferably 10 to 1000 m, per 1 g of solid titanium (i).
Used in an amount of l.

The solid titanium (i) and the polar compound (ii) are preferably brought into contact with each other under stirring in an inert gas atmosphere. For example, in a glass flask equipped with a stirrer that has been sufficiently replaced with nitrogen, solid titanium (i) and polar compound (ii)
The slurry of and is stirred at the above temperature with a stirrer for 100 to 100
It is desirable that the solid titanium (i) and the polar compound (ii) are brought into contact with each other by stirring at a rotation speed of 0 rpm, preferably 200 to 800 rpm, for the above time.

After contact, solid titanium (i) and polar compound (i)
It can be separated from i) by filtration.

Such solid titanium (i) and polar compound
By contacting with (ii), a solid titanium catalyst component having a titanium content lower than that of solid titanium (i) is obtained. Specifically, the titanium content is 25 than that of solid titanium (i).
Solid titanium catalyst component (A) in an amount of at least 50% by weight, preferably less than 30 to 95% by weight, more preferably less than 40 to 90% by weight.
Is obtained.

The solid titanium catalyst component (A) according to the present invention obtained as above is magnesium, titanium,
Contains halogen and electron donors, and (1) ~
(5) is satisfied.

(1) The titanium content of the solid titanium catalyst component (A) is 2.5 wt% or less, preferably 2.2 to 0.2.
The content is more preferably 1% by weight, more preferably 2.0 to 0.2% by weight, particularly preferably 1.8 to 0.3% by weight, most preferably 1.4 to 0.4% by weight.

(2) The total content of magnesium and halogen is 65% by weight or more and less than 92% by weight. (3) The electron donor content is 8 to 30% by weight.

(4) The electron donor / titanium (weight ratio) is 7
It is preferably 7.5 to 35, more preferably 8 to 30, and most preferably 8.5 to 25. (5) In the solid titanium catalyst component (A), titanium is not substantially desorbed by washing with hexane at room temperature.
The hexane washing of the solid titanium catalyst component means washing with hexane in an amount of usually 10 to 500 ml, preferably 20 to 100 ml, for 5 minutes with respect to 1 g of the solid titanium catalyst component. Room temperature is 15 to 25 ° C.

The solid titanium catalyst component (A) according to the present invention has a titanium content reduction rate of less than 15% by weight, preferably less than 10% by weight, when washed with o-dichlorobenzene at 90 ° C. is there. Solid titanium catalyst component (A)
Specifically, the washing with o-dichlorobenzene mentioned above means that 0.5 g of the solid titanium catalyst component (A) is brought into contact with 100 ml of o-dichlorobenzene at 90 ° C. for 1 hour.

Here, the amounts of magnesium, halogen, titanium and electron donor are respectively weight% per unit weight of the solid titanium catalyst component (A), and magnesium, halogen and titanium are measured by plasma emission spectroscopy (I
(CP method), the electron donor is quantified by gas chromatography.

When the solid titanium catalyst component (A) according to the present invention as described above is used as a catalyst component for olefin polymerization, it is possible to polymerize olefins with high activity and produce a polyolefin having low stereoregularity. A small amount of highly stereoregular polyolefin can be produced.

(B) Organometallic Compound In the present invention, when forming the olefin polymerization catalyst, an organometallic compound is used together with the solid titanium catalyst component (A) as described above. The organometallic compound preferably contains a metal selected from Group I to Group III of the periodic table, specifically, an organoaluminum compound, a complex alkyl compound of a Group I metal and aluminum,
Examples thereof include organometallic compounds of Group II metals.

Such an organoaluminum compound is represented by the following formula, for example. R ^a _n AlX _3-n (In the formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms;
Is halogen or hydrogen, and n is 1 to 3. ) ^Ra is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group. Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum, and alkenyl such as isoprenylaluminum. Dialkyl aluminum halides such as aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, and dimethyl aluminum bromide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesqui Bu Alkylaluminum sesquihalide such as bromide, methyl aluminum dichloride, ethyl aluminum dichloride,
Examples thereof include alkyl aluminum dihalides such as isopropyl aluminum dichloride and ethyl aluminum dibromide, and alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound, compounds represented by the following formula can also be mentioned. R ^a _n AlY _{3-n In the} above formula, R ^a is the same as above, and Y is -OR.
^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR
^e ₂ group, a -SiR ^f ₃ group or -N (R ^g) AlR ^h ₂ group, n is ^{1~2, R b, R c,} R d and R ^h
Is a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group or the like, R ^e is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group or the like, and R ^f and R ^g Is a methyl group, an ethyl group or the like.

Specific examples of such an organoaluminum compound include the following compounds. (i) R ^a _n Al (OR ^b ) _3-n dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide and the like, (ii) R ^a _n Al (OSiR ^c ) _3-n Et ₂ Al (OSiMe ₃ ), (Iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc., (iii) R ^a _n Al (OAlR ^d ₂ ) _3-n Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu)
Such as _{^{2, (iv) R a n}} Al (NR e 2) 3-n Me 2 AlNEt 2, Et 2 AlNHMe, Me 2 AlNHEt,
Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN (Me ₃ Si
) ₂ etc., (v) R ^a _n Al (SiR ^f ₃ ) _3-n (iso-Bu) ₂ AlSiMe _3, etc., (vi) R ^a _n Al [N (R ^g ) -AlR ^h ₂ ] _3-n such as _{Et 2 AlN (Me) -AlEt 2} (iso-Bu) 2 AlN (Et) Al (iso-Bu) 2.

Further, a compound similar to this, for example, an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can be mentioned. More specifically, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C
_{4 H 9) 2 AlOAl (C} 4 H 9) 2, (C 2 H 5) 2 AlN
(C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and the like, as well as aluminoxanes such as methylaluminoxane.

Among the above organoaluminum compounds, R ^a ₃ Al, R ^a _n Al (OR ^b ) _3-n and R ^a _n Al
Organoaluminum compounds represented by (OAlR ^d _{2) 3-n} is preferably used.

A complex alkyl compound of a Group I metal and aluminum is represented by the following general formula. M ¹ AlR ^j ₄ (M ¹ is Li, Na, K, and R ^j has 1 to 15 carbon atoms.
Specifically, LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ )
₄ and so on.

The organometallic compound of Group II metal is represented by the following general formula. R ^k R ^l M ² (R ^k and R ^l are a hydrocarbon group having 1 to 15 carbon atoms or halogen and may be the same or different from each other.
Except when both are halogen. M ² is Mg, Z
Specific examples include diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, and the like.

Two or more of these compounds can be used in combination.

(C) Organosilane Compound When the catalyst for olefin polymerization according to the present invention is prepared,
In addition to the above solid titanium catalyst component (A) and organometallic compound (B), an organosilane compound having at least one alkoxy group represented by the following general formula (c) is used.

R _n Si (OR ') _4-n (c) (In the formula, R and R'are a hydrocarbon group having 1 to 20 carbon atoms, and n is 1, 2 or 3.) Specific examples of the organic silane compound represented by the formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysisilane, diisopropyldimethoxysilane,
t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane , Screw p-
Tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane,
Decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltrisilane Ethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxysilane, methyltriallyloxy (all
yloxy) silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. Further, ethyl silicate, butyl silicate and the like can also be used.

In the present invention, the organosilane compound represented by the above formula (c) is particularly preferably represented by the following formula (ci). R ^a _n Si (OR ^b ) _4-n ... (ci) (where n is 1, 2 or 3, and when n is 1, R ^a is a secondary or tertiary carbon number 1 to 20) When n is 2 or 3, at least one of R ^a is a secondary or tertiary hydrocarbon group, R ^a may be the same or different, R a ^b has 1 to 4 carbon atoms
When (4-n) is 2 or 3, OR ^b may be the same or different. ) In the organosilane compound having a bulky group represented by the formula (ci), the secondary or tertiary hydrocarbon group has a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a substituent. These groups and S
A hydrocarbon group in which the carbon adjacent to i is secondary or tertiary is included. More specifically, the substituted cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,4-dimethyl Cyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group, 2,3,4-triethylcyclopentyl group, tetra Examples thereof include a cyclopentyl group having an alkyl group such as a methylcyclopentyl group and a tetraethylcyclopentyl group.

The substituted cyclopentenyl group includes 2-methylcyclopentenyl group, 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethyl Examples thereof include a cyclopentenyl group having an alkyl group such as a cyclopentenyl group, a 2,3,5-trimethylcyclopentenyl group, a 2,3,4-triethylcyclopentenyl group, a tetramethylcyclopentenyl group and a tetraethylcyclopentenyl group.

Examples of the substituted cyclopentadienyl group include 2-
Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethyl Cyclopentadienyl group, 2,5-
Dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group, 2,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4, Examples thereof include a cyclopentadienyl group having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-pentaethylcyclopentadienyl group.

Examples of the hydrocarbon group in which the carbon adjacent to Si is secondary carbon include i-propyl group, s-butyl group, s-amyl group, α-methylbenzyl group and the like, which are adjacent to Si. A hydrocarbon group whose carbon is a tertiary carbon includes t-
Butyl group, t-amyl group, α, α'-dimethylbenzyl group,
Examples thereof include an admantyl group.

As the organosilane compound represented by the formula (ci), when n is 1, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane Trialkoxysilanes such as cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, and 2-norbornanetriethoxysilane. And when n is 2,
Dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-
Examples thereof include dialkoxysilanes such as amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

In the organosilane compound represented by the formula (ci), when n is 2, the following formula
A preferred example is the dimethoxysilane compound represented by (c-ii).

[0117]

[Chemical 3]

In the formula, R ^a and R ^c are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or
A hydrocarbon group in which the carbon adjacent to Si is a secondary carbon or a tertiary carbon.

Examples of the organic silane compound represented by the formula (c-ii) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane and dicyclopentadienyldimethoxysilane. (2-Methylcyclopentyl) dimethoxysilane, Di (3-methylcyclopentyl) dimethoxysilane, Di (2-ethylcyclopentyl) dimethoxysilane, Di (2,3-dimethylcyclopentyl) dimethoxysilane, Di (2,4-dimethylcyclopentyl) Dimethoxysilane, di (2,5-dimethylcyclopentyl) dimethoxysilane, di (2,3-diethylcyclopentyl) dimethoxysilane, di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5-trimethyl Cyclopentyl) dimethoxysilane, di (2,3,4-triethylsilane) Lopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane, di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclo) (Pentenyl) dimethoxysilane, di (2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-dimethylcyclopentenyl) dimethoxysilane, di (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5- Dimethylcyclopentenyl) dimethoxysilane, di (2,3,4-trimethylcyclopentenyl) dimethoxysilane, di (2,3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-triethylcyclopentenyl) dimethoxy Silane, di (tetramethylcyclopenteni ) Dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxysilane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxy Silane, di (2-
n-Butylcyclopentenyl) dimethoxysilane, di (2,
3-dimethylcyclopentadienyl) dimethoxysilane,
Di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopentadienyl) dimethoxysilane, di (2,3-diethylcyclopentadienyl)
Dimethoxysilane, di (2,3,4-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,4-triethylcyclopentadienyl) ) Dimethoxysilane, di (2,3,4,5-tetramethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3 , 4,5-Pentamethylcyclopentadienyl) dimethoxysilane, di (1,2,
3,4,5-Pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethylbenzyl) dimethoxysilane, di (adamantyl) dimethoxysilane, adamantyl-t-butyldimethoxy Examples thereof include silane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, dis-butyldimethoxysilane, dis-amyldimethoxysilane, and isopropyl-s-butyldimethoxysilane.

Further, as the organosilane compound represented by the formula (ci), when n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentyl. Examples thereof include monoalkoxysilanes such as methylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and formula (c-ii) The dimethoxysilanes represented by are preferred. Particularly, dimethoxysilanes represented by the formula (c-ii) are preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) Dimethoxysilane, di-t-amyldimethoxysilane and the like are preferable.

These may be used in combination of two or more kinds.

Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention has the above-mentioned (A) solid titanium catalyst component, (B) organometallic compound, and (C) at least one alkoxy group. It is formed from an organic silane compound.

In the present invention, each of these components (A),
When forming the olefin polymerization catalyst from (B) and (C), other components may be used, if desired. For example, the above-mentioned polyether compounds, 2,6-substituted piperidines, 2,5 -Substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-substituted methylenediamines such as tetraethylmethylenediamine, 1,3-dibenzylimidazolidine, 1 Nitrogen-containing electron donors such as substituted imidazolidines such as 1,3-dibenzyl-2-phenylimidazolidine, triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite Fight, diethyl n-
Phosphorus-containing electron donors such as phosphites such as butyl phosphite and diethylphenyl phosphite, 2,6-
It is also possible to use substituted tetrahydropyrans, oxygen-containing electron donors such as 2,5-substituted tetrahydropyrans,
Two or more of these may be used in combination.

Further, in the present invention, the prepolymerization catalyst may be formed from each of the above components. The prepolymerization catalyst is prepared by preliminarily (co) polymerizing olefins or the like in the presence of the solid titanium catalyst component (A), the organometallic compound (B) and, if necessary, the organosilane compound (C). It is formed.

Examples of olefins used in the prepolymerization include ethylene, propylene, 1-butene, 1-
Pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-
1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene,
4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, Examples include α-olefins having 2 or more carbon atoms such as 1-eicosene. In addition, other vinyl compounds as described below,
A polyene compound can also be used at the time of prepolymerization. You may use these 2 or more types together.

The α-olefin used in the prepolymerization is
It may be the same as or different from the α-olefin used in the main polymerization described later.

In the present invention, the method for carrying out the prepolymerization is not particularly limited, and it can be carried out, for example, in a state where the olefins and the polyene compound are in a liquid state, or can be carried out in the presence of an inert solvent. Can also be carried out under gas phase conditions. Of these, it is preferable to carry out prepolymerization under relatively mild conditions by adding olefins and respective catalyst components to the inert solvent in the presence of an inert solvent. At this time, it may be carried out under conditions in which the formed prepolymer is dissolved in the polymerization medium or may be dissolved therein, but it is preferably carried out under conditions in which it is not dissolved.

The prepolymerization is usually about -20 to + 100 ° C, preferably about -20 to + 80 ° C, more preferably -10 to 10.
It is desirable to carry out at + 40 ° C. Further, the prepolymerization can be carried out in any of batch system, semi-continuous system and continuous system.

In the preliminary polymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. Although the concentration of the catalyst component in the prepolymerization varies depending on the catalyst component used and the like, the concentration of the solid titanium catalyst component (A) is calculated as titanium atom per liter of the polymerization volume.
Usually about 0.001 to 5000 mmol, preferably about 0.0
It is desirable that it is 1 to 1000 mmol, particularly preferably 0.1 to 500 mmol.

The organometallic compound (B) is used in an amount of 0.01 to 2000 g, preferably 0.03 to 1000 g, and more preferably 0.05 to 200, per 1 g of the solid titanium catalyst component (A).
used in an amount such that g of the preliminary (co) polymer is formed,
It is usually about 0.1 to 1000 mol, preferably about 0.5 to 500, per 1 mol of titanium in the solid titanium catalyst component (A).
Mol Especially preferably used in an amount of 1 to 100 mol.

During the prepolymerization, the organosilane compound (C) is usually added in an amount of 0.01 to 50 mol, preferably 0.05 to 5 mol, per 1 mol of titanium atom in the solid titanium catalyst component (A).
It can be used in an amount of 30 mol, more preferably 0.1 to 10 mol, if necessary.

In the prepolymerization, a molecular weight modifier such as hydrogen can be used. When the prepolymerized catalyst is obtained in a suspended state as described above, the prepolymerized catalyst can be used in the suspended state in the (main) polymerization of the next step, or can be produced from the suspension. It is also possible to separate and use the prepared prepolymerization catalyst.

The prepolymerization catalyst as described above usually forms an olefin polymerization catalyst together with the organometallic compound (B) and the organosilane compound (C), but only the prepolymerization catalyst can be used as the olefin polymerization catalyst. In some cases. When the organosilane compound (C) is not used during the prepolymerization, the olefin polymerization catalyst may be formed by using the organosilane compound (C) together with the prepolymerization catalyst during the main polymerization.

The olefin polymerization catalyst according to the present invention may contain other components useful for the polymerization of olefins, in addition to the above components.

Olefin Polymerization Method In the olefin polymerization method according to the present invention, an olefin polymerization catalyst comprising the solid titanium catalyst component (A), the organometallic compound (B) and the organosilane compound (C) as described above or The olefin is polymerized or copolymerized in the presence of a catalyst containing a prepolymerization catalyst.

As such an olefin, specifically, an α-olefin having 2 or more carbon atoms similar to that used in the prepolymerization can be used, and further, cyclopentene, cycloheptene, norbornene, 5-ethyl-2- Norbornene, tetracyclododecene, 2-ethyl-1,4,5,8
-Cycloolefins such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, styrene, dimethylstyrene, allylnaphthalene, allylnorbornane, vinylnaphthalene, allyltoluene, allylbenzene, vinylcyclopentane It is also possible to use vinyl compounds such as vinyl cyclohexane, vinyl cycloheptane, and allyltrialkylsilanes.

Of these, ethylene, propylene, 1-
Butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-
Methyl-1-pentene, vinylcyclohexane, dimethylstyrene, allyltrimethylsilane, allylnaphthalene and the like are preferably used.

Further, a small amount of a diene compound may be copolymerized with the olefin. As such a diene compound, specifically, 1,3-butadiene, 1,3-pentadiene,
1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5
-Methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6 -Butyl-1,6-
Octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,
6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,
6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,
Examples thereof include 6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene. They are,
You may use it in combination of 2 or more type.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. When the polymerization takes the reaction form of slurry polymerization, the above-mentioned inert organic solvent can be used as the reaction solvent, or a liquid olefin at the reaction temperature can be used.

In the polymerization, the solid titanium catalyst component (A) or the prepolymerization catalyst is generally about 0.001 to 100 mmol, preferably about 0.005 in terms of titanium atom per liter of polymerization volume. Used in an amount of 20 mmol.

The organometallic compound (B) is the compound (B)
It is used in an amount such that the metal atom therein is usually about 1-2000 mol , preferably about 2-500 mol , per 1 mol of titanium atom in the polymerization system.

The organic silane compound (C) is generally used in an amount of about 0.001 mol to 10 mol , preferably 0.01 mol to 5 mol, based on 1 mol of the metal atom of the organometallic compound (B).

If a prepolymerization catalyst is used during this polymerization, it may not be necessary to add the organometallic compound (B) and the organosilane compound (C). When the olefin polymerization catalyst is formed from the components (B) and / or (C) together with the prepolymerization catalyst, these components (B) and (C) can be used in the amounts as described above.

If hydrogen is used during the polymerization, the molecular weight of the obtained polymer can be adjusted and a polymer having a high melt flow rate can be obtained.

In the olefin polymerization method according to the present invention,
Although it varies depending on the type of olefin, the form of polymerization, etc., the polymerization is usually about 20 to 300 ° C., preferably about 50 to
It is carried out at a temperature of 150 ° C. and under normal pressure to 100 kg / cm ^2, preferably about ² to 50 kg / cm ² .

In the polymerization method of the present invention, the polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Furthermore, polymerization can be performed by changing the reaction conditions.
It can also be divided into more than one step.

In the present invention, an olefin homopolymer may be produced, or a random copolymer or a block copolymer may be produced from two or more kinds of olefins. The method of the present invention is particularly suitable for producing a highly stereoregular propylene homopolymer and a random copolymer having a low decane-soluble content of propylene and ethylene and / or an olefin having 4 to 20 carbon atoms. There is. In the random copolymer, the amount of the comonomer to be reacted with propylene is 0 to 50 ethylene per 1 kg of propylene.
0 g, preferably 0.5 to 100 g, more preferably 5
-10 g, olefin having 4 or more carbon atoms 0-2000 g,
Preferably 10-1000 g, more preferably 50-5
It is 00 g. The obtained copolymer contains propylene units in an amount of 85 mol% or more, preferably 90 mol% or more, more preferably 93 mol% or more.

The ethylene content of propylene and ethylene and / or the α-olefin copolymer having 4 to 20 carbon atoms or the α-olefin content of 4 to 20 carbon atoms can be measured as follows.

Ethylene with an ethylene content is an isolated ethylene
It refers to Solitary ethylene means that in the polymer chain
The part of the part where three or more thylene units are continuously polymerized is
Means a unit of ethylene, and the isolated ethylene content (C² ) Is
It is measured as follows. That is, 0.5 g of sample
From Toho Press Seisakusho using a hydraulic molding machine, 2 minutes 30
After heating for 2 seconds and degassing at 20 atm,
Press for 10 seconds at 0 atm. Then, the cooling water is circulated.
Press for 1 minute at 100 bar using the hydraulic molding machine
Get the film. At this time, the thickness of the obtained film is
Use an iron spacer to be about 0.3 mm.
About the obtained film, JASCO DS-701G
Type diffraction grating infrared spectrophotometer 800-650cm
^-1The infrared absorption spectrum of the region is measured by the transmittance. Profit
760 cm of the chart^-1Near and 700 cm^-1With
Draw the common tangent line of the local maximum points and use it as the baseline. 7
33 cm^-1Transmittance (T%) at the absorption minimum point of 733c
m^-1Draw a perpendicular to the wavenumber line from the absorption minimum point of
Transmission at the intersection of the line and the baseline (T₀ %) Read
733 cm^-1Absorbance of (D₇₃₃ = Log (T₀ /
T)) is calculated. Next, the isolated ethylene content (C² )
733 cm^-1Absorbance of (D ₇₃₃ ) And the frame used for measurement
The thickness is calculated from the film thickness (L (mm)) by the following formula.

[0151] Isolated ethylene content (%) = 6.17 x (D₇₃₃ / L) C_Four~ C₂₀1-Butene as a typical α-olefin content
Content rate (C^Four ) Can be measured as follows:
Wear. That is, from 0.5 g of the sample, in the same manner as described above,
Get the film. At this time, the thickness of the obtained film is about
Use an iron spacer to have a thickness of 0.3 mm. Profit
The film obtained, JASCO Corporation A-302 type diffraction
800-700 cm using a lattice infrared spectrophotometer^-1region
The infrared absorption spectrum of is measured by the transmittance. can get
775 cm of chart^-1Near and 750 cm^-1Near pole
Draw the common tangent of the major points and use it as the baseline. 765c
m ^-1Transmittance (T%) at the absorption minimum point of 765 cm^-1of
Draw a perpendicular to the wavenumber line from the absorption minimum point and
Transmissivity (T₀ %) And read 7
65 cm^-1Absorbance of (D₇₆₅ = Log (T₀ / T))
Calculate Next, the 1-butene content (C^Four ) Is 733 cm^-1
Absorbance of (D₇₆₅ ) And the thickness of the film used for measurement
It is calculated from (L (mm)) by the following formula.

1-Butene content (%) = 7.77 × (D ₇₆₅ / L)

[0153]

When the olefin polymerization catalyst containing the solid titanium catalyst component according to the present invention as described above is used, a polyolefin having a low stereoregularity is produced in a small amount and a polyolefin having a high stereoregularity is polymerized at an extremely high level. It can be made active.

[0154]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0155]

Example 1 [Preparation of solid titanium catalyst component (A-1)] Preparation of solid titanium (i) 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 2-ethylhexyl alcohol 3
5.1 ml (225 mmol) were mixed and the mixture was mixed at 130 ° C. for 2 hours.
Heated for a period of time to give a homogeneous solution. Then, 1.67 g (11.5 mmol) of phthalic anhydride was added to this solution, and 1
The mixture was further stirred and mixed at 30 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

After cooling the homogeneous solution thus obtained to room temperature, titanium tetrachloride (T
The whole amount was added dropwise to 200 ml (1.8 mol) of iCl ₄ over 1 hour. After the dropping, the temperature of the obtained solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.03 ml (18.8 mmol) of diisobutyl phthalate was added. It was stirred for another 2 hours at the above temperature.

After the completion of the reaction for 2 hours, solid matter (1) was collected by hot filtration, the solid matter was resuspended in 275 ml of TiCl _{4 and} then heated again at 110 ° C. for 2 hours. After the reaction is completed, the solid part (2) is collected by hot filtration and the temperature is 100 ° C.
Washed with toluene and hexane. The solid part (2) was suspended in 100 ml of hexane, stirred with a spatula for about 30 seconds, and then filtered. This operation was repeated until no titanium compound was detected in the filtrate.

Solid titanium obtained as described above
(i) was obtained as a hexane slurry. A part of this solid titanium (i) was sampled and dried, and its composition was analyzed. The solid titanium (i) contained 2.4% by weight of titanium, 60% by weight of chlorine, 20% by weight of magnesium and 13% by weight of diisobutylphthalate.

Contact with o-dichlorobenzene Next, 100 ml of o-dichlorobenzene was placed in a 200 ml glass reactor sufficiently replaced with nitrogen, and the solid titanium (i) obtained above was converted into titanium atom. Charged 1.0 mmol.

The inside of the reactor was kept at 70 ° C., and the mixture was stirred for 1 hour at a rotation speed of 400 rpm using a stirring blade. After heating and stirring, the solid portion was collected by filtration and washed with hexane three times to obtain a solid titanium catalyst component (A-1).

A part of the solid titanium catalyst component (A-1) obtained as described above was sampled and dried, and then its composition was analyzed. The solid titanium catalyst component (A-1) comprises 1.3% by weight of titanium, 60.0% by weight of chlorine and 2% of magnesium.
0.0% by weight, 11.3% by weight of diisobutyl phthalate
Contained. Therefore, the electron donor / titanium (weight ratio) was 8.69, and the titanium content was 45.8% by weight lower than that before the contact (solid titanium (i)).

[90 ° C. of solid titanium catalyst component (A-1)
Dichlorobenzene Washing] 0.5 g of the solid titanium catalyst component (A-1) obtained above was sampled and put in a 200 ml glass reactor sufficiently replaced with nitrogen, and 100 ml of o-dichlorobenzene was added. The inside of the reactor was maintained at 90 ° C., and the mixture was stirred at 400 rpm of a stirring blade for 1 hour. After completion of stirring, the solid part was collected by filtration, washed twice with hexane, and then dried under reduced pressure.

The titanium content of the solid titanium catalyst component (A-1) after washing was 1.2% by weight. Therefore 90
The reduction rate of the titanium content due to the washing with ° C o-dichlorobenzene was 7.7% by weight.

[Preparation of prepolymerization catalyst (I-1)] Purified hexane 10 was added to a 200 ml glass reactor purged with nitrogen.
0 ml was added, 2 mmol of triethylaluminum, 0.4 mmol of dicyclopentyldimethoxysilane, and 0.2 mmol of the solid titanium catalyst component (A-1) obtained above in terms of titanium atom were charged, and then 1.0 Propylene was fed in an amount of liter / hour for 1 hour.

After the completion of the propylene supply, the solid portion obtained by filtration was washed twice with purified hexane, resuspended in decane and transferred to the catalyst bottle to obtain the prepolymerized catalyst (I-1).

[Main Polymerization] 400 ml of purified heptane was charged into an autoclave having an internal volume of 1 liter, and 0.4 mmol of triethylaluminum, 0.4 mmol of dicyclopentyldimethoxysilane and the above-obtained product were obtained at 60 ° C. in a propylene atmosphere. After adding 0.008 mmol of the prepolymerized catalyst (I-1) in terms of titanium atom, 100 m of hydrogen was added.
After the addition of 1 liter, the temperature was raised to 70 ° C. and maintained for 1 hour to polymerize propylene. During the polymerization, the pressure is 5 kg / cm ² G
Kept at. After the completion of the polymerization, the slurry containing the produced polymer was filtered to separate it into a white granular polymer and a liquid phase part. The results are shown in Table 1.

[0167]

Example 2 [Preparation of Solid Titanium Catalyst Component (A-2)] Contact with o-dichlorobenzene A 200 ml glass reactor fully nitrogen-substituted,
100 ml of o-dichlorobenzene was added, and 1.0 mmol of the solid titanium (i) obtained in Example 1 in terms of titanium atom was charged.

The inside of the reactor was kept at 100 ° C., and the mixture was stirred for 1 hour at a rotation speed of 400 rpm using a stirring blade. After heating and stirring, the solid portion was collected by filtration and washed with hexane three times to obtain a solid titanium catalyst component (A-2).

A part of the solid titanium catalyst component (A-2) obtained as described above was sampled and dried, and then its composition was analyzed. The solid titanium catalyst component (A-2) comprises 1.1% by weight of titanium, 60.0% by weight of chlorine and 2% of magnesium.
0.5 wt%, diisobutyl phthalate 11.4 wt%
Contained. Therefore, the electron donor / titanium (weight ratio) was 10.36, and the titanium content was 54.2% by weight lower than that before the contact (solid titanium (i)).

[90 ° C.-of solid titanium catalyst component (A-2)
Dichlorobenzene cleaning] 90 ° C o-dichlorobenzene cleaning was performed in the same manner as in Example 1 except that the solid titanium catalyst component (A-2) was used in place of the solid titanium catalyst component (A-1). .

The titanium content of the solid titanium catalyst component (A-2) after washing was 1.1% by weight. Therefore 90
The reduction rate of the titanium content by the washing with ° C o-dichlorobenzene was 0% by weight.

[Preparation of Prepolymerized Catalyst (I-2)] In Example 1, the solid titanium catalyst component (A-2) was replaced with the solid titanium catalyst component (A-1) in an amount of 0.1 in terms of titanium atom. In the same manner as in Example 1 except that 2 mmol was used, the prepolymerization catalyst (I-
2) got

[Main Polymerization] Same as in Example 1 except that 0.008 mmol of the titanium atom in terms of the prepolymerization catalyst (I-2) was used in place of the prepolymerization catalyst (I-1). Then, propylene was polymerized. The results are shown in Table 1.

[0174]

[Example 3] [Preparation of solid titanium catalyst component (A-3)] Contact with α, α, α-trichlorotoluene In Example 2, instead of o-dichlorobenzene, α, α,
A solid titanium catalyst component (A-3) was obtained in the same manner as in Example 2 except that 100 ml of α-trichlorotoluene was used.

The solid titanium catalyst component (A-3) comprises 1.0% by weight of titanium, 60.0% by weight of chlorine and 2% of magnesium.
0.0% by weight, 11.3% by weight of diisobutyl phthalate
Contained. Therefore, the electron donor / titanium (weight ratio) was 11.3, and the titanium content was 58.3% by weight lower than that before the contact (solid titanium (i)).

[90 ° C.-of solid titanium catalyst component (A-3)]
Dichlorobenzene washing] 90 ° C o-dichlorobenzene washing was repeated in the same manner as in Example 1 except that the solid titanium catalyst component (A-3) was used in place of the solid titanium catalyst component (A-1). .

The titanium content of the solid titanium catalyst component (A-3) after washing was 1.0% by weight. Therefore 90
The reduction rate of the titanium content by the washing with ° C o-dichlorobenzene was 0% by weight.

[Preparation of Prepolymerization Catalyst (I-3)] In Example 1, the solid titanium catalyst component (A-3) was replaced with the solid titanium catalyst component (A-1) in an amount of 0.1. In the same manner as in Example 1 except that 2 mmol was used, the prepolymerization catalyst (I-
3) got

[Main Polymerization] Same as in Example 1 except that the prepolymerization catalyst (I-1) was replaced by 0.008 mmol of titanium atom in place of the prepolymerization catalyst (I-1). Then, propylene was polymerized. The results are shown in Table 1.

[0180]

[Comparative Example 1] [Preparation of solid titanium catalyst component (A-4)] Example 1 except that solid titanium (i) was replaced with o-dichlorobenzene and contacted with 100 ml of toluene. Similarly, a solid titanium catalyst component (A-4) was obtained.

The solid titanium catalyst component (A-4) comprises 1.5% by weight of titanium, 60.5% by weight of chlorine and 2% of magnesium.
It contained 0.0% by weight and 8.7% by weight of diisobutyl phthalate. Therefore electron donor / titanium (weight ratio)
Is 5.8, the titanium content is before contact (solid titanium
It was 37.5% by weight less than (i)).

[90 ° C. o of solid titanium catalyst component (A-4)
Dichlorobenzene Washing] 90 ° C. o-dichlorobenzene was washed in the same manner as in Example 1 except that the solid titanium catalyst component (A-1) was used in place of the solid titanium catalyst component (A-1). .

The titanium content of the solid titanium catalyst component (A-4) after washing was 1.2% by weight. Therefore 90
The reduction rate of the titanium content by the washing with ° C o-dichlorobenzene was 20% by weight.

[Preparation of Prepolymerized Catalyst (I-4)] In Example 1, the solid titanium catalyst component (A-4) was replaced with the solid titanium catalyst component (A-1) in an amount of 0.1. In the same manner as in Example 1 except that 2 mmol was used, the prepolymerization catalyst (I-
4) got

[Main Polymerization] Same as in Example 1 except that the prepolymerization catalyst (I-1) was replaced by 0.008 mmol of titanium atom in place of the prepolymerization catalyst (I-1). Then, propylene was polymerized. The results are shown in Table 1.

[0186]

[Comparative Example 2] [Preparation of solid titanium catalyst component (A-5)] In Example 1, solid titanium (i) was replaced with o-dichlorobenzene and ter.
In the same manner as in Example 1 except that 100 ml of t-butyl chloride was contacted at 40 ° C., the solid titanium catalyst component (A
-5) got.

The obtained solid titanium catalyst component (A-5) is
Titanium 1.6% by weight, chlorine 60.0% by weight, magnesium 20.0% by weight, diisobutyl phthalate 9.5.
% By weight. Therefore, the electron donor / titanium (weight ratio) was 5.93, and the titanium content was 33.3% by weight lower than that before the contact (solid titanium (i)).

[90 ° C. of solid titanium catalyst component (A-4)
Dichlorobenzene cleaning] 90 ° C o-dichlorobenzene cleaning was performed in the same manner as in Example 1 except that the solid titanium catalyst component (A-5) was used in place of the solid titanium catalyst component (A-1). .

The titanium content of the solid titanium catalyst component (A-5) after washing was 1.2% by weight. Therefore 90
The reduction rate of the titanium content by the washing with ° C o-dichlorobenzene was 25% by weight.

[Preparation of Prepolymerization Catalyst (I-5)] In Example 1, the solid titanium catalyst component (A-5) was replaced with the solid titanium catalyst component (A-1) in an amount of 0.1. In the same manner as in Example 1 except that 2 mmol was used, the prepolymerization catalyst (I-
5) got

[Main Polymerization] Same as in Example 1 except that the prepolymerization catalyst (I-5) was replaced by 0.008 mmol of titanium atom in place of the prepolymerization catalyst (I-1). Then, propylene was polymerized. The results are shown in Table 1.

[0192]

[Comparative Example 3] [Washing of solid titanium (i) at 90 ° C with o-dichlorobenzene]
90 ° C. o-dichlorobenzene was washed in the same manner as in Example 1 except that the solid titanium (i) obtained in Example 1 was used instead of the solid titanium catalyst component (A-1).

The titanium content of the solid titanium (i) after washing was 1.2% by weight. Therefore, the reduction rate of titanium content by 90 ° C. o-dichlorobenzene washing was 50% by weight. The electron donor / titanium (weight ratio) of this solid titanium (i) is 5.42.

[Preparation of Prepolymerized Catalyst (I-6)] In Example 1, instead of the solid titanium catalyst component (A-1), the solid titanium (i) obtained in Example 1 was replaced with a titanium atom. Converted to 0.2
A prepolymerization catalyst (I-6) was obtained in the same manner as in Example 1 except that the amount of the catalyst used was 1 mmol.

[Main Polymerization] Same as Example 1 except that the prepolymerization catalyst (I-1) was replaced by 0.008 mmol of titanium atom in place of the prepolymerization catalyst (I-1). Then, propylene was polymerized. The results are shown in Table 1.

The melting point (Tm) of a propylene homopolymer or a copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms was measured as follows. The melting point (Tm) is DSK- manufactured by PERKIN-ELMER.
7 was used and measured according to ASTM-1. That is, the temperature is raised from room temperature to 200 ° C. at 320 ° C./minute,
After holding at 0 ° C for 10 minutes, the temperature was lowered to 30 ° C at 10 ° C / minute. The exothermic amount curve when polypropylene crystallizes during this temperature decrease is processed by the analysis program of DSC-7 to determine the temperature at the apex of the exothermic peak as Tc. Subsequently, after holding at 30 ° C. for 5 minutes, 200 at 10 ° C./minute
The temperature was raised to ° C. The endothermic curve when polypropylene is melted at this temperature rise is processed by the analysis program of DSC-7 to determine the temperature at the top of the endothermic peak to determine the melting point (Tm).
And

The amount of decane-soluble component of the polymer was measured as follows. 3g sample in 1 liter flask, 20
mg 2,6-di-tert-butyl-4-methylphenol, 500m
1 n-decane was added and heated at 145 ° C. to dissolve. It cooled to 23 degreeC over 8 hours after melt | dissolution, and maintained at 23 degreeC for 8 hours. The precipitated solid and the n-decane solution containing the dissolved polymer were separated by filtration with a glass filter. The liquid phase was dried under reduced pressure at 150 ° C. until a constant weight was obtained, and its weight was measured. The amount of polymer dissolved was calculated and determined as a percentage of the weight of the sample.

The molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined by gel permeation chromatography.
TSK mixed polystyrene gel column (G3000-G7
000) and eluting with o-dichlorobenzene at 140 ° C.

The bulk specific gravity was measured according to JIS K-6721.

[0200]

[Table 1]

[0201]

[Example 4] [Preparation of solid titanium catalyst component (A-6)] In Example 1, except that the contact temperature of solid titanium (i) with o-dichlorobenzene was changed from 70 ° C to 130 ° C. In the same manner as in Example 1, a solid titanium catalyst component (A-6) was obtained.

The solid titanium catalyst component (A-6) contained 0.9% by weight of titanium, 61% by weight of chlorine and 20.
It contained 5% by weight and 8.7% by weight of diisobutyl phthalate. Therefore, the electron donor / titanium (weight ratio) was 9.67, and the titanium content was before contact (solid titanium
It was 62.5% by weight less than that of (i)).

[90 ° C. of solid titanium catalyst component (A-6)
Dichlorobenzene Washing] 90 ° C. o-dichlorobenzene was washed in the same manner as in Example 1 except that the solid titanium catalyst component (A-6) was used in place of the solid titanium catalyst component (A-1). However, the titanium content of the solid titanium catalyst component (A-6) after washing was 0.9% by weight. Therefore 9
The reduction rate of titanium content by 0 ° C. o-dichlorobenzene washing was 0% by weight.

[Preparation of Prepolymerization Catalyst (I-7)] In Example 1, the solid titanium catalyst component (A-6) was replaced with the solid titanium catalyst component (A-1) in an amount of 0.1. In the same manner as in Example 1 except that 2 mmol was used, the prepolymerization catalyst (I-
7) got

[Main Polymerization] Same as Example 1 except that the prepolymerization catalyst (I-7) was used in place of the prepolymerization catalyst (I-1) in 0.008 mmol in terms of titanium atom. Then, propylene was polymerized. The polymer (granular) yield was 90.0 g, and the solvent-soluble content was 0.0 g. Therefore, the polymerization activity was 2200 g-PP / g-cat. The granular polymer, that is, the decane-soluble component in the whole polymer was 0.12% by weight.

The melting point (Tm) of the obtained polymer is 16
4.5 ° C., bulk specific gravity 0.41 g / ml, Mw 438,00
0, Mw / Mn was 3.79.

[0207]

Example 5 [Preparation of solid titanium catalyst component (A-7)] Preparation of solid titanium (i) -2 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 2-ethylhexyl alcohol 3
5.1 ml (225 mmol) were mixed and the mixture was mixed at 130 ° C. for 2 hours.
Heated for a period of time to give a homogeneous solution. Then, 1.67 g (11.5 mmol) of phthalic anhydride was added to this solution, and 1
The mixture was further stirred and mixed at 30 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

After cooling the homogeneous solution thus obtained to room temperature, titanium tetrachloride (T
The whole amount was added dropwise to 200 ml (1.8 mol) of iCl ₄ over 1 hour. After the dropping, the temperature of the obtained solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.03 ml (18.8 mmol) of diisobutyl phthalate was added. It was stirred for another 2 hours at the above temperature.

After completion of the reaction for 2 hours, the solid part (1) was collected by hot filtration and washed with decane at 110 ° C. and hexane at room temperature. The solid part (1) was suspended in 100 ml of hexane and stirred with a spatula for about 30 seconds. This operation was repeated until no titanium compound was detected in the filtrate.

Solid titanium (i) -obtained in this way
Sample No. 2 contained 3.9% by weight of titanium, 52.0% by weight of chlorine, 17.5% by weight of magnesium and 17.2% by weight of diisobutyl phthalate.

Contact with 1,2,4-trichlorobenzene The solid titanium (i) -2 obtained above was treated with 375 ml of 1,2
After resuspending in 2,4-trichlorobenzene, it was heated at 130 ° C. for 1 hour.

After completion of the reaction, a solid portion was collected by hot filtration,
It was washed with 110 ° C. decane and hexane. The solid part was suspended in 100 ml of hexane and stirred with a spatula for about 30 seconds. This operation was repeated until no titanium compound was detected in the filtrate.

The solid titanium catalyst component (A-7) obtained as described above was obtained as a hexane slurry. A part of the solid titanium catalyst component (A-7) was collected and dried to analyze the composition of the solid titanium catalyst component (A-7).

The solid titanium catalyst component (A-7) comprises 1.4% by weight of titanium, 60% by weight of chlorine and 20% of magnesium.
%, And 13.6% by weight of diisobutyl phthalate. Therefore, the electron donor / titanium (weight ratio) was 9.71, and the titanium content was 64.1% by weight more than before contact with 1,2,4-trichlorobenzene (solid titanium (i) -2).
It was decreasing.

[90 ° C.-of solid titanium catalyst component (A-7)
Dichlorobenzene Washing] 0.5 g of the solid titanium catalyst component (A-7) obtained above was sampled and put in a 200 ml glass reactor sufficiently replaced with nitrogen, and 100 ml of o-dichlorobenzene was added. The inside of the reactor was maintained at 90 ° C., and the mixture was stirred at 400 rpm of a stirring blade for 1 hour. After completion of stirring, the solid part was collected by filtration, washed twice with hexane, and then dried under reduced pressure.

The titanium content of the solid titanium catalyst component (A-7) after washing was 1.4% by weight. Therefore 90
The reduction rate of the titanium content by the washing with ° C o-dichlorobenzene was 0% by weight.

[Preparation of Prepolymerized Catalyst (I-8)] In Example 1, the solid titanium catalyst component (A-7) obtained above was used in place of the solid titanium catalyst component (A-1). A prepolymerization catalyst (I-8) was obtained in the same manner as in Example 1 except that the above was used.

[Main Polymerization] Same as in Example 1 except that 0.008 mmol of titanium atom in terms of the prepolymerization catalyst (I-8) was used in place of the prepolymerization catalyst (I-1). Then, propylene was polymerized. The results are shown in Table 2.

[0219]

Example 6 [Preparation of solid titanium catalyst component (A-8)] In Example 5, instead of 11.5 mmol of phthalic anhydride at the time of preparing solid titanium (i) -2, 2-n-butoxy was used. A solid titanium catalyst component (A-8) was obtained in the same manner as in Example 5 except that 11.5 mmol of ethanol was used.

The solid titanium catalyst component (A-8) obtained by contacting with 1,2,4-trichlorobenzene was prepared by mixing titanium with 1.
It contained 0% by weight, 56% by weight of chlorine, 18% by weight of magnesium and 19.5% by weight of diisobutyl phthalate. Therefore, the electron donor / titanium (weight ratio) is 1
It was 9.5, and the titanium content was 83.3% by weight lower than that before the contact with 1,2,4-trichlorobenzene.

[90 ° C.- of solid titanium catalyst component (A-8)
Dichlorobenzene Washing] 90 ° C. o-dichlorobenzene was washed in the same manner as in Example 1 except that the solid titanium catalyst component (A-8) was used in place of the solid titanium catalyst component (A-1). However, the titanium content of the solid titanium catalyst component (A-8) after washing was 1.0% by weight. Therefore 9
The reduction rate of titanium content by 0 ° C. o-dichlorobenzene washing was 0% by weight.

[Preparation of Prepolymerized Catalyst (I-9)] In Example 1, the solid titanium catalyst component (A-8) was replaced with the solid titanium catalyst component (A-1) in an amount of 0.1. In the same manner as in Example 1 except that 2 mmol was used, the prepolymerization catalyst (I-
9) got

[Main Polymerization] The same as Example 1 except that 0.008 mmol of the prepolymerization catalyst (I-9) was used in place of the prepolymerization catalyst (I-1) in terms of titanium atom. Then, propylene was polymerized. The results are shown in Table 2.

[0224]

Example 7 In [Solid titanium catalyst component (A-9) Preparation of Example 5, the solid titanium (i) -2 when prepared, TiO ₂ 0.06 g to TiCl ₄ held in -20 ° C. In the same manner as in Example 5 except that the solid titanium catalyst component (A-9) was suspended.
Got

The solid titanium catalyst component (A-9) obtained by contacting with 1,2,4-trichlorobenzene was obtained by mixing titanium with 2.
It contained 1% by weight, 56% by weight of chlorine, 19% by weight of magnesium and 18.0% by weight of diisobutyl phthalate. Therefore, the electron donor / titanium (weight ratio) is 8.
6, and the titanium content was reduced by 53% by weight as compared with that before contact with 1,2,4-trichlorobenzene.

[90 ° C. o of solid titanium catalyst component (A-9)
Dichlorobenzene Washing] 90 ° C. o-dichlorobenzene was washed in the same manner as in Example 1 except that the solid titanium catalyst component (A-8) was used in place of the solid titanium catalyst component (A-1). However, the titanium content of the solid titanium catalyst component (A-9) after washing was 2.1% by weight. Therefore 9
The reduction rate of titanium content by 0 ° C. o-dichlorobenzene washing was 0% by weight.

[Preparation of Prepolymerization Catalyst (I-10)] In Example 1, the solid titanium catalyst component (A-9) was replaced with the solid titanium catalyst component (A-1) in an amount of 0.1 in terms of titanium atom. The prepolymerization catalyst (I-1) was used in the same manner as in Example 1 except that 2 mmol was used.
I got 0).

[Main Polymerization] Same as in Example 1 except that 0.008 mmol of titanium atom of the prepolymerization catalyst (I-10) was used in place of the prepolymerization catalyst (I-1). Then, propylene was polymerized. The results are shown in Table 2.

[0229]

[Table 2]

[0230]

Example 8 [Main Polymerization] 400 g of propylene, 3.0 liters of ethylene and 4.5 liters of hydrogen were charged into an autoclave having an internal volume of 2 liters, and the temperature was raised to 60 ° C. and triethylaluminum 0.6 After adding 0.003 mmol of dicyclopentyldimethoxysilane and 0.003 mmol of the prepolymerization catalyst (I-7) obtained in Example 4 in terms of titanium atom, the mixture was kept at 70 ° C. for 30 minutes to obtain propylene. Copolymerized with ethylene. The results are shown in Table 3.

[0231]

Example 9 [Main Polymerization] Propylene and ethylene were copolymerized in the same manner as in Example 8 except that the amount of ethylene was changed to 4.0 liter. The results are shown in Table 3.

[0232]

Example 10 [Main Polymerization] In Example 8, the amount of ethylene was changed to 2.5 liters, the amount of triethylaluminum was changed to 0.8 mmol, and the amount of dicyclopentyldimethoxysilane was changed to 0.8 mmol. Propylene and ethylene were copolymerized in the same manner as in Example 8 except that the preliminary polymerization catalyst (I-8) obtained in Example 5 was used instead of 7) and 0.004 millimolar in terms of titanium atom was used. . The results are shown in Table 3.

[0233]

Example 11 [Main Polymerization] In Example 10, propylene and ethylene were copolymerized in the same manner as in Example 10 except that the amount of ethylene was changed to 3.0 liters. The results are shown in Table 3.

[0234]

[Table 3]

[0235]

Example 12 [Preparation of solid titanium catalyst component (A-10)] Preparation of solid titanium (i) 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 2-ethylhexyl alcohol 3
5.1 ml (225 mmol) were mixed and the mixture was mixed at 130 ° C. for 2 hours.
Heated for a period of time to give a homogeneous solution. Then, 1.67 g (11.5 mmol) of phthalic anhydride was added to this solution, and 1
The mixture was further stirred and mixed at 30 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

After cooling the homogeneous solution thus obtained to room temperature, titanium tetrachloride (T
The total amount was added dropwise to 200 ml (1.8 mol) of iCl ₄ over 1 hour. After the dropping, the temperature of the obtained solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.03 ml (18.8 mmol) of diisobutyl phthalate was added. It was stirred for another 2 hours at the above temperature.

After the completion of the reaction for 2 hours, solid matter (1) was collected by hot filtration, and this solid matter was treated with 275 ml of TiCl ₄
After re-suspending in, heated again at 110 ° C. for 2 hours.
After the reaction was completed, the solid part (2) was collected by hot filtration, and 100
C. Washed with toluene and hexane. The solid part (2) was suspended in 100 ml of hexane and stirred with a spatula for about 30 seconds. This operation was repeated until no titanium compound was detected in the filtrate.

Solid titanium obtained as described above
(i) was obtained as a hexane slurry. A part of this solid titanium (i) was sampled and dried, and its composition was analyzed.

Solid titanium (i) contained 2.5% by weight of titanium, 60% by weight of chlorine, 20% by weight of magnesium and 13% by weight of diisobutyl phthalate.

Catalytic treatment with polar compound Next, 100 ml of o-dichlorobenzene was placed in a 200 ml glass reactor sufficiently replaced with nitrogen, and the solid titanium (i) obtained in Example 1 was converted into titanium atom. Charged 1.0 mmol.

The inside of the reactor was maintained at 100 ° C., and the mixture was stirred for 1 hour at a rotation speed of 400 rpm using a stirring blade. After heating and stirring, the solid portion was collected by filtration and washed with hexane three times to obtain a solid titanium catalyst component (A-10).

A part of the solid titanium catalyst component (A-10) obtained as described above was collected and dried, and then its composition was analyzed. The solid titanium catalyst component (A-10) contained 0.95% by weight of titanium, 60.0% by weight of chlorine, 20.5% by weight of magnesium and 11.4% by weight of diisobutylphthalate.

[Preparation of prepolymerization catalyst (I-11)] Purified hexane 10 was added to a 200 ml glass reactor purged with nitrogen.
0 ml was added, triethylaluminum (2 mmol), dicyclopentyldimethoxysilane (0.4 mmol) and the solid titanium catalyst component (A-10) obtained above were charged in an amount of 0.2 mmol in terms of titanium atom. Propylene was fed in an amount of liter / hour for 1 hour.

After the completion of the propylene supply, the solid portion obtained by filtration was washed twice with purified hexane, resuspended in decane and transferred to the catalyst bottle to obtain the prepolymerized catalyst (I-11).

[Main Polymerization] 400 ml of purified heptane was charged into an autoclave having an internal volume of 1 liter, and 0.4 mmol of triethylaluminum, 0.4 mmol of dicyclopentyldimethoxysilane and the above-obtained product were obtained at 60 ° C. in a propylene atmosphere. After adding 0.008 mmol of the prepolymerized catalyst (I-11) in terms of titanium atom, hydrogen 100 m
After the addition of 1 liter, the temperature was raised to 70 ° C. and maintained for 1 hour to polymerize propylene. During the polymerization, the pressure is 5 kg / cm ² G
Kept at. After the completion of the polymerization, the slurry containing the produced polymer was filtered to separate it into a white granular polymer and a liquid phase part. The results are shown in Table 5.

[0246]

Examples 13 to 15 Example 1 was repeated except that a polar compound as shown in Table 4 was used in place of o-dichlorobenzene at the “contact treatment with polar compound” in Example 12.
The same operation as in 2 was performed. The polymerization results are shown in Table 5.

[0247]

Comparative Example 4 The same operation as in Example 12 was carried out except that the “contact treatment with polar compound” was not carried out. The polymerization results are shown in Table 5.

[0248]

[Comparative Example 5] The same operation as in Example 12 was carried out except that toluene shown in Table 4 was used in place of o-dichlorobenzene in "contact treatment with a polar compound" in Example 12. The polymerization results are shown in Table 5.

[0249]

Examples 16 to 17 In Example 12, instead of o-dichlorobenzene at the time of “contact treatment with polar compound”
The same operation as in Example 12 was performed, except that 1,2,4-trichlorobenzene was diluted with decane to a concentration shown in Table 4 and used. The polymerization results are shown in Table 5.

[0250]

Examples 18 to 19 The same as Example 12 except that the contact temperature between solid titanium and o-dichlorobenzene was changed to the temperature shown in Table 4 during the “contact treatment with a polar compound”. The same operation was performed. The polymerization results are shown in Table 5.

[0251]

Example 20 The same operation as in Example 12 was carried out except that diphenyldichlorosilane shown in Table 4 was used in place of o-dichlorobenzene in the “contact treatment with a polar compound” in Example 12. The polymerization results are shown in Table 5.

[0252]

[Comparative Example 6] In Example 12, at the time of "contact treatment with a polar compound", phthalic acid chloride shown in Table 4 was used in place of o-dichlorobenzene and brought into contact with solid titanium at 70 ° C. The polymerization results are shown in Table 5.

[0253]

[Table 4]

[0254]

[Table 5]

[Brief description of drawings]

FIG. 1 shows an example of a preparation process of a solid titanium catalyst component and an example of a preparation process of an olefin polymerization catalyst according to the present invention.

Continuation of front page (56) Reference JP-A-6-271611 (JP, A) JP-A-6-336503 (JP, A) JP-A-62-104813 (JP, A) JP-A-59-122505 (JP , A) JP-A-64-56708 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (9)

(57) [Claims] 1. (i) Magnesium, titanium, halogen and
And an electron donor, and by washing with hexane at room temperature.
A solid titanium never titanium desorbed I, is contacted with (ii) a 40 ° C. or more halogen-containing aromatic hydrocarbon
And the titanium content in the solid titanium (i) is 25% by weight.
Obtained by reducing or, (1) a titanium content of 2.5 wt% or less, (2) a total content of magnesium and halogen is less than 65 wt% or more 92 wt%, (3) Electronic The donor content is 8 to 30% by weight, (4) the electron donor / titanium (weight ratio) is 7 or more , and (5) titanium is substantially desorbed by washing with hexane at room temperature. A solid titanium catalyst component characterized in that the titanium content is less than 15% by weight when washed with o-dichlorobenzene at 90 ° C. 2. Solid titanium containing (i) magnesium, titanium, a halogen and an electron donor, and titanium is not desorbed by hexane washing at room temperature, and (ii) a halogen-containing aromatic hydrocarbon. Are contacted at 40 ° C. or higher, and the titanium content in the solid titanium (i) is 25% by weight.
By reducing or, (1) the titanium content is 2.5 wt% or less, (2) the total content of magnesium and halogen 65wt
% And less than 92 wt%, (3) an electron donor content of from 8 to 30% by weight, (4) an electron donor / titanium (weight ratio) Ri der least 7, (5) at room temperature Titanium is substantially removed by washing with hexane.
90 ° C o- dichlorobenzene that is not separated
The reduction rate of titanium content when washed with
A method for producing a solid titanium catalyst component, comprising producing a solid titanium catalyst component. 3. The method for producing a solid titanium catalyst component according to claim 2 , wherein the electron donor / titanium (weight ratio) in the solid titanium (i) is 6 or less. 4. A solid titanium (i) is a solid (1) obtained by contacting (a) a magnesium compound in a liquid state, (b) a titanium compound in a liquid state, and (c) an electron donor. The method for producing a solid titanium catalyst component according to claim 2 or 3 , wherein 5. A solid titanium (i), which is obtained by contacting (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c) an electron donor. ,
The method for producing a solid titanium catalyst component according to claim 2 or 3 , further comprising (b) a solid (2) obtained by contacting the titanium compound in a liquid state. 6. A solid titanium catalyst component according to claim 1, (B) an organometallic compound, and (C) an organosilane compound having at least one alkoxy group. And a catalyst for olefin polymerization. 7. An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 6 . 8. The (A) solid titanium catalyst component according to claim 1, (B) an organometallic compound, and (C) an organosilane compound having at least one alkoxy group if necessary, A prepolymerization catalyst in which an olefin is prepolymerized or precopolymerized. 9. An olefin polymerization comprising the prepolymerization catalyst according to claim 8 and, if necessary, (B) an organometallic compound and / or (C) an organosilane compound having at least one alkoxy group. An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of a catalyst.