JP2811325B2 - Catalyst component for olefin polymerization - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a catalyst for the polymerization of alpha-olefins, in particular, a titanium halide catalyst component supported on a magnesium compound and a catalyst system containing such a component. It is about.

[Conventional technology and its problems] Magnesium-containing supported catalysts with high catalytic activity and good stereospecificity have been developed, and these can easily treat catalyst residues in the produced polymer. It is well known that it is suitable for gas-phase alpha olefin polymerization because the removal of components is unnecessary.

In order to obtain good operability, the gas phase alpha olefin polymerization catalyst is required to have a good particle shape, a narrow particle size distribution, good crush resistance, a high particle bulk density, and the like. I have. As one method of improving the catalyst particle morphology, JP-A-63-54405 discloses that a magnesium compound is dissolved in an alcohol in the presence of carbon dioxide, treated with a mixture of a titanium halide and an organosilane, and precipitated to form a cyclic ether. A method is described in which a carrier having a good shape is obtained by adding a compound and then re-dissolving and recrystallizing, and the carrier is activated to be used as a catalyst.

Unlike the suspension polymerization method, a large number of copolymers have been produced in the gas-phase olefin olefin polymerization by utilizing the characteristic that a rubber component produced as a by-product is not extracted by a solvent or the like. For the production of a highly tacky polymer having a rubber component, it is necessary to maintain good flowability of the produced polymer powder, and for this purpose, the particle size of the powder needs to be large,
A catalyst component having a large particle size is required to provide such a powder.

In general, catalyst particles produced by a precipitation method from a solution are such that even if the carrier particles are clean and the particle size distribution can be sharply produced, some of the particles must be broken in the subsequent activation treatment step and the like. There was no place. Also,
The larger the particles, the more likely they are to break.In the invention of JP-A-63-54405, the particle diameter is 30 μm.
When the particle size becomes large, the amount of the particles to be collapsed increases during the activation treatment with titanium halide or the like, and there is room for improvement such that the fine powder increases.

[Problems to be Solved by the Invention] In the present invention, when a catalyst component is produced by a precipitation method from a solution, particularly when a catalyst component having a large particle size is produced, particles are broken during titanium halide treatment. The present invention relates to a method for producing a supported catalyst having no or very little collapse.

JP-A-63-54405 discloses that an alkaline earth alcoholate is made into an alcohol solution using carbon dioxide, and a silicone compound is used when forming a catalyst component therefrom.
Further, there is described a method for obtaining a catalyst component having a good shape by complexing magnesium with tetrahydrofuran.

There are many examples of using a silicon compound in the formation of the catalyst component, but no example using a boron compound instead of the silicon compound has been disclosed. JP
JP-A-63-277204 discloses the use of a boron compound in combination with a silicon compound, but does not clearly show the effect of the boron compound. It does not indicate that it is superior to a silicon compound in terms of the purpose of the invention.

The present inventors, while maintaining the high activity of the above-mentioned catalyst system, high stereoregularity polymerization performance, when controlling the catalyst component from small particle size to large particle size, especially particles with large particle size As a result of intensive studies on a method for improving the shape and the particle size distribution, the present inventors have reached the present invention capable of preventing the particles from being crushed during the catalyst production process and obtaining a catalyst component having a sharper particle size distribution and a uniform shape.

That is, the present invention is based on the method disclosed in JP-A-63-54405, in which a solid precipitate is formed from an alcohol solution of a magnesium compound with a titanium halide and reprecipitated from a solution containing a cyclic ether. However, at the time of the re-praying, by performing this in the presence of a boron compound, the precipitate of the obtained magnesium compound is made hard to collapse, and the particle crushing in the subsequent titanium halide treatment step is prevented. It is an object of the present invention to provide a catalyst component having a sharp particle size distribution obtained by the method and an olefin polymerization catalyst obtained by combining the catalyst component with an organometallic compound.

[Means for Solving the Problems] The present invention has the following configurations (1) to (4).

(1) An olefin polymerization catalyst in which a titanium halide, a vanadyl halide, or a vanadium halide is supported on a carrier containing a Mg compound precipitated from a solution state as a main component, A. General formula Mg (OR ¹ ) _N (OR ² ) _2-n or MgR ³ _m (OR ⁴ ) _2-m
Or a mixture thereof (wherein R ¹ , R ² , R ³ , and R ⁴ are an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, or a 5 carbon atom) From 20 to 20 aromatic groups, m,
n is a number from 0 to 2), in the presence of carbon dioxide, a saturated or unsaturated mono- or polyhydric alcohol having 1 to 20 carbon atoms represented by the general formula R ⁵ OH and an inert hydrocarbon solvent. B. A mixture of (Component A) and a titanium halide represented by the general formula TiX _p (OR ⁶ ) _4-p (where X is C 1 Or Br and R ⁶ are an alkyl group having 1 to 20 carbon atoms, an aryl group or
And / or p is 1 to 4) and / or a vanadyl halide represented by the general formula VOX _q (OR ⁷ ) _3-q and / or a general formula VX _r (OR ⁸ ) _4- vanadium halide represented by _r (where X is C1 or Br,
R ⁷ and R ⁸ are each an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms,
q is from 1 3, r is 1 to 4.) and / or the general formula SiX _s (OR ⁹⁾ in _4-s with a halogenated silane represented (wherein, X is C1 or Br, R ⁹ is the number of carbon atoms An alkyl group, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, wherein s is 1 to 4) and a general formula BR ¹⁰ _t (OR
¹¹ ) A boron compound represented by _3-t or a mixture of a plurality of the boron compounds (where R ¹⁰ and R ¹¹ are each a carbon atom having 1 to ¹⁰ carbon atoms)
An alkyl group, an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic group having 5 to 20 carbon atoms, and t is a number of 0 to 3). C. reacting the solid product (I) with a cyclic ether, dissolving and reprecipitating to obtain a solid product (II); D. A titanium halide represented by the formula TiX _p (OR ⁶ ) _4-p (where X is C 1 or Br, R ⁶ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl having 3 to 20 carbon atoms) And / or p is 1 to 4) and / or a vanadyl halide represented by the general formula VOX _q (OR ⁷ ) _3-q and / or a general formula VX _r (OR ⁸ ) _4-r
Wherein X is C1 or Br, R ⁷ and R ⁸ are each an alkyl group having 1 to 20 carbon atoms,
(Component B) consisting of an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, wherein q is 1 to 3 and r is 1 to 4) is reacted to obtain a solid product (III). Reacting a mixture of (Component B) with an electron donor,
Or a catalyst component comprising a solid product (IV) obtained by reacting with a solid product (III) ′ obtained by reacting with a solid product (II).

(2) The catalyst component according to (1), wherein the molar ratio of titanium / magnesium is 0.5 to 10, and the molar ratio of electron donor / titanium is 0.2 to 20.

(3) The solid product (IV) described in the above (1) is further added to a titanium halide represented by the general formula TiX _p (OR ⁶ ) _4-p (where X is C1 or Br, and R ⁶ is carbon An alkyl group of the formulas 1 to 20,
An aryl group or a cycloalkyl group having 3 to 20 carbon atoms, p is 1 to 4) and / or a general formula VOX
_q Halogen vanadyl represented by (OR ⁷ ) _3-q and / or vanadium halide represented by general formula VX _r (OR ⁸ ) _4-r (where X is C 1 or Br, R ⁷ , R ⁸ is an alkyl group having 1 to 20 carbon atoms, an aryl group or 3 to 20 carbon atoms, respectively.
Wherein q is 1 to 3 and r is 1 to 4) (component B).

(4) An alpha olefin polymerization catalyst comprising a combination of the catalyst component described in the above (1) and a cocatalyst component comprising an organometallic compound, or a combination thereof with an electron donor as a third component.

The configuration and effect of the present invention will be described in detail below.

 Step A will be described first.

In Step A, in the presence of carbon dioxide, a magnesium compound represented by the general formula Mg (OR ¹ ) _n (OR ² ) _2-n or MgR ³ _m (OR ⁴ ) _2-m or a mixture thereof (here, Wherein R ¹ , R ² , R ³ , and R ⁴ are an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic group having 5 to 20 carbon atoms; , n is a number from 0 to 2) from a carbon number 1 represented by the general formula R ⁵ OH
A 20- or 2-saturated monohydric or polyhydric alcohol is mixed with an inert hydrocarbon solvent in the presence of carbon dioxide to cause reaction and dissolution to obtain (Component A).

Mg (OCH ₃ ) ₂ , Mg (OC ₂ H ₅ ) ₂ , Mg (OC ₃ H ₇ ) ₂ , Mg
(OC ₄ H ₉ ), Mg (OCH (CH ₃ ) C ₂ H ₅ ) ₂ , ₂ Mg (OC
_{8 H 17) 2, Mg (} OCH 2 CH (C 2 H 5) C 4 H 9) 2, Mg (OCH 2 CHCH
₂ ) ₂ , Mg (OC ₆ H ₅ ) ₂ , Mg (OC ₆ H ₁₁ ) ₂ , Mg (OC ₆ H ₄ C
H ₃ ) ₂ , Mg (OC ₁₀ H ₇ ) ₂ , Mg (OC ₁₀ H ₆ CH ₃ ) ₂ , Mg (OC
₁₀ H ₁₇ ) ₂ , Mg (OC ₁₀ H ₁₆ CH ₃ ) ₂ , Mg (OCH ₃ ) (OC
_{2 H 5), Mg (OC} 2 H 5) (OC 6 H 13), Mg (OC 2 H 5) (OC
₈ H _17), mention may be made of _{Mg (OC 3 H 7) (} OC 6 H 5) or the like.

In addition, Mg (CH
_{3) 2, Mg (C 2} H 5) 2, Mg (C 3 H 5) 2, Mg (C 4 H 9) 2, M
g (C ₆ H ₁₃ ) ₂ , Mg (C ₈ H ₁₇ ) ₂ , Mg (CHCHC ₂ H ₅ ) ₂ , Mg
(C ₆ H ₅ ) ₂ , Mg (C ₆ H ₄ CH ₃ ) ₂ , Mg (C ₆ H ₁₁ ) ₂ , Mg (C
_{10 H 7) 2, Mg (} CH 3) (C 2 H 5), Mg (C 2 H 5) (C 6 H 11),
Mg (C ₃ H ₇ ) (C ₆ H ₅ ) and the like, and mixtures thereof, Mg (OC ₂ H ₅ ) (C ₄ H ₉ ), Mg (OC ₃ H ₇ ) (C ₆ H ₅ ) ) Can also be used.

As the component alcohol, aliphatic saturated and unsaturated alcohols can be used. Specifically, methanol, ethanol, propanol, isopropanol,
Examples thereof include isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol, dodecanol, propenyl alcohol, butenyl alcohol, and ethylene glycol and trimethylene glycol. Among them, aliphatic alcohols having 2 to 10 carbon atoms are preferable.

Next, in Step B, (Component A) and the general formula BR ¹⁰ _t
(OR ¹¹ ) A boron compound represented by _3-t alone or a mixture of a plurality of the boron compounds (where R ¹⁰ and R ¹¹ are an alkyl group having 1 to 20 carbon atoms, an aryl group, or a 3 to 20 carbon atoms) A cycloalkyl group or an aromatic group having 5 to 20 carbon atoms, and t is a number of 0 to 3) in the presence of a halogenated compound represented by the general formula TiX _p (OR ⁶ ) _4-p titanium (wherein, X is C1 or Br, R ⁶ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group an aryl group or a C 3 to 20, an aromatic group, p is is 1 to 4) And / or a vanadyl halide represented by the general formula VOX _q (OR ⁷ ) _3-q and / or a vanadium halide represented by the general formula VX _r (OR ⁸ ) _4-r (where X is C1 or Br, R ⁷ ,
R ⁸ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, q is 1 to 3, r is 1 to 4) and / or a general formula
Reaction with a halogenated silane represented by SiX _s (OR ⁹ ) _4-s gives a solid product (I).

This reaction is desirably carried out in a suitable amount of an inert aromatic or aliphatic hydrocarbon solvent.

Boron compounds include methyl borate, ethyl borate, propyl borate, isopropyl borate, butyl borate, isobutyl borate, tertiary butyl borate, pentyl borate, actyl borate,
-Chlorobuty, allyl borate, phenyl borate, toluyl borate, diethyl cyclohexyl borate, ethyl dibutoxy borane, dibutyl monoethoxy borane, triethyl borane, triisopropyl borane, tributyl borane, tricyclohexyl borane and the like.

B / of the boron compound used in Step B and (Component A)
The molar ratio of Mg is typically 0.1 / 1 to 2.0 / 1, preferably 0.3 /
It is 1 to 1/1.

The titanium halides represented by the general formula TiX _p (OR ⁶ ) _4-p include titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride Hexoxytitanium trichloride, octoxytitanium trichloride, cyclohexoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide, butoxytitanium tribromide, diethoxytitanium dichloride,
Dipropoxy titanium dichloride, dibutoxy titanium dichloride,
Octoxytitanium dichloride, diphenoxytitanium dichloride,
Examples thereof include dicyclohexoxytitanium dichloride, diethoxytitanium dibromide, dibutoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, triethoxytitanium bromide, and triphenoxytitanium bromide.

Titanium halides other than titanium tetrachloride and titanium tetrabromide can be made by the reaction of titanium tetrahalide and orthotitanate, but instead of those made by this reaction, titanium tetrahalide and orthotitanate Mixtures with titanates can also be used. Among these titanium halides, titanium tetrachloride is most preferred.

The vanadyl halide and vanadium halide represented by the general formulas VOX _q (OR ⁷ ) _3-q and VX _r (OR ⁸ ) _4-r include vanadyl trichloride, vanadyl tribromide, and ethoxy vanadyl dichloride. , Butoxyvanadyl dichloride, phenoxyvanadyl dichloride, methoxyvanadyl dibromide, propoxyvanadyl dibromide, cyclohexoxyvanadyl dibromide, dimethoxyvanadyl chloride, diethoxyvanadyl chloride, dicyclohexoxyvanadyl chloride, dipropoxy vanadyl bromide ,
Dibutoxy vanadyl bromide, vanadium tetrachloride, vanadium tetrachloride, methoxy vanadium trichloride, ethoxy vanadium tribromide, butoxy vanadium trichloride, cyclohexoxy vanadium tribromide, phenoxy vanadium trichloride,
Diethoxy vanadium dichloride, dibutoxy vanadium dibromide, phenoxy vanadium dichloride, trimethoxy vanadium chloride, triethoxy vanadium bromide, tripropoxy vanadium chloride, tributoxy vanadium bromide, triphenoxy vanadium chloride and the like can be mentioned. .

As the halogenated silane represented by the general formula SiX _r (OR ⁹ ) _4-r , silicon tetrachloride, silicon tetrabromide, methoxysilicon tribromide, ethoxysilicon trichloride, propoxysilicon tribromide, butoxysilicon trichloride , Cyclohexoxy silicon trichloride, dimethoxy silicon dichloride, diethoxy silicon dibromide, dipropoxy silicon dichloride, dibutoxy silicon dibromide, diphenoxy silicon dichloride, trimethoxy silicon bromide, triethoxy silicon chloride, tripropoxy silicon bromide, chloride Tributoxy silicon and the like can be mentioned. Further, a mixture of these can also be used.

The molar ratio of the total number of moles of the metal of the titanium halide or / and / or the vanadyl halide or / and the vanadium / or the halogenated silane used in Step B to the Mg of the component A is from 1 / 0.3 to 20 / 1, preferably 1 / 0.5 to 5/1.

In Step C, the solid product (I) is dissolved in a solvent containing a cyclic ether and reprecipitated to obtain a solid product (II). Once the whole is dissolved and reprecipitated, the particle shape,
A carrier having a uniform particle size (solid product (II)) is obtained.

In the mother liquor of the stage C, the boron compound in the mother liquor of the stage B is present, and the mechanism thereof has not been elucidated yet.
It has been found that it is effective in preventing particle crushing in the subsequent processing steps.

As the cyclic ether, tetrahydrofuran, tetrahydropyran, methyltetrahydrofuran, dimethyltetrahydropyran, tetramethyltetrahydrofuran,
Examples thereof include dioxane, dioxolan, trioxane, pyran, benzopyran, and dihydrobenzofuran. Among them, tetrahydrofuran is the best.

In step D, the solid product (II) is treated with a titanium halide represented by the general formula TiX _p (OR ⁶ ) _4-p and / or a general formula VOX _q (OR ⁷ ) _3-q
A vanadyl halide represented by the formula and / or the general formula VX
_r (OR ₈ ) A mixture of a vanadium halide represented by _4-r (component B) and an electron donor is reacted to obtain a solid product (III) (where X is C1 or Br , R
⁶ , R ⁷ and R ⁸ are each an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms,
q is 1 to 3, p and r are 1 to 4), before or after the reaction (Component B) with the solid product (II) or (II
It is desirable to process I).

Here, (Component B) can be selected from titanium halide, vanadyl halide, or vanadium halide described in Step B. Even if (Component B) is added to the solid product (II) or (III),
(Component B) may be charged with the solid product (II) or (III).

Suitable electron donors for the preparation of the mixture are the aromatic mono- and polycarboxylic esters. Examples of the aromatic polycarboxylic acid esters include benzene polycarboxylic acid esters and naphthalene polycarboxylic acid esters.

Specifically, as the benzene polycarboxylic acid ester, monomethyl phthalate, dimethyl phthalate, monoethyl phthalate, diethyl phthalate, dipropyl phthalate,
Mono-n-butyl phthalate, di-n-butyl phthalate,
Monoisobutyl phthalate, diisobutyl phthalate, di-n-hexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, didecyl phthalate, dibenzyl phthalate, diphenyl phthalate, diethyl isophthalate, isophthalate Mono- and diesters of benzyl carboxylic acids such as dipropyl acrylate, dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, dibenzyl terephthalate and diphenyl terephthalate, hemimetry Monobutyl acid, dibutyl hemimetriate, tributyl hemimetriate,
Mono, di and triesters of benzenetricarboxylic acid such as monoethyl trimellitate, dipropyl trimellitate, tributyl trimellitate, diethyl trimesate, tributyl trimesate and tri-2-ethylhexyl trimesate, monomethyl prenitate, diethyl prenitate, prenitite Tripropyl benzoate, tetrabutyl prenitate, diethyl dibutyl prenitate, dibutyl melophanate, tetrabutyl pyromellitate and dimethyl dipropyl pyromellitate
Di, tri, and tetraesters, and mono, di, tri, tetra, penta, and hexaesters of benzenepentacarboxylic acid and melittic acid, and the like can be used.

Also, as naphthalene polycarboxylic acid ester,
Naphthalene dicarboxylic acid, naphthalene tricarboxylic acid,
Mono, di, tri, tetra and pentaesters of naphthalenetetracarboxylic acid and naphthalenepentacarboxylic acid can be used.

As the aromatic monocarboxylic acid ester, methyl benzoate, ethyl benzoate, butyl benzoate, isobutyl benzoate, cyclohexyl benzoate,
Examples thereof include benzoic acid esters such as methyl-p-toluate, ethyl-p-toluate, methyl-p-anisate, butyl-p-anisate, ethylchlorobenzoate and methylbromobenzoate, and benzoic esters having a substituent.

The electron donor used in Step D is used in an amount ranging from about 0.0001 to 1.0 mole per gram atom of titanium or vanadium, preferably 0.005 to 0.8 mole per gram atom.

Diluents useful in the production of the catalyst component of the present invention include aromatics such as benzene, toluene, xylene, ethylbenzene, halogenated aromatics such as chlorobenzene, dialomobenzene, hexane, heptane, octane, nonane, decane. And alkanes such as undecane, cyclohexane and methylcyclohexane, halogenated alkanes such as 1,2-dichloroethane, 1,1,2-trichloroethane and carbon tetrachloride, isoparaffinic hydrocarbons, kerosene and the like.

As described above, the solid product (III) is obtained by the reaction between the solid product (II) and the (component B), and the solid product (III) is obtained by the reaction of the (mixture of the (component B) and the electron donor). A solid product (IV), the catalyst component of the invention, is obtained.

In the reaction from the solid product (II) to the solid product (IV), the above reaction order is reversed, and the solid product (II)
To obtain a solid product (III) ', and then to react with the solid product (III)' to obtain a solid product (IV).

The catalyst component of the present invention is made under an atmosphere of an inert gas such as nitrogen or argon gas or an alpha olefin, while eliminating catalyst poisons such as water and oxygen carbon monoxide.
Purification of the diluents and raw materials used also helps to remove catalyst poisons from the catalyst production system. The above preparation results in a solid product (IV) which is applicable for use as a catalyst component.

Prior to using the solid product (IV), it is desirable to remove unreacted starting materials from the solid product. This removal
This is conveniently accomplished by washing the solid with a suitable solvent, such as liquid hydrocarbons or chlorocarbons, after separation from the manufacturing diluent, within a short time after completion of the solid product preparation reaction. This is because prolonged contact between the catalyst component and the unreacted starting material may adversely affect the performance of the catalyst component.

Although not an essential step, the solid product (IV) obtained as described above may be brought into contact with at least one liquid electron acceptor before use in the polymerization. Electron acceptors useful in the present invention are liquid at the processing temperature and are sufficient to remove impurities such as unreacted starting materials and poorly bound compounds from the surface of the solid product (IV) described above. It has a very high Lewis acidity. Preferred electron acceptors include those III-V which are liquid at temperatures up to about 170 ° C.
Including halides of group metals.

Specific examples thereof include BCl ₃ , AlBr ₃ , TiCl ₄ , TiBr ₄ , S
iCl ₄ , GeCl ₄ , SnCl ₄ , PCl ₃ and SbCl ₅ . Preferred electron acceptor are TiCl ₄ and SiCl _4. It can also be used as an electron acceptor mixture. Such an electron acceptor may be used in a compatible diluent.

Furthermore, although these are also not essential steps, if the solid product described above is washed with an inert liquid hydrocarbon or halogenated hydrocarbon prior to contact with the electron acceptor, the washed solid and the electron acceptor It is preferred that the inert liquid is substantially removed before contacting the liquid.

Although the chemical structures of the catalyst components according to the invention described herein are not currently known, they are preferably from about 1 to about 6% by weight of titanium, from about 10 to about 25% by weight of magnesium, and about 45% by weight of magnesium. From about 65% by weight of halogen. A preferred catalyst component made in accordance with the present invention is about 1.
It contains 0 to about 3% by weight titanium, about 15 to about 21% by weight magnesium and about 55 to about 65% by weight chlorine.

The titanium-containing catalyst component of the present invention may be prepolymerized with an alpha olefin prior to use as a polymerization catalyst component.
In the prepolymerization, the catalyst component and an organoaluminum compound cocatalyst such as triethylamine are polymerized with an alpha olefin such as propylene under polymerization conditions, preferably in the presence of a modifier such as silane, and a non-polymer such as hexane. Contact in activated hydrocarbon.

Preferably, the resulting prepolymerized catalyst component has a polymer / catalyst weight ratio of about 0.1: 1 to about 20: 1. Prepolymerization forms a coating of polymer around the catalyst particles, which in many cases improves particle morphology, activity, stereospecificity and abrasion resistance. A particularly useful prepolymerization procedure is described in U.S. Patent No. 457, cited in the aforementioned JP-A-63-54405.
9836.

The titanium-containing catalyst component of the present invention comprises a Group II or III
It is used in a polymerization catalyst comprising a co-catalyst component, including the metal alkyl of the Group metal, and typically one or more modifier compounds.

Group II and Group III metal alkyl useful are compounds of formula MR _m, wherein, M is a Group II or Group II, A metals, each R is independently from 1 to about 20 Is an alkyl group of carbon atoms, and m corresponds to the valence of M.

Examples of organometallics, M, are magnesium, calcium, zinc, cadmium, aluminum and potassium.

Examples of suitable alkyl groups, R, include methyl, ethyl, butyl, hexyl, decyl, tetrodecyl and eicosyl.

From the viewpoint of catalyst component performance, preferred Group II and Group II
Group A metal alkyls are of magnesium, zinc and aluminum, wherein the alkyl group contains 1 to 12 carbon atoms.

Specific examples of such compounds are Mg (CH ₃ ) ₂ , Mg (C ₂ H ₅ )
_{2, Mg (C 2 H 5} ) (C 4 H 9), Mg (C 4 H 9) 2, Mg (C 6 H 13)
_{2, Mg (C 12 H 25} ) 2, Zn (CH 3) 2, Zn (C 2 H 5) 2, Zn
(C ₄ H ₉ ) ₂ , Zn (C ₄ H ₉ ) (C ₈ H ₁₇ ), Zn (C ₆ H ₁₃ ) ₂ , Zn
(C ₁₂ H ₂₅ ) ₂ , Al (CH ₂ ) ₃ , Al (C ₂ H ₅ ) ₃ , Al (C
₃ H ₇ ) ₃ , Al (C ₄ H ₉ ) ₃ , Al (C ₆ H ₁₃ ) ₃ , and Al (C ₁₂ H
₂₅ ) Including ₃ .

More preferably, magnesium-, zinc-, or aluminum alkyls containing from 1 to about 6 carbon atoms per alkyl group are used. Best results are achieved by using trialkylaluminums containing from 1 to about 6 carbon atoms per alkyl group, especially triethylaluminum and triisobutylaluminum.

As the organoaluminum compound, one or one
Metals with more than one halogen or hydride group,
For example, ethyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum sesquichloride, diisobutyl aluminum, and hydride can be used.

An exemplary catalyst composition is formed by combining a supported titanium-containing compound and an alkylaluminum compound described in this invention with a modifier comprising an electron donor and preferably a silane. The atomic ratio of aluminum to titanium in such catalyst compositions is from about 10 to about 500, preferably from about 30 to about 300. Also, the molar ratio of the aluminum compound to the electron donor is from about 5 to about 40. Further, the preferred molar ratio of aluminum compound to silane compound is from about 8 to about 30.

In the catalyst of the present invention, in order to maximize catalytic activity and stereospecificity, it is preferable to combine one or more modifiers. The modifier is an electron donor, and silanes, mineral acids, organometallic chalcogenide derivatives of hydrogen sulfide, organic acids, organic acid esters and mixtures thereof can be used.

Organic electron donors useful as co-catalyst modifiers of the present invention are organic compounds containing oxygen, silicon, nitrogen, sulfur, and / or phosphorus.

Such compounds include organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, aldehydes, ketones,
Includes silanes, amines, amine oxides, amides, thiols, various phosphate esters and amides, and the like. If necessary, a mixture of organic electron donors can be used.

Preferred organic acids and esters are benzoic acid, halobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, their alkyl esters wherein the alkyl group contains from 1 to about 6 carbon atoms, such as methyl benzoate, bromobenzoic acid Methyl, ethyl benzoate, ethyl chlorobenzoate, butyl benzoate, isobutyl benzoate, methyl anisate, ethyl anisate, methyl p-toluate, benzoic acid-hexyl, and cyclohexyl benzoate, and isobutyl phthalate; They give good results in terms of activity and stereospecificity and are convenient to use.

Further, the co-catalyst modifier for polymerization useful in the present invention preferably includes an aliphatic or aromatic silane modifier. As co-catalyst modifiers according to the present invention, silanes may be alkyl-, aryl- and / or alkoxy- containing hydrocarbon components having from 1 to about 20 carbon atoms.
It is a substituted silane.

Especially preferred are silanes having a SiR _4, wherein, R
Is independently R 'or OR', wherein R 'has 1 to about 20 carbon atoms.

Preferred aromatic silanes include diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane, and methylphenyldimethoxysilane. Preferred aliphatic silanes include isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t
-Butyl-dimethoxysilane and t-butyltrimethoxysilane.

The above-described catalyst according to the present invention is useful in the polymerization of alpha-olefins such as ethylene and propylene,
Three or more carbon atoms such as propylene, butene-1, pentene-1, 4-methylpentene-1, and hexene-1, octene-1 and mixtures thereof and mixtures thereof with ethylene. It is most useful in the stereospecific polymerization of alpha olefins.

With the catalyst component according to the invention, a highly crystalline polyalphaolefin is made by contacting at least one alphaolefin with the above-described catalyst composition under polymerization conditions. Such conditions include polymerization temperature and time, monomer pressure, avoidance of catalyst contaminants, selection of polymerization media in the slurry process, use of polymer molecular weight control additives, and others well known to those skilled in the art. Including conditions.

As the type of polymerization, suspension-, bulk-, and gas-phase polymerization methods can be used.

The amount of catalyst to be used will vary depending on the polymerization method, reactor dimensions, monomers to be polymerized, and other factors known to those skilled in the art, but can be determined by reference to the examples below. Typically, the catalyst of the present invention is used in a catalytic amount ranging from about 0.2 to 0.02 mg / g of polymer produced.

Irrespective of the polymerization method employed, the polymerization is carried out at a sufficiently high temperature to guarantee a reasonable polymerization rate and to avoid unduly long reactor residence times, but unreasonably low levels of steric imbalance due to premature polymerization rates. It is performed at a temperature that is not high enough to result in the production of an ordered product. The polymerization temperature is generally in the range of about 0 ° C. to about 120 ° C., and from about 20 ° C. to about 95 ° C. in view of good catalyst performance and high production rate.
C is preferred. More preferably, the polymerization according to the invention is about
It is carried out at a temperature in the range from 50 ° C to about 80 ° C.

The polymerization of the alpha-olefins according to the invention is carried out at atmospheric pressure or at monomer pressures above. Generally, the monomer pressure is in the range of about 0.550 kg / cm ₂ G, except that in the gas phase polymerization, the monomer pressure must not be lower than the vapor pressure at the polymerization temperature of the alpha olefin to be polymerized. .

The polymerization time generally ranges from about 1/2 to several hours in a batch process. This time corresponds to the average residence time in a continuous process. Polymerization times of about 1 hour to about 4 hours are common in autoclave type reactions. In the slurry method, the polymerization time can be adjusted as desired.
Polymerization times of about 1/2 hour to several hours are generally sufficient in continuous slurry processes.

Suitable diluents for use in the slurry polymerization process include alkanes and cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, and methylcyclohexane: toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n Alkylaromatics such as propylbenzene, diethylbenzene and mono- and di-alkylnaphthalenes: chlorobenzene, chloronaphthalene,
Ortho-dichlorobenzene, tetrahydronaphthalene,
Halogenated and hydrogenated aromatics such as decahydronaphthalene: high molecular weight liquid paraffins or mixtures thereof,
And other known diluents.

It is often desirable to purify the polymerization medium prior to use, for example, by distillation, percolation through molecular sieves, contact with a compound such as an alkyl aluminum compound capable of removing trace impurities, or other suitable means.

Examples of gas phase polymerization processes in which the catalysts of the present invention are useful include both stirred bed reactor systems and fluidized bed reactor systems, and are disclosed in U.S. Pat.
7,448: 3,965,083; 3,971,768: 3,970,611: 4,129,701; 4,10
1,289: 3,652,572: and 4,003,712, which are cited as references in the above-mentioned JP-A-63-54405. A typical gas phase olefin polymerization reactor system consists of a reaction vessel to which olefin monomers and catalyst components are added and which includes a stirred bed of the polymer particles to be formed.

Typically, they are added together or separately through one or more valve control ports in the catalyst component reactor. Olefin monomers are typically fed to the reactor through a circulating gas system, in which the monomers withdrawn as off-gas and fresh feed monomers are mixed and injected into the reactor. A quenching liquid, which can be a liquid monomer, can be added to the olefin being polymerized through a circulating gas system for temperature control.

Regardless of the type of polymerization, the polymerization is carried out under conditions that exclude oxygen, water, and other materials that act as catalyst poisons.

Further, according to the polymerization method of the present invention, the polymerization can be carried out in the presence of an additive for controlling the molecular weight of the polymer. Hydrogen is used for this purpose in a manner familiar to those skilled in the art.

Although not always necessary, upon completion of the polymerization, or when terminating the polymerization or deactivating the catalyst of the present invention, the catalyst may be combined with water, alcohol, acetone, or other suitable catalyst deactivator. Contact can be made in a manner known to those skilled in the art.

The products produced according to the process of the present invention are usually solid and predominantly isotactic polyalphaolefins. The polymer yield is sufficiently high with respect to the amount of catalyst used, so that useful products can be obtained without separating the catalyst residues. Furthermore, the levels of stereoregular by-products are low enough that useful products are obtained without separating them.

The polymer product made in the presence of the catalyst according to the invention can be processed into useful articles by extrusion, injection molding and other common techniques.

[Effect of the Invention] The effect of the present invention is that, even if the particle diameter of the catalyst for polyolefin polymerization is changed from small to large, the particles are not or do not collapse in the production process. Even in some cases, the amount can be significantly reduced as compared with the case where a conventional silane compound is used as a shape control agent. Also, a large particle catalyst having a sharp particle size distribution can be produced.

Large particle catalysts with a sharp particle size distribution retain their large shape as a replica in the polymer produced by polymerization, so even if they become sticky polymer particles, the fluidity is dramatically higher than that of small particles. The improvement is well known to those skilled in the art, which makes it extremely useful for producing a copolymer having a high rubber component content by gas phase polymerization with good operability.

The invention described herein is illustrated, but not limited, by the following Examples and Comparative Examples.

Example 1 Step A Formation of a Magnesium Carbonate Solution: In a 3 L autoclave equipped with a stirrer, a pressure gauge and a thermometer and charged with high purity nitrogen, 230 g of magnesium ethoxide was taken, and 415 ml of 2-ethyl-1-hexanol and 1650 ml of toluene was added.

The mixture was heated at 90 ° C. for 3 hours with stirring at 500 rpm under ² kg / cm ² G of carbon dioxide. The resulting solution was cooled and purged with carbon dioxide gas and handled mainly at atmospheric pressure. The solution contained 0.1 mg / ml magnesium ethoxide.

Stage B Formation of solid particles: into a 1500 ml baffled flat bottom flask (baffle ratio 0.15) with stirrer, thermometer, condenser, nitrogen seal line (baffle ratio 0.15), toluene 300 ml, TiCl ₄ 19 ml, B (OC ₄
H ₉ ) _{3 After} 20 ml was added and mixed at room temperature for 5 minutes at 300 rpm,
150 ml of the solution of step A were introduced in 10 minutes. Immediately after the introduction, solid particles (I) precipitated.

Step C Reprecipitation of solid particles: To this was added 50 ml of tetrahydrofuran (THF) using a syringe. The stirring was maintained at 300 rpm, and the temperature was raised to 60 ° C. within 15 minutes. The precipitated particles dissolved in the THF solution and began to sediment again within 15 minutes and solid formation was completed within 10 minutes. 60
After stirring was continued at 45 ° C. for 45 minutes, the stirring was stopped and the resulting solid (II) was allowed to settle. The supernatant was removed by decantation, and the remaining solid (II) was washed twice with 200 ml of toluene.

Step D Titanium (IV) compound treatment: 200 ml of toluene and 100 ml of TiCl are added to the solid (II) of Step C.
₄ was added.

The temperature was raised to 135 ° C. within 20 minutes while stirring at 600 rpm, and this temperature was maintained for 1 hour. Stirring was stopped and the resulting solid (II
I) was allowed to settle and the supernatant was decanted.

100 ml of TiCl ₄ , 250 ml of toluene, 2.1 ml of diisobutyl phthalate are added to the resulting solid (III) and the mixture is
The mixture was stirred at 135 ° C. for 1.5 hours at rpm. The supernatant was removed by decantation.

200 ml of TiCl ₄ was added, and the mixture was heated and refluxed for 10 minutes while stirring at 600 rpm. The supernatant was removed by decantation and washed three times with 200 ml of toluene and four times with 200 ml of hexane.

A total of 17.4 g of solid product (IV) was recovered. The analysis of this solid product (IV) was 16.9 g of magnesium, 2.4% of titanium, 55.1% of chlorine and 7.2% of di-n-butylphthalate.

Particle size distribution of carrier and catalyst: Laser diffraction method using a part of toluene suspension of solid product (II) obtained in Step C and a suspension of solid product (IV) in hexane after washing with hexane in Step D The particle size distribution was measured. Table 1 shows the results.

Gas phase polymerization: 2 mmol of triethylaluminum, 0.3 mmol of diphenyldimethoxysilane, and 16.2 m of solid product (IV) were placed in a nitrogen-substituted stainless steel reactor having an internal volume of 3 L with a multi-stage stirrer.
g and hydrogen after adding 0.8 L, the total pressure is 22 kg / cm ² G at 70 ° C.
The polymerization was carried out for 2 hours while continuously introducing propylene such that

Thereafter, unreacted propylene was discharged to obtain 389 g of powdery propylene. Most of the polypropylene particles had a cubic or inclined hexagonal columnar crystal shape.
The 6-hour extraction residue of the polymer with boiling n-hexane was 1.
It was 2% and the bulk density was 0.46 g / cm ³ .

Particle size distribution of polymer powder is> 2000μ 1.2%, 1
000-2000μ 45.9%, 710-1000μ 27.7%, 500-710
μ 9.5%, 350-500μ 2.8%, 250-350 0.1%, 149
-250μ 0%, <149μ 0.1%, average particle size 108
4μ.

Example 2 Using 114 ml of the solution from step A of example 1, using 100 ml of toluene, 100 ml of chlorobenzene, 15 ml of tri-n-butyl borate in step B and 60 ml in step C
Example 1 was repeated, except that in step D, the third TiCl ₄ treatment was carried out at 135 ° C. for 1 hour with 200 ml of TiCl ₄ as solvent in step D, and 13.1 g of solid product (I
V). The average particle size of the solid product (IV) was 35.2 μm, and particles of 5 μm or smaller were 5.0%.

Example 3 Using a 1 L autoclave for the reaction after Step B, using 170 ml of the solution of Step A of Example 1 for Step B, using 200 ml of toluene and 24 ml of tri-n-butyl borate,
Steps B through C are performed using 70 ml of THF
The stirring was performed at 00 rpm under a carbon dioxide pressure adjusted to 3 kg / cm ² G. During the second TiCl ₄ treatment in Step D, diisobutyl phthalate was used instead of dinormal butyphthalate.
Example 1 was repeated except that 2.1 ml was used.

The yield of solid product (IV) is 20.0 g and the average particle size is 3
The percentage of particles having a size of 1.8 μm or less was 5% or less. Analysis of the solid product was 18.1% Mg, 2.2% Ti, 56.0% Cl, 8.4% diisobutyl phthalate.

Example 4 In step B, 150 ml of the solution of step A of example 1 are used, using 100 ml of toluene, 100 ml of chlorobenzene, 24 ml of triisopropyl borate,
Example 1 was repeated except that ml of THF was used. The average particle size of the solid product (IV) was 27.2 μm, and particles of 5 μm or smaller were 3.1%.

Example 5 In step B, use 114 ml of the solution of step A of example 1, using 140 ml of toluene, 60 ml of isoparaffin (Isobar G), 14 ml of TiCl ₄ , in step C 27 ml
The THF was used, and the TiCl ₄ treatment in Step D was performed in two stages.
Example 1 was repeated except that the second TiCl ₄ wash was not performed.

Example 6 In step A, 286 g of magnesium propoxide was used instead of magnesium ethoxide, and 383 ml of 2
Example 1 except that -ethyl-1-hexanol was used.
Was repeated.

Example 7 1 L of toluene was placed in a 5 L stainless steel reactor having a stirrer, a thermometer, a condenser, a nitrogen seal line, a raw material feed line, a heating jacket, and four flat baffles (baffle ratio 0.15) inside. , 100 ml of bird
n-Butyl borate, 100 ml of TiCl ₄ were charged, and
After stirring at 0 rpm for 5 minutes, 750 ml of the solution of Example 1, Step A
For 30 minutes (Step B). 250 ml of THF was added thereto, and the stirring speed was increased to 180 rpm. Then, the temperature was raised to 60 ° C. within 15 minutes, and the temperature was maintained for 45 minutes (Step C).

The slurry after the reaction was transferred under a nitrogen seal to a 5 L filter having a stirrer, a condenser, a thermometer, a nitrogen seal line, a heating jacket and a filtration unit at the bottom under a nitrogen seal, filtered, and then filtered with 500 ml of toluene. Washed twice.

500 ml of TiCl ₄ , 500 ml to the solid product (II) in the filter
Was maintained at 135 ° C. and 180 rpm for 1 hour. After filtering this, 500 ml of TiCl ₄ , 10.5 ml of di-n-butyl phthalate and 1000 ml of toluene were added, and 135 ° C. and 180 rp were added.
After 1.5 h at m, filtration was carried out (stage D).

The solid product (IV) was further added with 1000 ml of TiCl ₄ , heated under reflux for 10 minutes, filtered, and washed three times with 500 ml of toluene and four times with 500 ml of hexane. The solid product (IV) remaining in the filter was dried with hot nitrogen gas flowing at about 60 ° C. to obtain 81.6 g of a catalyst.

Analytical value of solid product (IV) is Mg 18.6%, Ti 2.1%,
Di-n-butyl phthalate was 6.6%. The average particle size of the solid product (IV) is 42.1μ,
2.2%.

Comparative Example 1 In step B of Example 1, 14.3 g of a solid product (IV) was obtained in the same manner as in Example 1 except that no boron compound was used. In this case, a long time was required for precipitation due to the decantation in steps C to D, and some fine particles were lost. As shown in Table 1, the amount of fine powder in the obtained solid product (IV) was very large.

Comparative Example 2 In step B of Example 1, instead of the boron compound
Example 1 was repeated except that 20 ml of tetraethoxysilane was used to obtain 17.1 g of a solid product (IV). Table 1 shows the particle size distribution of the solid product.

Comparative Example 3 In Step B of Example 4, instead of the boron compound,
Example 4 except that 20 ml of trimethylchlorosilane was used.
Was repeated.

Gas phase polymerization evaluation: Using the solid products (IV) obtained in Examples 2 to 7 and Comparative Examples 1 to 3, gas phase polymerization was carried out in the same manner as in Example 1. Table 2 shows the results.

Example 8 Example 1 was repeated, except that in Step B of Example 1, 2 ml of trinormal borane was used together with 18 ml of trinormal butyl borate to obtain 17.3 g of a solid product (IV). The average particle size of the solid product (IV) was 33 μ, and particles of 5 μ or less were 5.1%.

Example 9 Example 1 was repeated, except that in Step C of Example 1, 60 ml of tetrahydrofuran was used instead of 50 ml of THF, to obtain 17.3 g of a solid product (IV). The average particle size of the solid product (IV) was 25.1 μm, and particles of 5 μm or smaller were 7.2%.

Example 10 In step C of Example 1, 50 ml of isobutyl borate were used instead of 20 ml of normal butyl borate.
Example 1 was repeated except that 60 ml of 2-methyltetrahydrofuran was used instead of ml of THF to obtain 17.5 g of a solid product (IV). The average particle size of the solid product (IV) is 2
The particle size was 8.4 μm, and particles having a particle size of 5 μm or less were 5.9%.

Comparative Example 4 In Step B of Example 9, instead of the boron compound,
Example 9 was repeated except that 20 ml of tetraethoxysilane was used to obtain 16.3 g of solid product (IV). The solid product (IV) was rich in fine particles, and particles having a particle size of 5 μ or less were> 25% or less.

Comparative Example 5 In Step B of Example 10, instead of the boron compound
Example 10 was repeated, except that 20 ml of trimethylethoxysilane was used, yielding 16.6 g of solid product (IV). The average particle size of the solid product (IV) was 16.4 μm, and 13% of particles of 5 μm or smaller.

Slurry polymerization evaluation: Propylene was subjected to hexane slurry polymerization using the catalysts (solid products (IV)) obtained in Examples 8 to 10 and Comparative Examples 4 to 5.

Take 1,000 ml of hexane in a 1.5 L autoclave,
2 mmol, diphenyldimethoxysilane 0.2 mmol, catalyst 15 mg
Was added, 60 ml of hydrogen was introduced, and polymerization was performed at 70 ° C. for 2 hours while maintaining the pressure at 7 kg / cm ² G with propylene. After completion of the reaction, the monomer gas was purged, and 50 g of methinol was added.
After stirring at 0 ° C. for 10 minutes, the mixture was separated by filtration and the polymer was dried, and the polymer yield per used amount of the catalyst was calculated. The polymer dissolved in hexane was recovered from the filtrate. Table 3 shows the results.

Example 11 Using the catalyst obtained in Example 2, bulk polymerization was carried out.

TEA 2 mmol, phenyltriethoxysilane 0.3 mmol, catalyst 10 mg, hydrogen 300 ml, propylene 50
It was added together with 0 g, and polymerized at 70 ° C. and 35 kg / cm ² G for 30 minutes.
Purge unreacted propylene monomer and dry powder 17
0 g was obtained. The polymer yield per 1 g of the catalyst is 17,000 g,
The amount extracted by hexane reflux for 6 hours was 1.2%, and the apparent bulk density of the polymer was 0.50 g / cm ³ .

Example 12 Using 10 mg of the catalyst obtained in Example 7, after performing bulk polymerization for 20 minutes in exactly the same manner as in Example 11, unreacted propylene was purged, and a mixed gas of propylene / ethylene = 2/1 and Introduce 150ml of hydrogen gas, 70 ℃, 18kg / cm ² G
For 30 minutes. The yield of the polymer was 180 g, and the ethylene content in the polymer was 10.3 g.

Example 13 16.5 mg of the catalyst obtained in Example 7 was added to the polymerization vessel of Example 1,
TEA 2mmol, diphenyldimethoxysilane 0.2mmol, hydrogen
150 ml was charged with propylene monomer, and a mixed gas of propylene / ethylene = 4/1 was introduced.
Propylene-ethylene copolymerization was performed at cm ² G for 1 hour.
The yield of the polymer was 190 g, and the ethylene content in the polymer was 50%.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a production process diagram (flow sheet) for explaining a production method of a catalyst component of the present invention.

Claims (4)

(57) [Claims] An olefin polymerization catalyst comprising a titanium compound, a vanadyl halide or a vanadium halide supported on a carrier having a Mg compound precipitated from a solution state as a main component, comprising: A. a general formula Mg ( OR ¹ ) _n (OR ² ) _2-n or MgR ³ _m (OR ⁴ ) _2-m
Or a mixture thereof (wherein R ¹ , R ² , R ³ , and R ⁴ are an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, or a 5 carbon atom) From 20 to 20 aromatic groups, m,
n is a number from 0 to 2), in the presence of carbon dioxide, a saturated or unsaturated mono- or polyhydric alcohol having 1 to 20 carbon atoms represented by the general formula R ⁵ OH and an inert hydrocarbon solvent. B. A mixture of (Component A) and a titanium halide represented by the general formula TiX _p (OR ⁶ ) _4-p (where X is C 1 Or Br and R ⁶ are an alkyl group having 1 to 20 carbon atoms, an aryl group or
And / or p is 1 to 4) and / or a vanadyl halide represented by the general formula VOX _q (OR ⁷ ) _3-q and / or a general formula VX _r (OR ⁸ ) _4- vanadium halide represented by _r (where X is C1 or Br,
R ⁷ and R ⁸ are each an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms,
q is from 1 3, r is 1 to 4.) and / or the general formula SiX _s (OR ⁹⁾ in _4-s with a halogenated silane represented (wherein, X is C1 or Br, R ⁹ is the number of carbon atoms An alkyl group, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, wherein s is 1 to 4) and a general formula BR ¹⁰ _t (OR
¹¹ ) A boron compound represented by _3-t or a mixture of a plurality of the boron compounds (where R ¹⁰ and R ¹¹ are each a carbon atom having 1 to ¹⁰ carbon atoms)
An alkyl group, an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic group having 5 to 20 carbon atoms, and t is a number of 0 to 3). C. reacting the solid product (I) with a cyclic ether, dissolving and reprecipitating to obtain a solid product (II), D. the solid product (II) having the general formula TiX _p (OR ⁶ ) Titanium halide represented by _4-p (where X is C1 or Br, and R ⁶ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms) And / or p is 1 to 4) and / or a vanadyl halide represented by the general formula VOX _q (OR ⁷ ) _3-q and / or a general formula VX _r (OR ⁸ ) _4-r
Wherein X is C1 or Br, R ⁷ and R ⁸ are each an alkyl group having 1 to 20 carbon atoms,
Which is an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, wherein q is 1 to 3 and r is 1 to 4), thereby obtaining a solid product (III). Reacting a mixture of (Component B) with an electron donor,
Or a catalyst component comprising a solid product (IV) obtained by reacting with a solid product (III) ′ obtained by reacting with a solid product (II). 2. A titanium / magnesium molar ratio of 0.5 to 1
The catalyst component according to claim 1, wherein the molar ratio of 0, electron donor / titanium is 0.2 to 20. 3. The solid product (IV) according to claim 1, further comprising a titanium halide represented by the general formula TiX _p (OR ⁶ ) _4-p , wherein X is C1 or Br. , R ⁶ has 1 to 20 carbon atoms
An alkyl group, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, p is 1 to 4) and / or a vanadyl halide represented by the general formula VOX _q (OR ⁷ ) _3-q and / or Or a vanadium halide represented by the general formula VX _r (OR ⁸ ) _4-r (where X is C1 or Br, R ⁷ and R ⁸ are an alkyl group, an aryl group or a carbon number having 1 to 20 carbon atoms, respectively) 3 to 20 cycloalkyl groups, q is 1 to 3,
r is 1 to 4) (component B). 4. An alpha-olefin comprising a combination of the catalyst component according to claim 1 and a co-catalyst component comprising an organometallic compound, or a combination thereof with an electron donor as a third component. Catalyst for polymerization.