JPH0384006A - Catalyst component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the subject component containing large particle diameter with uniform shape giving a polymer having excellent fluidity by reacting Ti compound and B compound with a carrier containing specific Mg compound, CO2 and alcohols and reacting with cyclic ether, Ti compound and electron donor. CONSTITUTION:Mg compound expressed by formula I (R<1> and R<2> are 1-20C alkyl or aryl, etc.; (n) is 0-2) is reacted with alcohols expressed by the formula R<5>OH (R<5> is 1-20C alkyl, etc.) in the presence of carbon dioxide and dissolved in an inert solvent, then resultant system is mixed with Ti halide, etc., expressed by formula II (X is Cl or Br; R<6> is 1-20C alkyl or aryl, etc.; (p) is 1-4) and B compound expressed by formula III (R<10> and R<11> are 1-20C alkyl or aryl, etc.; (t) is 0-3) and reacted to obtain a solid product, thus resultant product is reacted with cyclic ether and dissolved, then re-precipitated, thus resultant solid product is reacted with Ti halide expressed by formula IV (R<6> is 1-20C alkyl or aryl, etc., (p) is 1-4), etc., and reacted with electron donor, etc., to afford the objective catalyst component.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst for alpha olefin polymerization, and in particular to a titanium halide catalyst component supported on a magnesium compound and a catalyst system containing such a component. It is related to.

[Conventional technology and its problems]

Magnesium-containing supported catalysts have been developed that have high catalytic activity and good stereospecificity, and these are easy to remove catalyst residues in the produced polymer and do not require removal of App components. It is well known that it is suitable for phase alpha olefin polymerization.

Gas-phase alpha olefin 1 combination catalysts are also required to have good particle shape, narrow particle size distribution, good crushing resistance, and high particle bulk density in order to obtain good operability. There is. As one method for improving the morphology of these catalyst particles, JP-A No. 63-54, R05 discloses that a magnesium compound is dissolved in alcohol in the presence of carbon dioxide, treated with a mixture of titanium halide and organosilane, and precipitated. A method is described in which a well-shaped carrier is obtained by adding a cyclic ether compound, redissolving and recrystallizing, and activating the carrier to use it as a catalyst.

In gas phase alpha olefin polymerization, unlike suspension polymerization,
Many copolymers are also being produced, taking advantage of the fact that the rubber component produced by the process is not extracted by solvents. In order to produce a highly adhesive polymer with a rubber component, it is necessary to maintain good fluidity of the resulting polymer powder, and for this purpose, the particle size of the powder must be large. A catalyst component with a large particle size is required to produce powder.

In general, catalyst particles produced by precipitation from a solution may have clean carrier particles and a sharp particle size distribution, but some of the particles may collapse during the subsequent activation process, etc. It was unavoidable. In addition, the larger the particle, the more easily it breaks, and in the invention of JP-A-63-54, R05, when the particle size becomes large, such as 30μ, activation treatment with titanium halide, etc. Meanwhile, there was still room for improvement, as the amount of particles that crumbled increased and the amount of fine powder increased.

(Problems to be Solved by the Invention) The present invention solves the problem that particles collapse during titanium halide treatment when producing a catalyst component, especially when producing a catalyst component with a large particle size, by a precipitation method from a solution. The present invention relates to a method for producing a supported catalyst that does not collapse or collapses only slightly.

JP-A No. 1i3-54,405 discloses that an alkaline earth alcoholate is made into an alcohol solution using carbon dioxide, a silicone compound is used when forming a catalyst component from this, and further, tetra and hydrofuran are used. A method for obtaining a well-shaped catalyst component by complexing magnesium is described.

Although there are many examples of using silicon compounds in the formation of catalyst components, no example of using boron compounds in place of silicon compounds has ever been disclosed. indicates the use of a boron compound in combination with a silicon compound, but the effects of the boron compound have not been clearly shown, and furthermore, as in the present invention, it is possible to completely replace the silicon compound. This does not indicate that they are superior to silicon compounds in terms of the purpose of the invention.

The present inventors have found that, while maintaining the high activity and highly stereoregular polymerization performance of the catalyst system described above, when controlling the catalyst components from a small particle size to a large particle size, in particular, particles with a large particle size As a result of intensive research into methods for improving the shape and particle size distribution, we have arrived at the present invention, which prevents particle crushing during the catalyst component manufacturing process and allows a catalyst component with a sharper particle size distribution and a well-shaped shape to be obtained.

That is, the present invention is based on the method disclosed in JP-A No. 63-54, R05, in which a solid precipitate is formed with titanium halide from an alcoholic solution of a magnesium compound, and the solid precipitate is redeposited from a solution containing a cyclic ether. However, by performing this redecipitation in the presence of a boron compound, the obtained magnesium compound precipitate is made to be difficult to break down, and particles in the subsequent titanium halide treatment step are The object of the present invention is to provide a catalyst component with a sharp particle size distribution obtained by preventing crushing, and an olefin polymerization catalyst obtained by combining the catalyst component with an organometallic compound.

(Means to solve problems) The present invention has the following configurations (1) to (4).

(1) A catalyst component for olefin polymerization in which titanium halide, vanadyl halide, or vanadium halide is supported on a carrier whose main component is an Mg compound precipitated from a solution state, A, general formula Mg (ORJn
(OR6) 2-n or MgR'.

(OR6) Magnesium compound represented by 2-11 or a mixture thereof (where Hl, R243, R4
is an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkyl group having 5 carbon atoms.
to 20 aromatic groups, m and n are numbers from O to 2), into a saturated or unsaturated monovalent group having 1 to 20 carbon atoms represented by the general formula R5OH in the presence of carbon dioxide (2). Alternatively, (component A) is obtained by mixing and reacting with polyhydric alcohol (■) in an inert hydrocarbon solvent, and (component A) is combined with the general formula TIXp (OR6) 4
-p Titanium halide (where X is Cl
or Br%R6 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and p is 1 to 4) and/or the general formula VOL (
OR6) Vanadyl halide represented by s-* and/or general formula VX, (OR6) Vanadium halide represented by n-r (where X is Cl or Br,
nl and na are each an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and q is 1 to 3. r is 1 to 4) and/or a halogenated silane [d] represented by the general formula SiXm(OR6)4-* (where X is Cl or Br%R9 is an alkyl group having 1 to 20 carbon atoms) , aryl group or 3 carbon atoms
~20 cycloalkyl groups, S is 1-4)
and a boron compound represented by the general formula 8R"t(OR")s-t or a mixture of a plurality of boron compounds [a](
Here, 110411 is 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, and t
is a number from 0 to 3) to obtain a solid product (r), and convert the C0 solid product (1) into a cyclic ether Φ
A solid product (!■) is obtained by reacting with, dissolving and reprecipitating, D. The solid product (II) has the general formula TiXp (OR
6) Titanium halide represented by a-p (where X
is Cl or Br, R' is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and p is 1 to 4) and/or the general formula V
, OXa (OR6) 3-Q halogenated vanadyl and/or general formula VXr (OR6) 4-
Vanadium halide represented by r (where X is Cl
or Br, R7, and R8 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, and r is 1 to 4. B) [g] is reacted to produce a solid product (Ill
) is reacted with a mixture [h] of (component B) and an electron donor, or a solid product (II) and [h] are obtained.
A solid product obtained by reacting [g] with Cl11)'
IV).

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

(3) The solid product (rV) described in the above item 1 further contains a titanium halide represented by the general formula TiXp (OR6) a-p (where X is Ct or Br, and R6 has 1 to 1 carbon atoms). 20 alkyl groups, aryl groups or 3 to 2 carbon atoms
0 cycloalkyl group, p is 1 to 4) Oyohi/Mataha general formula VOL (OR6) S-q halogenated vanadyl and/or general formula V
(OR') vanadium halide represented by a-r (here, X is Cl or Br, R7, R8 Ct
Sot'L is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms,
(component B) [
A catalyst component formed by reacting [g].

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

The configuration and effects of the present invention will be explained in detail below.

First, stage A will be described.

In step A, in the presence of carbon dioxide ■, the general formula M
g (OR6)n (OR6) x-n or MgR'
s (OR6) , -.

Magnesium compound or mixture thereof [d] represented by (here, HI42.R344 has 1 to 2 carbon atoms)
0 alkyl group, aryl group, Schiff-roalkyl group having 3 to 20 carbon atoms, or aromatic group having 5 to 20 carbon atoms, a+, n are numbers from 0 to 2), with the general formula R5OH Saturated or unsaturated monohydric or polyhydric alcohol O having 1 to 20 carbon atoms and carbon dioxide ■
(component A) is obtained by mixing and reacting in an inert hydrocarbon solvent in the presence of (component A).

Mg (OCH3) 2 , Mg (QC2)18 as component 0 magnesium alcoholate useful in the present invention
) 2, Mg(QCsHy)*, vg(oc4
o, ), Mg(OCH((:R3)CJs)2.2
Mg(OCaH17)2. Mg(QC)ItCl((
CJs) (:4H*)2. Mg(OCH2CHCJ)
2゜Mg(OCsHs)2. Mg(Oll:a)I+
+)2. Mg(OCsH4CHs)i, Mg(OC
+oHt)z, Mg(OC+oHsC)Is)zlM
g(OC+oH+y)ioMg(OC+oH+5CHs
)2. Mg(OCHs)(QC2)1s), Mg(
OCJs) (OCsLs), Mg(OCJs) (
QCsHtt), Mg(OCsHy)(OCsHs
) etc.

In addition, Mg(C
Hs)2. Mg(CJi)2.1g(CsHs)2.
Mg(CJi)z.

Mg(CaH+s)2. Mg(CaH+y)i, M
g(CHCHCJs)*, Mg(CaHs)2. M
g(CaH4CHs)2. Mg(CsH++)2.
Mg(Co.

R7)2. Mg(CHs) (C2HI), Mg
([:2)1s) (Cll)Il+), Mg(C3
87) (C6)Is), mixtures of these and Mg(OCJs) (C41'111)
, Mg(QCsHt) (CaHs) can also be used.

As the alcohol of component (2), aliphatic saturated and unsaturated alcohols can be used. Specifically, methanol, ethanol, propatool, isoproptool, isobutanol, tertiary butanol, octatool, 2-ethylhexanol, cyclohexanol,
Examples include dodecanol, propenyl alcohol, butenyl alcohol, as well as ethylene glycol, trimethylene glycol, etc., among which carbon atoms with 2 to 10 carbon atoms are used.
Preferred are aliphatic alcohols.

Next step is L! In IB, (component A) is represented by the general formula B
A single boron compound or a mixture of a plurality of boron compounds (herein, R1
0411 is 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, and t is a number from O to 3). Below, the general formula TIXp(OR6)4-p
Titanium halide represented by 1 to 4) and/or general formula VOX
, (OR6) vanadyl halide represented by s□ and/or vanadium halide represented by the general formula VX, (OR6) 4-r (where X is Cl or B
r, R7''6 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, and r is 1 to 4) and/or a halogenated silane represented by the general formula SiX, (OR"), A solid product (I) is obtained.

This reaction is preferably carried out in an appropriate amount of an aromatic or aliphatic inert hydrocarbon solvent.

■Boron compounds include methyl borate, ethyl borate, propyl borate, isopropyl borate, butyl borate, isobutyl borate, tert-butyl borate, pentyl borate, octyl borate, 4-
Examples include chlorobuty, allylborate, phenylborate, tolylborate, diethylcyclohexylborate, ethyldibutoxyborane, dibutylmonoethoxyborane, triethylborane, triisopropylborane, tributylborane, tricyclohexylborane, and the like.

87 of the boron compound used in step B and (component A)
The molar ratio of 1 g is typically 0.171 to 2.0/1
Preferably it is OJ/1 to 1/1.

As the titanium halide represented by the general formula TiXw (OR6) 4-p, titanium tetrachloride 1. Titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride,
Propoxy titanium trichloride, butoxy titanium trichloride, hexoxy titanium trichloride, octoxy titanium trichloride, cyclohexoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide, butoxy titanium tribromide, jetoxy titanium dichloride, Dipropoxytitanium chloride, dibutoxytitanium dichloride, octoxytitanium dichloride, diphenoxytitanium dichloride, dicyclohexoxytitanium dichloride, jetoxytitanium tribromide, dibutoxytitanium tribromide, trimethoxytitanium chloride, chloride Examples include triethoxytitanium, triethoxytitanium bromide, and triphenoxytitanium bromide.

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

Mata, general formula VOL (OR6)! -4, VX, (O
Examples of vanadyl halides and vanadium halides represented by R'')4-r include vanadyl trichloride, vanadyl tribromide, ethoxyvanadyl dichloride, butoxyvanadyl dichloride, phenoxyvanadyl dichloride, methoxyvanadyl tribromide, Propoxyvanadyl tribromide, cyclohexoxyvanadyl tribromide, dimethoxyvanadyl chloride, jetoxyvanadyl chloride, dicyclohexoxyvanadyl chloride, dipropoxyvanadyl bromide, dibutoxyvanadyl bromide, vanadium tetrachloride, vanadium tetrabromide, Methoxyvanadium chloride, ethoxyvanadium tribromide, butoxyvanadium trichloride, cyclohexoxyvanadium tribromide, phenoxyvanadium trichloride, jetoxyvanadium dichloride, dibutoxyvanadium tribromide, phenoxyvanadium dichloride, trimethoxyvanadium chloride, Examples include triethoxyvanadium bromide, tripropoquine vanadium chloride, tributoxyvanadium bromide, and triphenoxyvanadium chloride.

Halogenated silanes represented by the general formula SiX Silicon, cyclohexoxy silicon trichloride, dimethoxy silicon dichloride, jetoxy silicon tribromide,
Examples include dipropoxy silicon dichloride, dibutoxy silicon tribromide, diphenoxy silicon dichloride, trimethoxy silicon bromide, triethoxy silicon chloride, tripropoxy silicon bromide, and tributoxy silicon chloride. Moreover, a mixture of these can also be used.

The molar ratio of the total number of moles of metals of titanium halide or/and vanadyl halide or/and vanadium halide or/and halogenated silane used in step B to Mg of component A is 110.3-20/ 1, preferably 110.5 to 5/1.

Dan I! In IC, solid product (I) is dissolved in a solvent containing a cyclic ether and reprecipitated to obtain solid product (TI6). A carrier (solid product (II)) having a uniform particle shape and particle size can be obtained by dissolving all of the particles and re-precipitating the particles.

The boron compounds in the mother liquor of Stage B are present in the precipitation mother liquor of Stage C, and although the mechanism has not yet been elucidated, the presence of boron compounds during this re-precipitation indicates that the boron compounds are present in the subsequent treatment steps. It has been found that this method is effective in preventing particle crushing.

Examples of the cyclic ether include tetrahydrofuran, tetrahydropyran, methyltetrahydrofuran, dimethyltetrahydropyran, tetramethyltetrahydrofuran, dioxane, dioxolane, trioxane, pyran, benzopyran, dihydrobenzofuran, and the like. Among them, tetrahydrofuran is the best.

In stage FID, the solid product (II) has the general formula TIXp (OR6)
4-p Titanium halide represented by Te and/or general formula VOXQ (OR6), vanadyl halide represented by -+ and/or general formula VXr (OR6)
A solid product (III) is obtained by reacting a mixture of vanadium halide (component B) [g] with an electron donor represented by 4-r (where X is C
l or Br, R', R7, R6 each have 1 carbon number
~2G alkyl group, aryl group or carbon number 3-20
is a cycloalkyl group, q゛ is 1 to 3, and p and r are!
~4), before or after this reaction (component B) [g]
It is desirable to treat the solid product (II) or (2) with

Here, (component B) can be selected from among titanium halides, vanadyl halides, and vanadium halides as explained in step B. Even if (component B) is added to solid product (II) or (Ill), solid product (II6) or (Ill) is added to (component B).
l> may also be input.

Suitable electron donors for the preparation of mixture (1) are aromatic mono- and polycarboxylic acid esters. Examples of the aromatic polycarboxylic acid ester include benzene polycarboxylic acid ester and naphthalene polycarboxylic acid ester.

Specifically, benzene polycarboxylic acid esters include 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, isophthalic acid Mono- and diesters of benzyl carboxylic acids, such as dipropyl, dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, dibenzyl terephthalate and diphenyl terephthalate; Mono-, di- and benzenetricarboxylic acids such as monobutyl methrate, dibutyl hemimetriate, tributyl hemimetriate, monoethyl trimellidate, dipropyl trimelinate, tributyl trimeldate, diethyl trimesate, tributyl trimesate and tri-2-ethylhexyl trimesate. Triesters, mono- and di-benzenetetracarboxylic acids such as monomethyl brenidate, diethyl brenidate, tripropyl brenidate, tetrabutyl brenidate, diethyldibutyl brenidate, dibutyl merophanate, tetrabutyl pyromellitate and dimethyldipropyl pyromellitate; Tri- and tetra-esters, mono-, di-, tri-, tetra-, penta- and hexa-esters of benzenepentacarboxylic acid and mellitic acid, etc. can be used.

Examples of naphthalene polycarboxylic acid esters include mono-, di-, and tri-carboxylic acid of naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, and naphthalene pentacarboxylic acid.

Tetra and pentaesters can be used.

Examples of aromatic monocarboxylic acid esters include methyl benzoate, ethyl benzoate, butyl benzoate, isobutyl benzoate, cyclohexyl benzoate,
Benzoic acid esters and benzoic acid esters having substituents such as methyl p-toluate, ethyl p-toluate, methyl p-anisate, butyl p-anisate, ethyl chlorobenzoate, and methyl bromobenzoate can be mentioned.

The electron donor used in the step is about 0.0001 to 1.0 mol per titanium or panadium dulam atom, preferably from o,oos to 0.8 mol per dulam atom.
Used in amounts in the molar range.

Diluents useful in the preparation of the catalyst components of the present invention include:
Aromatics such as benzene, toluene, xylene, ethylbenzene, halogenated aromatics such as chlorobenzene, dibromobenzene, alkanes such as hexane, heptane, octane, nonane, decane, undecane, cyclohexane, methylcyclohexane, 1.2- Dichloroethane! , 1,2-trichloroethane, halogenated alkanes such as carbon tetrachloride, isoparaffinic hydrocarbons, kerosene, and the like.

As mentioned above, the reaction between solid product (II) and (component B) [g] yields solid product (III 6), which is mixed with (mixture of (component B) and electron donor) A solid product (IV), the catalyst component of the present invention, is obtained by the reaction.

The reaction from the solid product (■) to the solid product (IV) involves reversing the above reaction order and first reacting the solid product (■) with [h] to form the solid product (III)'. The solid product (IV) may be obtained by reacting [g] with the solid product (■■)°.

The catalyst component of the present invention is prepared under an atmosphere of an inert gas such as nitrogen or argon gas or an alpha olefin, with exclusion of catalyst poisons such as water and oxygen-carbon oxides. Purification of the diluents and raw materials used also helps remove catalyst poisons from the catalyst production system. As a result of the above-mentioned preparation, a solid product (IV) is obtained which is suitable for use as catalyst component.

It is desirable to remove unreacted starting materials from the solid product (rV) prior to its use.

This removal is conveniently accomplished by washing the solid product with a suitable solvent, such as a liquid hydrocarbon or chlorocarbon, within a short time after completion of the solid product preparation reaction after separation from the production diluent. Become a distant relative. This is because prolonged contact between the catalyst component and unreacted starting material may adversely affect the performance of the catalyst component.

Although not an essential step, the solid product (rV) thus obtained may be contacted with at least one liquid electron acceptor prior to use in the polymerization. is a substance that is liquid at the processing temperature and has a sufficiently high Lewis acidity to remove impurities such as unreacted starting materials and poorly bound compounds from the surface of the solid product (rV). be. Preferred electron acceptors include the first I, which is liquid at temperatures up to about 170°C.
Contains halides of group IV metals.

A specific example is acIL3. Al1 Br3.
TiClta.

TIBra, 5iClla, GeCl1a,
5nCl24. PrJA S, and 5bCj2 s. Preferred electron acceptors are TiCjl 4 and 5i
It is Cl14. It can also be used as an electron acceptor mixture. Such electron acceptors may be used in compatible diluents.

Additionally, although this is also not a necessary step, 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 may be washed with an inert liquid hydrocarbon or a halogenated hydrocarbon. Preferably, the inert liquid is substantially removed before contacting the inert liquid.

Although the chemical structure of the catalyst components of the invention described herein is not currently known, they preferably contain from about 1 to about all percent titanium, from about 10 to about 25! !
A preferred catalyst component made in accordance with the present invention comprises from about 1.0 to about 3 Ii weight percent titanium, from about 15 to about 21 weight percent magnesium, and from about 45 to about 65 weight percent halogen. 55 to about 65
Contains % chlorine by weight.

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 which the catalyst component and an organoaluminum compound cocatalyst such as triethylamine are combined with an alpha olefin such as propylene. The olefin is contacted under polymerization conditions, preferably in the presence of a modifier such as a silane and in an inert hydrocarbon such as hexane.

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. Pat.

The titanium-containing catalyst component of the present invention is Group Ⅰ or Tl+
They are used in polymerization catalysts that include a cocatalyst component, including a group metal metal alkyl, and typically one or more modifier compounds.

Useful Group 1I and Group 1II metal alkyls include
m, where M is $ Group II or Group I
A Group A metal, each R is independently an alkyl group of 1 to about 20 carbon atoms, and m corresponds to the valency of M.

Examples of organometallics, Ml, 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 point of view of catalyst component performance, preferred Group 1I and Group 1IA metal alkyls are those based on magnesium, zinc, and aluminum, where the alkyl group contains 1 to 12 carbon atoms.

Specific examples of such compounds are Mg(CHs)*, Mg(
CmHs) z, Mg (CJ@) (CJs)
1Mg(CaH.)*, Mg(CaHtt)t.

Mg(C+1His)a, Zn(CHs)z, Zn(C
Js)z, Zn(C4L)2. Zn(C4Hs)(Ca
Htt), Zn(CaHtt)2.2n(Cl2Has
)i, An (CHs)s, ^J! (CzHs)
s, A1(CsHy)s, A11(C4
H1l) s, ^j! (CaHtt)s, and ^
It (Cl2Ls).

More preferably, magnesium-1zinc- or argonium 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.

Examples of organic aluminum compounds include metals having one or more than one halogen or hydride group;
For example, ethylaluminum dichloride, diethylaluminum chloride, Eizral mainium sesquichloride, diisobutylaluminum, hydride can be used.

A typical catalyst composition is formed by combining a supported titanium-containing compound described in this invention and a metal alkyl aluminide together with a modifier containing 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 aluminum compound to electron donor ratio is about 5 to about 40. Additionally, the preferred molar ratio of aluminum compound to silane compound is from about 8 to about 30.

In order to maximize catalytic activity and stereospecificity in the catalyst of the present invention, 1f! It is preferable to combine modifiers of Z fl class or Z fl class or higher, the modifier being an electron donor, silane, mineral acids, organometallic chalcogenide derivatives of hydrogen sulfide, organic acids, organic acid esters and mixtures thereof. can be used.

Organic electron donors useful as cocatalyst 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, silanes, acetones, amine oxides, acids, thiols,
Mixtures of organic electron donors, including various phosphoric acid esters, amides, etc., can also be used as required.

Preferred organic acids and esters include benzoic acid, halobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, alkyl esters thereof in which 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 Gl-toluate, hexyl benzoate, and cyclohexyl benzoate, and isobutyl phthalate, They give good results in terms of activity and stereospecificity and are convenient to use.

Furthermore, the polymerization cocatalyst useful in the present invention may preferably include aliphatic or aromatic silane modifiers.
Alkyl-, aryl-1 and/or alkoxy-substituted silanes containing a hydrocarbon component having 5 carbon atoms.

Particularly preferred are silanes having the formula SiR, where R is independently Ro or OR' and Ro has from 1 to about 20 carbon atoms.

Preferred aromatic silanes include diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane, and methylphenyldimethoxysilane. Preferred aliphatic silanes include isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisobutyldimethoxysilane, di-
Mention may be made of t-butyl-dimethoxysilane and t-butyltrimethoxysilane.

The above catalysts according to the invention are useful in the polymerization of alpha olefins such as ethylene and propylene;
Alpha olefins containing 3 [or more than 3 carbon atoms such as propylene, butene-11 pentene-1,4-methylpentene-11 and hexene-11 octene-1 and mixtures thereof and mixtures thereof with ethylene. most useful in the stereospecific polymerization of

Using the catalyst component according to the invention, highly crystalline polyalphaolefins are produced by contacting at least one alphaolefin with the catalyst composition described above under polymerization conditions. Such conditions include polymerization temperature and time, monomer pressure, avoidance of catalyst contaminants, selection of polymerization medium 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 polymerization method, suspension-5 bulk-1 and gas phase polymerization methods are available.

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 produces polymers,
Catalytic amounts ranging from about 0.2 to 0.02 B per gram are used.

Regardless of the polymerization method employed, the polymerization is carried out at sufficiently high temperatures to ensure a reasonable polymerization rate and avoid unreasonably long reactor residence times, but with unreasonably low levels of steric inertia due to too fast a polymerization rate. It is carried out at temperatures not so high as to result in the production of regular products. The polymerization temperature is
- numerically in the range from about 0°C to about 120°C, and from about 20°C to about 9°C in terms of good catalytic performance and high production rate.
5°C is preferred, and more preferably the polymerization according to the invention is carried out at a temperature in the range of about 50°C to about 80°C.

The polymerization of alpha olefins according to the present invention is carried out at monomer pressures at or above atmospheric pressure. - Numerically, the monomer pressure is in the range of about 0.550 kg/c+a'G, provided that in gas phase polymerization the monomer pressure is not below the vapor pressure at the polymerization temperature of the alpha olefin to be polymerized. No.

In the patch method, the polymerization time is generally in the range of about a minute to several hours. This time corresponds to the average residence time in the continuous method. 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. Approximately H
Polymerization times of hours to several hours are generally sufficient in continuous slurry processes.

Diluents suitable for use in slurry polymerization include:
Alkanes and cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, and methylcyclohexane: toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene, and mono-alkanes and alkylaromatics such as di-alkylnaphthalene; halogenated and hydrogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, tetrahydronaphthalene, decahydronaphthalene; high molecular weight liquid paraffins or mixtures thereof, and others. The well-known diluent.

It is often desirable to purify the polymerization medium before use, for example by distillation, percolation through molecular sieves, contact with compounds such as alkyl aluminum compounds 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, U.S. Pat.
957,448.3,965,083.3,971,7
68°3.970,611, R, 129,701, R,
101,289.3,652,527° and 4,00
3,712, and these are cited in JP-A No. 63-54,405, which has already been mentioned as a document.A typical gas phase olefin polymerization reactor system is a system in which olefin monomers and catalyst components are added. The reaction vessel consists of a reactor containing an agitated bed of polymer particles that are heated and formed.

Typically, the catalyst components are added together or separately through one or more valve control ports in the reactor. Olefin monomer is typically fed to the reactor through a recycle gas system in which the monomer removed as an off-gas and fresh feed monomer are mixed and injected into the reactor. A quenching liquid, which can be a liquid monomer, can be added to the olefin during polymerization through the circulating gas system for temperature control.

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

Moreover, according to the polymerization method according to the present invention, the polymerization can be carried out in the presence of additives that adjust the polymer molecular weight. 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 treated with water, alcohol, acetone, or other suitable catalyst deactivating agent. 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 typically solid and predominantly isotactic polyalphaolefins. The polymer yield is sufficiently high for the amount of catalyst used so that useful products can be obtained without separation of catalyst residues. Furthermore, the levels of stereoregular by-products are sufficiently low that useful products can be obtained without their separation.

Polymer products made in the presence of the catalysts of this invention can be processed into useful articles by extrusion, injection molding, and other conventional techniques.

[Effect of the invention] The effect of the invention is that the catalyst particle size for polyolefin polymerization,
Even if particles are made from small to large particles under different conditions, the particles do not collapse during the manufacturing process, or even if they do collapse, compared to when conventional silane compounds are used as shape control agents. This can be reduced to a very low level. Another advantage is that it has become possible to produce large particle catalysts with a particularly sharp particle size distribution.

Large particle catalysts with a sharp particle size distribution retain their thick shape as a replica of the polymer produced during polymerization, so even if they become sticky polymer particles, their fluidity is dramatically greater than that of small particles. It is well known among those skilled in the art that heat rays can be improved, and this makes it extremely useful for producing copolymers with 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 magnesium carbonate solution: 230 g of magnesium ethoxide was placed in a 3 L autoclave equipped with a stirrer, pressure gauge, thermometer and purged with high purity nitrogen, 4151 Ift of 2-ethyl-1-hexanol and 1650 mJZ. of toluene was added.

This mixture was heated with 2 kg/c1G of carbon dioxide.
The mixture was heated at 90° C. for 3 hours while stirring at 00 rpm+1.

The resulting solution was cooled, purged of carbon dioxide gas, and handled primarily under atmospheric pressure. The solution is 0.1B/+lIL
of magnesium ethoxide.

Step B Formation of solid particles: Toluene: lOOmjl into a 1500aj2 baffled flat bottom flask (baffle ratio 0.15) with stirrer, thermometer, condenser and nitrogen seal line.
, TiCTiCl4l9, B (OC4) 1g)
320*j! After charging at room temperature for 5 minutes at 300 rpm, step A solution ISOmjl was charged for 10 minutes. Immediately after charging, solid particles (1) precipitated.

Step C Reprecipitation of solid particles: To this was added 50+al of tetrahydrofuran (THF) using a syringe. Stirring is maintained at 3 GO rpm 1
The temperature was raised to 60°C within 5 minutes. The precipitated particles dissolved in the THF solution and began to precipitate again within 15 minutes, and solid formation was complete within 10 minutes. After continuing stirring at 60° C. for 45 minutes, stirring was stopped and the produced solid (II) was allowed to settle. Remove the supernatant liquid by decantation and remove the remaining solid (
(2) was washed twice with 200if of toluene.

Step D Titanium (IV) compound treatment: 20 hj! to solid (II) of Step 1 IIC! of toluene and 1
001A of TlCl, was added.

The temperature was raised to 135° C. within 20 minutes while stirring at 6 GO rpm, and this temperature was maintained for 1 hour. Stirring was stopped, the solid produced was allowed to settle, and the supernatant liquid was removed by decantation.

100A of TlCl4, 25041 of toluene, 2.
la+j! of diisobutyl phthalate was added to the resulting solid (1) and the mixture was heated at 600.rps at 1.5
Stir for hours. The supernatant liquid was removed by decantation.

200 sIL of TiCl4 was added and refluxed by heating for 10 minutes while stirring at 600 rpm. The supernatant liquid was removed by decantation and washed three times with 20 G+sjl of toluene and then four times with 200 mJl of hexane.

A total of 11, Rg solid product (rV) was recovered.

The analysis value of this solid product (IV) is magnesium 16
．． 9%, titanium 2, R%, chlorine 55.1%, and di-
n-butyl phthalate was 7.2%.

Particle size distribution of support and catalyst: A toluene suspension of the solid product (!i) obtained in step C, a part of the hexane suspension of the solid product (rV) after the stepwise hexane washing was taken and subjected to laser diffraction. The particle size distribution was measured using the method. The results are shown in Table 1.

Gas phase polymerization: To a stainless steel reactor with a multi-stage stirrer and a nitrogen purged internal volume of 3 L, add 2 meals of triethylaluminum, 0.3 gmol of diphenyldimethoxysilane, 16.2 mg of solid product (mV), and 0.8 L of hydrogen. rear,
Polymerization was carried out at 70°C for 2 hours while continuously introducing propylene so that the total pressure was 22 kg/cm'G.

Thereafter, unreacted propylene was discharged to obtain 389 g of powdered propylene. The particle shape of the polypropylene was mostly cubic or inclined hexagonal columnar crystals. The residual ratio of the polymer after 6 hours of extraction with boiling Inn-hexane was 1.2%, and the bulk density was 0 and R6g/c+s'.

The particle size distribution of the polymer powder is 2000μm, 2%
, 1000-2000μ45.9%, yto-t
oooμ27.7%, 500-710μ 9.5%,
350-500μ 2.8%, 25G-350μ0.1
%, 149-210μ0%, 149μ·0.1%, and the average particle size was 1084μ.

Example 2 Using solution 114mjZ of stage vjjA of Example 1, in stage B using 100a+Il toluene, 1ooa°C chlorobenzene, 15mjL tri-n-butylborate, in step C using 60a+IL T)IF, In addition, during the third TiCl4 treatment, 200 mj2 of TiCl4 was used as a solvent at 135°C.
13.1 Repeat Example 1, except hold for 1 hour.
g of solid product (rV) was obtained. The average particle size of the solid product (IV) is 35.2μ, and the particles smaller than 5μ are 5.0
%Met.

Example 3 An IL autoclave was used for the reactions after step B, and 170 ml of the solution from step A of Example 1 was used for step B.
01J2 toluene, 24mA of Tory Herb Chilborate, in Stage C, 70mj! T)
The process from stage 19B to stage C was carried out using IF at 400r9m.
It was carried out under a carbon dioxide pressure adjusted to 3 kg/cm'G with stirring at Except for this, Example 1 was repeated.

The yield of solid product (IV) was 20.0 g, with an average particle size of 31.8 microns and 3.7% particles smaller than 5 microns.

Analytical values of the solid product are Mg 18.1%, Ti 2.2
%, Cl56.0%, diisobutyl phthalate 8,
It was R%.

Example 4 In Step B, 150 ffl of the solution of Step A of Example 1
Using j+, 100mj2 toluene, 100mj! of chlorobenzene, 24 mj2 of triisopropylborate, and in step C, 60+sJ2 of TH
Example 1 was repeated except that F was used. The average particle size of the solid product (IV) was 27.2μ, with 3.1% particles smaller than 5μ.

Example 5 In Step B, 114 mJ2 of the solution of Step A of Example 1
Using 140Ilj! toluene, 60+a4 isoparaffin (isopar G), 14mj2 TiC
Using l4, step l! In IC, 27a angle T)
Example 1 was repeated using IF, except that the TiCl4 IJ process in stages was performed in two stages and the third TiCl4 cleaning was not performed.

Example 6 In step A, 286 g of magnesium propoxide was used instead of magnesium ethoxide, 383
mj! Example 1 was repeated except using 2-ethyl-l-hexanol.

Example 7 Stirrer, thermometer, condenser, nitrogen seal line,
It has a raw material feed line, a heating jacket and
In a 5L stainless steel reactor with 4 flat baffles (baffle ratio 0.15) inside, IL of toluene, 1 oss cube of tri-herb chill borate, 100+mJ! of TiC
After stirring for 5 minutes at room temperature and 12 Orpm,
Example 1 Step A solution (&750 mL was charged in 30 minutes (Step B), to which 250+aA of THF was added, the stirring speed was increased to 180 rpm, and 6 mL was added within 15 minutes.
The temperature was increased to 0° C. and held at this temperature for 45 minutes (Step C).

The slurry after the reaction was transferred under a nitrogen seal to a 5Lfi filtration device equipped with an agitator, a condenser, a thermometer, a nitrogen seal line, a heating jacket, and a filtration unit at the bottom, filtered, and then heated with 500a+It of toluene. Washed twice.

50011IJZnot to the solid product (If) in the filter
Add ic14.500mf of toluene, 135℃, 18
It was kept at 0 rpm for 1 hour. After filtering this, 500
mj! of TiCl4.1G, 5 mJ2 of di-n-butyl phthalate, 1000111J217) toluene was added and kept at 135°C and 1 Borpm for 1.5 hours, then filtered (Step D).

Solid product (IV) further 7iCl at 10100O
4, heated and refluxed for 10 minutes, then filtered.
Washed three times with toluene at 500 mA and an additional four times with hexane at 500+aA. The solid product remaining in the filter (I
V) is dried with hot nitrogen gas at around 60°C,
81.8 g of catalyst was obtained.

The analysis value of the solid product (rV) is Mg 111.8%,
Ti was 2.1%, and di-n-butyl phthalate was 6.6%. The average particle size of the solid product (tV) is 42.1μ
The percentage of particles smaller than 5μ was 2.2%.

Comparative Example 1 In Step B of Example 1, 14.3 g of solid product (IV) were obtained according to the entire method of Example 1, except that no boron compound was used. In this case, stage C to stage l! The precipitation for decantation in the ID took a long time and some particles were lost.As shown in Table 1, there was a very large amount of fine powder in the obtained solid product (IV).

Comparative Example 2 In step B of Example 1, instead of the boron compound,
Example 1 was repeated except that 20 tails of tetraethoxysilane were used and 17.1 g of solid product (rV
) was obtained. The particle size distribution of the solid product is shown in Table 1.

Comparative Example 3 In step B of Example 4, instead of the boron compound,
Example 4 was repeated except using 20 mu of trimethylchlorsilane.

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. The results are shown in Table 2.

Example 8 In step B of Example 1, tri-normal borane 2 tall along with tri-normal butyl borate 18 mj2
Example 1 was repeated except that the solid product (I
V) 17.3g was obtained. The average particle size of the solid product (IV) was 33μ, with 5.1% of particles smaller than 5μ.

Example 9 In step C of Example 1, 50+oj! Example 1 was repeated, except that 60 mjL of tetrahydrobilane was used instead of THF, yielding 17.3 g of solid product (mV). The average particle size of the solid product (IV) is 2
The particle diameter was 5.1μ, and the proportion of particles smaller than 5μ was 7.2%.

Example 1O In step C of Example 1, 24 m 4 of isobutyl borate was used instead of 20 a+ IL of n-butyl borate and 60 a instead of 50 m j of THF.
Example 1 was repeated except that 2-methyltetrahydrofuran of It was used and 17.5 g of solid product (IV
) was obtained. The average particle size of the solid product (IV) is 28, Rμ
The percentage of particles smaller than 5μ was 5.9%.

Comparative Example 4 Stage I of Example 9! Example 9 was repeated, except that in i1B, 20 m IL of tetraethoxysilane was used instead of the boron compound, yielding 18.3 g of solid product (IV). The solid product (IV) contained many fine particles, with less than 25% of particles smaller than 5 microns.

Comparative Example 5 Example 10 was repeated, except that in step B of Example 10, 20 m Il of trimethylethoxysilane was used instead of the boron compound, yielding 16.6 g of solid product (IV). The average particle size of the solid product (IV) is 1
6, Rμ, and 13% of particles were 5μ or less.

Slurry polymerization evaluation: Hexane slurry polymerization of propylene was carried out using the catalysts (solid products (■)) obtained in Examples 8 to 10 and Comparative Examples 4 to 5.

1otioff1 hexane in a 1.5L autoclave
42 was taken, 2 mmol of TEA, 0.7 mmol of diphenyldimethoxysilane, 17B from the catalyst 15-a+g was added, 60IIIt of hydrogen was introduced, the pressure was maintained at 7 kg/cm'G with propylene, and the mixture was heated at 70°C for 2 hours. After the completion of the polymerized 0 reaction, the monomer gas was purged, 50 g of methanol was added, and the mixture was stirred for 70° C. 10 minutes, filtered, and the polymer was dried to calculate the polymer yield per amount of catalyst used.

The polymer dissolved in hexane was recovered from the filtrate. The results are shown in Table 3.

Example 11 Bulk polymerization was performed using the catalyst obtained in Example 2.

In the IL bulk polymerization vessel, TE A 2 ■ol, phenyltriethoxysilane 0.3 mmol, catalyst I Qff
lllllg, 300 mj2 of hydrogen, 500 mj2 of propylene
The unreacted propylene monomer was purged to obtain 170 g of dry powder. The polymer yield per 1 g of catalyst was 17,000 g, and it was extracted with hexane reflux for 6 hours. 1.2%, and the apparent bulk density of the polymer is 0.
It was 50g/c*'.

Example 12 Using 10 mg of the catalyst obtained in Example 7, bulk polymerization was carried out for 20 minutes in exactly the same manner as in Example 11, and then unreacted propylene was purged and propylene/ethylene = 2
/l of mixed gas and 150ml of hydrogen gas were introduced,
Gas phase polymerization was carried out at 70° C. and 18 kg/cm”G for 30 minutes. The yield of the polymer was 180 g, and the ethylene content in the polymer was 10.3%.

Example 13 The catalyst component 16 obtained in Example 7 was added to the polymerization vessel of Example 1.
5 mg, 2 mmol of TEA, 0.2 mmol of diphenyldimethoxysilane. Inject 150 m of hydrogen with propylene monomer, propylene/ethylene =
Introducing 4/1 mixed gas, 70℃ 22kg/ca+'
Propylene-ethylene copolymerization was carried out at G for 1 hour. The yield of polymer was 190 g, and the ethylene content in the polymer was 50%.

Table 1 solid product (II), (rV) particle size distribution table table 3

[Brief explanation of drawings]

FIG. 1 is a manufacturing process diagram (flow sheet) for explaining the method for manufacturing the catalyst component of the present invention. Patent applicant: Chisso Corporation

Claims (4)

[Claims] (1) A catalyst component for olefin polymerization in which titanium halide, vanadyl halide, or vanadium halide is supported on a carrier whose main component is an Mg compound precipitated from a solution state, A, general formula Mg (OR ^1)_n(OR^2)_2_-
Magnesium compound represented by _n or MgR^3_m(OR^4)_2_-_m or a mixture thereof [
a] (Here, R^1, R^2, R^3, R^4 are alkyl groups having 1 to 20 carbon atoms, aryl groups, or 3 carbon atoms
20 cycloalkyl group or 5 to 2 carbon atoms
0 aromatic group, and m and n are numbers from 0 to 2), in the presence of carbon dioxide [b], a saturated or unsaturated group having 1 to 20 carbon atoms represented by the general formula R^5OH (component A) is obtained by mixing with monohydric or polyhydric alcohol [c] in an inert hydrocarbon solvent and reacting and dissolving it, B. The (component A) and the general formula TiX_p(OR^6)_
Titanium halide represented by 4_-_p (where, 1 to 4) and/or general formula VO
Vanadyl halide represented by X_q(OR^7)_3_-_q and/or general formula VX_r(OR^8)_
Vanadium halide represented by 4_−_r (where,
X is Cl or Br, and R^7 and R^8 are each an alkyl group having 1 to 20 carbon atoms, an aryl group, or 3 to 2 carbon atoms.
0 cycloalkyl group, q is 1-3, r is 1-4
) and/or the general formula SiX_s(OR^9)
_4_-_s halogenated silane [d] (where X is Cl or Br, R^9 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms) , s is 1 to 4) and the general formula BR^
A boron compound represented by 1^0_t(OR^1^1)_3_-_t or a mixture of a plurality of boron compounds [e
] (Here, R^1^0 and R^1^1 are an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aryl group having 3 to 2 carbon atoms.
0 cycloalkyl group or an aromatic group having 5 to 20 carbon atoms, and t is a number from 0 to 3) to obtain a solid product (I), C, a solid product ( I) is reacted with a cyclic ether [f], dissolved and reprecipitated to obtain a solid product (II);
6) Titanium halide represented by_4_-_p (where X is Cl or Br, 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, p is 1 to 4) and/or vanadyl halide represented by the general formula VOX_q(OR^7)_3_-_q and/or the general formula VX_r(OR^
8) Vanadium halide represented by_4_-_r (where, is an alkyl group, q is 1 to 3, r is 1 to 4) (component B) [g] is reacted to obtain a solid product (III), to which (component B) and electron donor are reacted. react the mixture [h] with the solid product (I
Solid product (III)′ obtained by reacting I) and [h]
A catalyst component consisting of a solid product (IV) obtained by reacting [g] with [g]. (2) Titanium/magnesium molar ratio from 0.5 to 10
, a catalyst component according to claim 1, wherein the electron donor/titanium molar ratio is from 0.2 to 20. (3) Solid product (IV) according to claim 1
Furthermore, titanium halide represented by the general formula TiX_p(OR^6)_4_-_p (where X is Cl or Br
, 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 p is 1
~4) and/or the general formula VOX_q(OR^
7) Vanadyl halide represented by_3_-_q and/or vanadium halide represented by the general formula VX_r(OR^8)_4_-_r (where X is Cl 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) (component B) [g] Catalyst component made by reacting. (4) An alpha olefin polymerization catalyst comprising a combination of the catalyst component according to claim 1 and an organometallic compound, or a combination thereof with an electron donor as a third component.