JPH11310610A - Solid catalytic component for polymerizing olefin and catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decrease an incidence rate of low-molecular weight polymers soluble in a polymerization solvent or low-tacticity polymers and to obtain high-tacticity polymers at high yield, by polymerizing olefins in the presence of catalytic components prepared from a magnesium compound, a specific halogen-containing titanium compound, an aromatic dicarboxylic acid diester, or the like. SOLUTION: The purpose of this invention is achieved by polymerizing olefins in the presence of catalytic components prepared from (A) a magnesium compound (e.g. diethoxymagnesium or the like), (B) a halogen containing titanium(IV) compound (titanium tetrachloride or the like), (C) an aromatic dicarboxylic acid diestor (e.g. diethyl phthalate or the like), (D) an aromatic hydrocarbon (e.g. toluene or the like) and (E) an aluminum compound selected from a group consisting of a hydroxyl group-containing aluminum salt of an organic acid of the formula (R<1> CO2 )m Al(OH)3-m [wherein, (m) is 1 or 2; R<1> is H or a 1-21C hydrocarbon], e.g. (CH3 CO2 )Al(OH)2 , and aluminum hydroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a high stereoregular polymer in a high yield, which has a high activity and has a low generation rate of a low molecular weight or low stereoregular polymer soluble in a polymerization solvent. The present invention relates to a solid catalyst component and a catalyst for olefins polymerization, which can be obtained and can obtain a copolymer having excellent physical properties at a high yield when olefins are copolymerized.

[0002]

2. Description of the Related Art Conventionally, in the polymerization of olefins,
It is known to use a solid catalyst component containing magnesium, titanium, an electron-donating compound and a halogen as essential components. There have been proposed many olefin polymerization methods for polymerizing or copolymerizing olefins. For example,
JP-A-57-63310 and JP-A-57-63311 disclose a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor, an organoaluminum compound and an organosilicon compound having a Si-OC bond. In particular, there has been proposed a method of polymerizing an olefin having 3 or more carbon atoms by using a catalyst comprising a combination of the above. However, these methods are not always satisfactory for obtaining a high stereoregular polymer in a high yield, and further improvement has been desired.

[0003] Also, Japanese Patent Application Laid-Open No. 63-92614 discloses a solid catalyst for olefin polymerization obtained by contacting dialkoxymagnesium, aromatic dicarboxylic acid diester, aromatic hydrocarbon, titanium halide and calcium chloride. Ingredients have been proposed. On the other hand, JP
In 315406, a solid product is obtained by contacting titanium tetrachloride with a suspension formed of diethoxymagnesium and alkylbenzene and then adding and reacting phthalic acid dichloride,
A solid catalyst component prepared by further contacting the solid product with titanium tetrachloride in the presence of alkylbenzene, a catalyst for the polymerization of olefins comprising an organoaluminum compound and an organosilicon compound, and a catalyst in the presence of the catalyst. Olefin polymerization methods have been proposed. These prior arts have a high activity enough to omit a so-called deashing step for the purpose of removing catalyst residues such as chlorine and titanium remaining in the produced polymer, and collectively obtain a stereoregular polymer. The focus was on improving the conversion rate and increasing the sustainability of the catalyst activity during polymerization.

[0004]

By the way, in the case of the slurry polymerization method which requires a solvent at the time of polymerization, it is difficult to dissolve in a polymerization solvent.
A polymer having a low molecular weight or low stereoregularity, particularly a polymer called atactic polypropylene (hereinafter sometimes abbreviated as APP) in the case of propylene polymerization, is generated. If the rate of occurrence of this APP becomes high, there is a possibility that pipes may be blocked during polymerization,
After the polymerization, the highly stereoregular polymer which is the product
Is required, and there is a concern that the process operation and product manufacturing cost may be adversely affected. Furthermore, in the copolymerization of olefins, for example, in the random copolymerization of propylene and ethylene, it is necessary to increase the ethylene content in the copolymer to improve the physical properties of the copolymer, and to improve the randomness. When the content is increased, the rate of generation of the soluble component in the polymerization solvent tends to be extremely high in the slurry polymerization method, and the above-described problem occurs. However, when the above-mentioned conventional catalyst is used, it is not enough to solve such a problem.

Accordingly, an object of the present invention is to solve the problems remaining in the prior art, suppress the rate of occurrence of a low molecular weight or low stereoregular polymer soluble in a polymerization solvent, and achieve a high stereoregularity. A solid catalyst component and a catalyst for olefin polymerization, which can obtain a polymer of excellent physical properties when a copolymer of olefins is obtained in a high yield. To provide.

[0006]

Means for Solving the Problems The present inventor has conducted intensive studies to solve the problems left in the above prior art, and as a result, has found that magnesium compounds, tetravalent halogen-containing titanium compounds, aromatic dicarboxylic acid diesters, and the like. Polymerization of olefins using a solid catalyst component prepared from an aromatic hydrocarbon and a hydroxyl group-containing organic acid aluminum compound or aluminum hydroxide maintains a high degree of catalytic activity and stereoregularity of the resulting polymer. As it is, a low molecular weight or low stereoregular polymer soluble in a polymerization solvent, especially A
When an olefin polymer having a low PP generation rate is obtained and the solid catalyst component is subjected to copolymerization of olefins,
It has been found that a copolymer having excellent physical properties can be obtained in a high yield, and the present invention has been completed.

To achieve the above object, the solid catalyst component (A) for olefin polymerization according to the present invention comprises the following (a)
~ E is prepared using the component. (A) a magnesium compound, (b) a tetravalent halogen-containing titanium compound, (c) an aromatic dicarboxylic acid diester,
(D) an aromatic hydrocarbon, and (e) at least one aluminum compound selected from a hydroxyl group-containing organic acid aluminum compound represented by the following general formula (1) and aluminum hydroxide. (R ¹ CO ₂ ) _m Al (OH) _3-m (1) (wherein m is 1 or 2, R ¹ is a hydrogen atom or a linear or branched saturated group having ^{1 to} 21 carbon atoms or It represents an unsaturated hydrocarbon group.)

The olefin polymerization catalyst of the present invention is characterized by being formed from the following components (A), (B) and (C). (A) the solid catalyst component for olefin polymerization described above; (B) a general formula R ² _p AlQ _3-p (wherein R ² represents an alkyl group having 1 to 4 carbon atoms, and Q represents a hydrogen atom or a halogen atom. And p is 0 <p ≦ 3
Is a real number. An organoaluminum compound represented by
And (C) the general formula R ³ _q Si (OR ⁴⁾ in _4-q (wherein, R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, any aralkyl group And may be the same or different.
⁴ represents an alkyl group having 1 to ⁴ carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, an aralkyl group,
They may be the same or different. q is an integer of 0 ≦ q ≦ 3. An organosilicon compound represented by the formula:

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A magnesium compound (a) (hereinafter, referred to as "solid catalyst component (A)") used for preparing a solid catalyst component (A) for olefin polymerization of the present invention (hereinafter sometimes referred to as "solid catalyst component (A)"). Examples of the “component (a)” include magnesium dihalide, dialkyl magnesium, alkyl magnesium halide, dialkoxy magnesium, diaryloxy magnesium, alkoxy magnesium halide, and fatty acid magnesium.

Specific examples of the magnesium dihalide include magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium difluoride and the like. The dialkylmagnesium, the general formula R ⁵ R ⁶ Mg (wherein, R ⁵ and R ⁶ represents an alkyl group having 1 to 10 carbon atoms, each of which may be the same or different.) Is preferably a compound represented by, More specifically, dimethyl magnesium, diethyl magnesium, ethyl methyl magnesium, dipropyl magnesium, methyl propyl magnesium, ethyl propyl magnesium, dibutyl magnesium, butyl methyl magnesium, butyl ethyl magnesium and the like can be mentioned. These dialkylmagnesiums can also be obtained by reacting metal magnesium with a halogenated hydrocarbon or alcohol.

As the alkylmagnesium halide, a compound represented by the general formula R ⁷ MgD ¹ (wherein R ⁷ has 1 to 10 carbon atoms)
And D ¹ represents a halogen atom such as chlorine, bromine, iodine and fluorine. ) Are preferable, and more specifically, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride and the like can be mentioned. These alkylmagnesium halides can also be obtained by reacting metal magnesium with a halogenated hydrocarbon or alcohol.

As the dialkoxymagnesium or diaryloxymagnesium, the general formula Mg (OR ⁸ ) (
OR ⁹ ) (wherein, R ⁸ and R ⁹ each represent an alkyl group or an aryl group having 1 to 10 carbon atoms, which may be the same or different), and more specifically, , Dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, diphenoxymagnesium and the like. These dialkoxymagnesium or diaryloxymagnesium can also be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.

As the alkoxymagnesium halide, a compound represented by the general formula Mg (OR ¹⁰ ) D ² (wherein R ¹⁰ has 1 carbon atom)
And alkyl groups D to D ² represent halogen atoms such as chlorine, bromine, iodine, and fluorine. ) Are preferable, and more specifically, methoxymagnesium chloride,
Ethoxymagnesium chloride, propoxymagnesium chloride, butoxymagnesium chloride and the like.

The fatty acid magnesium is represented by the general formula (R
A compound represented by ¹¹ CO ₂ ) ₂ Mg (wherein R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms) is preferred, and more specifically, magnesium laurate, magnesium stearate, octanoic acid Magnesium and magnesium decanoate.

Of these magnesium compounds in the present invention, dialkoxymagnesium is preferred, and among them, diethoxymagnesium and dipropoxymagnesium are particularly preferred. The above magnesium compounds can be used alone or in combination of two or more.

Further, in the present invention, the solid catalyst component (A)
The dialkoxymagnesium used for the preparation of the compound is in the form of granules or powder, and its shape may be irregular or spherical. For example, when a spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved, and the produced polymer powder is used. Problems such as clogging caused by the contained fine powder are eliminated.

The above-mentioned spherical dialkoxymagnesium is
It is not always necessary to have a true spherical shape, and an elliptical or potato-shaped one can also be used. Specifically, the shape of the particles is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is 3
Or less, preferably from 1 to 2, more preferably from 1 to 1.5.

The dialkoxymagnesium may have an average particle size of 1 to 200 μm. Preferably it is 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 μm, preferably 5 to 50 μm, more preferably 10 to 40 μm. Further, as for the particle size, it is desirable to use a fine particle and coarse powder having a small particle size distribution. Specifically, particles having a size of 5 μm or less
% By weight or less, preferably 10% by weight or less.
On the other hand, particles having a size of 100 μm or more are 10% by weight or less of the whole, and preferably 5% by weight or less. Further, the particle size distribution is expressed by ln (D90 / D10) (where D90 is the particle size at 90% by weight of the integrated particle size, and D10 is 10% by the integrated particle size.
The particle size in% by weight. ) Is 3 or less,
Preferably it is 2 or less.

The tetravalent halogen-containing titanium compound (b) used for preparing the solid catalyst component (A) in the present invention
(Hereinafter sometimes referred to as “component (b)”) is preferably a compound represented by the general formula Ti (OR ¹² ) _n X _4-n (wherein R ¹² represents an alkyl group having 1 to 4 carbon atoms; Represents a halogen atom such as chlorine, bromine, iodine and the like, and n is an integer of 0 ≦ n ≦ 3.) And is one or more of titanium halide and alkoxytitanium halide.

Specifically, titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide as titanium halides; methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride and n-titanium as alkoxytitanium halides; Butoxytitanium trichloride,
Dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-
Examples thereof include butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride. Of these, titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred. These titanium compounds can be used alone or in combination of two or more.

The aromatic dicarboxylic acid diester (c) (hereinafter sometimes abbreviated as “component (c)”) used for preparing the solid product (A) in the present invention is phthalic acid or terephthalic acid. One or more diesters are preferred. More preferably, one or more diesters of phthalic acid or terephthalic acid having 1 to 12 carbon atoms in the alkyl group are used.

Specific examples of diesters of phthalic acid include:
Dimethyl phthalate, diethyl phthalate, di-n-phthalate
-Propyl, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate, ethyl methyl phthalate, methyl phthalate (iso-propyl), ethyl phthalate (n-propyl), Ethyl phthalate (n-butyl), ethyl phthalate (iso-butyl), di-n-pentyl phthalate, di-iso phthalate
-Pentyl, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-phthalic acid Nonyl, di-iso-decyl phthalate, bis (2,2-dimethylheptyl) phthalate, n-butyl phthalate (iso-hexyl),
N-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-pentyl phthalate (iso
-Hexyl), iso-pentyl phthalate (heptyl), n-pentyl phthalate (2-ethylhexyl),
N-pentyl phthalate (iso-nonyl), i-phthalic acid
So-pentyl (n-decyl), n-pentyl undecyl phthalate, iso-pentyl phthalate (iso-hexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (2- Ethylhexyl), n-hexyl phthalate (iso-nonyl), n-hexyl phthalate (n-decyl), n-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (i
so-nonyl), n-heptyl phthalate (neo-decyl), 2-ethylhexyl phthalate (iso-nonyl)
And one or more of these are used.

Specific examples of diesters of terephthalic acid include dimethyl terephthalate, diethyl terephthalate, di-n-propyl terephthalate, and di-iso terephthalate.
-Propyl, di-n-butyl terephthalate, di-iso-butyl terephthalate, ethyl methyl terephthalate, methyl terephthalate (iso-propyl), ethyl terephthalate (n-propyl), ethyl terephthalate (n-butyl) , Ethyl terephthalate (iso-butyl), di-n-pentyl terephthalate, di-iso-terephthalate
Pentyl, dihexyl terephthalate, di-terephthalate
n-heptyl, di-n-octyl terephthalate, bis (2,2-dimethylhexyl) terephthalate, bis (2-ethylhexyl) terephthalate, di-n-terephthalate
Nonyl, di-iso-decyl terephthalate, bis (2,2-dimethylheptyl) terephthalate, n terephthalate
-Butyl (iso-hexyl), n-butyl terephthalate (2-ethylhexyl), n-pentylhexyl terephthalate, n-pentyl terephthalate (iso-hexyl), iso-pentyl terephthalate (heptyl), n-terephthalate Pentyl (2-ethylhexyl), n-pentyl terephthalate (iso-nonyl), iso-pentyl terephthalate (n-decyl), n-terephthalate
Pentyl undecyl, iso-pentyl terephthalate (iso-hexyl), n-hexyl terephthalate (2
-Ethylhexyl), n-hexyl terephthalate (is
o-nonyl), n-hexyl terephthalate (n-decyl), n-heptyl terephthalate (2-ethylhexyl), n-heptyl terephthalate (iso-nonyl),
Examples thereof include n-heptyl terephthalate (neo-decyl) and 2-ethylhexyl terephthalate (iso-nonyl), and one or more of these are used.

Among the above, diesters of phthalic acid are preferred, and among them, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, and phthalic acid are particularly preferred. Di-iso-butyl,
Di-n-octyl phthalate, bis (2-ethylhexyl) phthalate, and di-iso-decyl phthalate are preferably used.

The aromatic hydrocarbon (d) (hereinafter sometimes abbreviated as “component (d)”) used in the preparation of the solid catalyst component (A) in the present invention is a hydrocarbon that is liquid at room temperature. Is preferred, specific examples include benzene,
Examples thereof include toluene, xylene, ethylbenzene, propylbenzene, and trimethylbenzene. Especially, toluene, xylene, and ethylbenzene are desirable. Further, in addition to the above-mentioned component (d), other inert organic solvents can be used in combination. Examples of the inert organic solvents used include saturated hydrocarbons such as hexane, heptane and cyclohexane, orthodichlorobenzene, Examples thereof include halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, and dichloroethane.

The hydroxyl group-containing organic aluminum compound or aluminum hydroxide (e) (hereinafter sometimes abbreviated as "component (e)") used in the preparation of the solid catalyst component (A) in the present invention. The contained organic acid aluminum compound is a compound represented by the following general formula (1). (R ¹ CO ₂ ) _m Al (OH) _3-m (1) (wherein m is 1 or 2, R ¹ is a hydrogen atom or a linear or branched saturated group having ^{1 to} 21 carbon atoms or It is an unsaturated hydrocarbon group.)

R ¹ is H, CH ₃ , C ₂ H ₅ , C
_{3 H 7, (CH 3)} 2 CHCH 2, CH 3 CH = CH,
CH ₃ (CH ₂ ) ₄ , C ₄ H ₉ CH (C ₂ H ₅ ), CH
₃ (CH ₂ ) ₆ , CH ₂ ＣＨCH (CH ₂ ) ₈ , CH
₃ (CH ₂ ) ₈ , C ₁₁ H ₂₃ , C ₁₃ H ₂₇ , C ₁₅ H ₃₁ , C ₁₇
H ₃₅ , the following hydrocarbon group:

[0028]

Embedded image

CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ )
₇ , CH ₃ (CH ₂ ) ₄ CH = CHCH ₂ CH = CH
(CH ₂ ) ₇ , C ₂₁ H _{43 and the} like.

Specific examples of the compound represented by the general formula (1)
Is (HCO_Two) Al (OH)_Two, (HCO_Two)_TwoAl
(OH), (CH_ThreeCO_Two) Al (OH)_Two, (CH_Three
CO _Two)_TwoAl (OH), (C_TwoH_FiveCO_Two) Al (O
H)_Two, (C_TwoH_FiveCO_Two) _TwoAl (OH), (C_ThreeH
₇CO_Two) Al (OH)_Two, (C_ThreeH₇CO_Two)_TwoAl
(OH), (CH_Three)_TwoCHCH_TwoCO_Two) Al (O
H)_Two, (CH_Three)_TwoCHCH_TwoCO_Two)_TwoAl (O
H), (CH_ThreeCH = CHCO_Two) Al (OH)_Two,
(CH_ThreeCH = CHCO_Two)_TwoAl (OH), (CH_Three
(CH_Two)_FourCO_Two) Al (OH)_Two, (CH_Three(CH
_Two)_FourCO_Two)_TwoAl (OH), (C_FourH₉CH (C_Two
H_Five) CO_Two) Al (OH)_Two, (C_FourH₉CH (C_Two
H_Five) CO_Two) _TwoAl (OH), (CH_Three(CH_Two)₆
CO_Two) Al (OH)_Two, (CH_Three(CH_Two)₆C
O_Two)_TwoAl (OH), (CH_Two= CH (CH_Two)₈C
O_Two) Al (OH)_Two, (CH_Two= CH (CH_Two)₈C
O_Two)_TwoAl (OH), (CH_Three(CH_Two)₈CO_Two)
Al (OH)_Two, (CH_Three(CH_Two)₈CO_Two)_TwoAl
(OH), (C₁₁H_{twenty three}CO_Two) Al (OH)_Two, (C₁₁
H_{twenty three}CO_Two)_TwoAl (OH), (C₁₃H₂₇CO_Two) Al
(OH)_Two, (C₁₃H₂₇CO_Two)_TwoAl (OH), (C
_FifteenH₃₁CO_Two) Al (OH)_Two, (C_FifteenH₃₁CO_Two)_Two
Al (OH), (C₁₇H ₃₅CO_Two) Al (OH)_Two,
(C₁₇H₃₅CO_Two)_TwoAl (OH), the following structural formula (2)
And (3) a hydroxyl group-containing isostearic acid
Luminium,

[0031]

Embedded image

[0032]

Embedded image

(CH_Three(CH_Two)₇CH = CH (C
H_Two)₇CO_Two) Al (OH)_Two, (CH _Three(CH_Two)
₇CH = CH (CH_Two)₇CO_Two)_TwoAl (OH),
(CH_Three(CH_Two)_FourCH = CHCH_TwoCH = CH (C
H_Two)₇CO_Two) Al (OH)_Two, (CH_Three(CH_Two)
_FourCH = CHCH_TwoCH = CH (CH_Two)₇CO_Two)_Two
Al (OH), (C_{twenty one}H₄₃CO_Two) Al (OH)_Two,
(C_{twenty one}H₄₃CO_Two)_TwoAl (OH) and the like.

The above-mentioned hydroxyl-containing organic acid aluminum compound
Of these, preferably (CH_ThreeCO_Two) Al (OH)_Two,
(CH_ThreeCO_Two)_TwoAl (OH), (C₁₃H₂₇CO_Two)
Al (OH)_Two, (C₁₃H₂₇CO_Two)_TwoAl (OH),
(C_FifteenH₃₁CO_Two) Al (OH)_Two, (C_FifteenH₃₁C
O_Two)_TwoAl (OH), (C₁₇H₃₅CO_Two) Al (O
H) _Two, (C₁₇H₃₅CO_Two)_TwoAl (OH), (CH_Three
(CH_Two)₇CH = CH (CH_Two)₇CO_Two) Al (O
H)_Two, (CH_Three(CH_Two)₇CH = CH (CH_Two) ₇
CO_Two)_TwoAl (OH), (CH_Three(CH_Two)_FourCH =
CHCH_TwoCH = CH (CH_Two)₇CO_Two) Al (O
H)_Two, (CH_Three(CH_Two)_FourCH = CHCH_TwoCH =
CH (CH_Two)₇CO_Two)_TwoAl (OH), (C_{twenty one}H₄₃
CO_Two) Al (OH)_Two, (C_{twenty one}H₄₃CO_Two)_TwoAl
(OH). More preferably R¹Has 15 to 15 carbon atoms
21 linear or branched saturated hydrocarbon groups,
Aluminum hydroxide of higher aliphatic carboxylic acid
And particularly preferably R¹Having 17 carbon atoms
Alternatively, stearic acid, which is a branched saturated hydrocarbon group
Or 1 or 2 aluminum hydroxide of isostearic acid
System. 1- or 2-hydroxylation of isostearic acid
Regarding aluminum, in addition to the compounds described above, 16-
Aluminum hydroxide of methyl heptadecanoic acid
Including. These may be a mixture of two or more, for example,
In the case of the aluminum hydroxide salt of theearic acid,
A mixture of a luminium salt and an aluminum dihydroxide salt may be used.
No.

The component (e) used in the preparation of the solid catalyst component (A) in the present invention includes aluminum hydroxide [A
1 (OH) ₃ ] is also used. The properties of the aluminum hydroxide are not particularly limited, but powdery or granular ones can be used, and it is desirable to carry out dehydration and degassing treatments such as vacuum drying before use in preparing the solid catalyst component (A). .

The above component (e) can be used alone or in combination of two or more. Component (e) is a hydrocarbon compound, for example, an aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene, propylbenzene, or trimethylbenzene, a saturated hydrocarbon such as hexane, heptane, or cyclohexane, orthodichlorobenzene, or chloride. It can also be used by suspending it in a halogenated hydrocarbon such as methylene, carbon tetrachloride or dichloroethane.

In the present invention, the above component (e) is an essential component in the preparation of the solid catalyst component. If this component is not used, the rate of generation of the polymer soluble in the polymerization solvent cannot be suppressed. In addition, favorable effects cannot be obtained on the bulk density and stereoregularity of the produced polymer.

In the preparation of the solid catalyst component (A) in the present invention, the following polysiloxanes can be used in addition to the components (a) to (e). As the polysiloxane, one or more of those represented by the following general formula (4) are used.

[0039]

Embedded image

(Where α represents the average degree of polymerization, 2 to 30)
000, the main component of R ^{13 to} R ²⁰ is a methyl group, and sometimes a part of R ^{13 to} R ²⁰ is a phenyl group, a hydrogen atom, a higher fatty acid residue having 10 to 20 carbon atoms, an epoxy-containing group, And the compound of the above general formula may form a cyclic polysiloxane in which R ¹⁶ and R ¹⁷ are methyl groups.

The polysiloxane is also collectively referred to as silicone oil and has a viscosity at 25 ° C. of 2 to 10,000 centistokes, more preferably 3 to 500 centistokes. And cyclic or modified polysiloxanes.

Dimethyl polysiloxane and methylphenyl polysiloxane are used as the chain polysiloxane, and hydrogenation ratio is 10 to 80% as the partially hydrogenated polysiloxane.
The methyl hydrogen polysiloxane of the following is a cyclic polysiloxane having hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8 -Tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane. By using the above polysiloxane for the preparation of the solid catalyst component (A), the bulk specific gravity and stereoregularity of the produced polymer can be further improved.

The solid catalyst component (A) includes the above-mentioned organic aluminum compound containing a hydroxyl group or aluminum hydroxide, a magnesium compound, a tetravalent halogen-containing titanium compound, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon, And by contacting with a polysiloxane.

As a method for preparing the solid catalyst component (A) of the present invention, the above-mentioned magnesium compound is dissolved in an alcohol or a titanium compound, and then a hydroxyl group-containing organic acid aluminum compound or aluminum hydroxide, aromatic dicarboxylic acid A method of obtaining a solid component by depositing a solid by contacting with a diester, a tetravalent halogen-containing titanium compound, an aromatic hydrocarbon, or the like, or by heating, or a method of converting a magnesium compound to a tetravalent halogen-containing titanium compound or an inert carbon. A method in which a solid component is obtained by suspending in a hydrogen solvent or the like and further subjecting a hydroxyl group-containing organic acid aluminum compound, an aromatic hydrocarbon, an aromatic dicarboxylic acid diester and, if necessary, a titanium compound to a contact treatment. Among these, the particles of the solid component obtained by the former method are almost spherical, and the particle size distribution is sharp. Also in the latter method, by using a spherical magnesium compound, it is possible to obtain a spherical and solid catalyst component having a sharp particle size distribution, and without using a spherical magnesium compound, for example, by using a spray device By spraying and drying the solution or suspension to form particles by a so-called spray-drying method, a spherical solid component having a sharp particle size distribution can be obtained.

The components are contacted in a container equipped with a stirrer under an atmosphere of an inert gas under a condition of removing water and the like.
This is performed while stirring. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact and stirred or mixed or dispersed or suspended for denaturation treatment. If you get
A temperature range of 40 to 130C is preferred. Reaction temperature is 4
When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and as a result, the performance of the prepared solid component becomes insufficient. When the temperature exceeds 130 ° C., the evaporation of the used solvent becomes remarkable, and the control of the reaction becomes difficult. It becomes difficult. The reaction time is at least 1 minute, preferably at least 10 minutes, more preferably at least 30 minutes.

Hereinafter, a method for preparing the solid catalyst component (A) will be exemplified. (1) An organomagnesium compound is synthesized by contacting a metal magnesium powder, an alkylmonohalogen compound and iodine, and then contacting a tetraalkoxytitanium, an acid halide, and an aliphatic alcohol in the presence of an aliphatic hydrocarbon. React to form a homogeneous solution, and contact the tetravalent halogen-containing titanium compound and aromatic hydrocarbon with the solution to precipitate a solid product;
A method in which an aromatic dicarboxylic acid diester and a hydroxyl group-containing organic acid aluminum compound or aluminum hydroxide are brought into contact with the solid product to prepare a solid catalyst component (A).

(2) An organomagnesium compound is synthesized by reacting metallic magnesium, butyl chloride and dibutyl ether, and tetrabutoxytitanium and tetraethoxytitanium are brought into contact with the organomagnesium compound to obtain a solid product. An aromatic dicarboxylic acid diester, dibutyl ether, tetravalent halogen-containing titanium compound, aromatic hydrocarbon and hydroxyl-containing organic acid aluminum or aluminum hydroxide compound are brought into contact with the solid product to prepare a solid catalyst component (A). how to.
At this time, the solid catalyst component (A) can be prepared by further polymerizing the solid catalyst component with an organoaluminum compound, an organosilicon compound and an olefin.

(3) A magnesium halide compound, an alkoxytitanium compound such as tetrabutoxytitanium, an aromatic dicarboxylic acid diester, an aliphatic hydrocarbon and an aliphatic alcohol are contacted and reacted to form a homogeneous solution. A solid component is precipitated by dropping into a valent halogen-containing titanium compound, and further contacted with an aromatic dicarboxylic acid diester, and then in the presence of an aromatic hydrocarbon, a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic aluminum compound or The contact reaction of aluminum hydroxide
A method for preparing the solid catalyst component (A).

(4) An aromatic dicarboxylic acid diester and an aromatic hydrocarbon are brought into contact with a dialkoxymagnesium such as diethoxymagnesium, and co-milled at a low temperature of 10 ° C. or less. And contacting a hydroxyl group-containing organic acid aluminum compound or aluminum hydroxide to prepare a solid catalyst component (A).

(5) Aliphatic magnesium such as calcium halide and magnesium stearate can be obtained by converting a tetravalent halogen-containing titanium compound, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon and a hydroxyl group-containing organic acid aluminum compound or aluminum hydroxide. A method for preparing a solid catalyst component (A) by contacting with a catalyst. At this time, organic aluminum or water can be further contacted with the solid catalyst component.

(6) An aromatic dicarboxylic acid diester such as fatty acid magnesium, dialkoxymagnesium, iso-butyl phthalate, an aromatic hydrocarbon and a hydroxyl group-containing organic acid aluminum compound or aluminum hydroxide may be used as a halogenated hydrocarbon. A method of obtaining a solid catalyst component (A) by suspending and then adding the suspension to a tetravalent halogen-containing titanium compound and performing a contact treatment.

(7) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contact-reacted with a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic aluminum compound or aluminum hydroxide. A method of preparing a solid catalyst component (A) by contacting an aromatic dicarboxylic acid diester at any point when repeating a contact reaction with a tetravalent halogen-containing titanium compound as necessary. At this time, a polysiloxane can be used in combination.

(8) A dialkoxymagnesium such as diethoxymagnesium and an aromatic dicarboxylic acid diester are suspended in an aromatic hydrocarbon, and the suspension is added to a tetravalent halogen-containing titanium compound and reacted. To obtain a solid product, and after washing the solid product with an aromatic hydrocarbon, contact a tetravalent halogen-containing titanium compound and a hydroxyl-containing organic aluminum compound or aluminum hydroxide in the presence of the aromatic hydrocarbon. To obtain the solid catalyst component (A). At this time, a polysiloxane can be used in combination.

(9) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contact-reacted with a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic aluminum compound or aluminum hydroxide. A method of preparing a solid catalyst component (A) by contacting an aromatic dicarboxylic acid diester and an inorganic salt such as calcium chloride at any time when repeating a contact reaction with a titanium compound as necessary.

(10) A dialkoxymagnesium such as diethoxymagnesium and a calcium compound such as calcium chloride are co-pulverized, and the obtained pulverized product is suspended in an aromatic hydrocarbon. And a contact reaction with a diester of an aromatic dicarboxylic acid,
Then, a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic acid aluminum compound or aluminum hydroxide are contact-reacted to prepare a solid catalyst component (A). At this time, the general formula Si (OR ²¹ ) ₄ (wherein R ²¹
Represents an alkyl group or an aryl group).

(11) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contact-reacted with a tetravalent halogen-containing titanium compound and a hydroxyl-containing organic aluminum compound or aluminum hydroxide, A method of obtaining the solid catalyst component (A) by bringing the aromatic dicarboxylic acid diester and a surfactant into contact at any point in the subsequent contact reaction with the titanium compound.

(12) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contact-reacted with a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic aluminum compound or aluminum hydroxide, When the contact reaction with the titanium compound is repeated as necessary, the solid component obtained by contact reaction with the aromatic dicarboxylic acid diester at any point is subjected to a heat treatment in the presence or absence of a hydrocarbon solvent to form a solid. A method for obtaining the catalyst component (A). At this time, a halogenated hydrocarbon may be allowed to coexist.

(13) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contacted with a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic aluminum compound or aluminum hydroxide, A method of obtaining a solid catalyst component (A) by bringing an aromatic dicarboxylic acid diester into contact with water at any time when repeating a contact reaction with a titanium compound as necessary. At this time, a halogenated hydrocarbon may be allowed to coexist.

(14) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contact-reacted with a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic aluminum compound or aluminum hydroxide. A method of obtaining a solid catalyst component (A) by contacting an aromatic dicarboxylic acid diester and an organoaluminum compound at any time when repeating contact with a titanium compound as necessary. At this time, an electron donating compound other than the aromatic dicarboxylic acid diester, for example, an organosilicon compound can be used in combination.

(15) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contacted and reacted with a tetravalent halogen-containing titanium compound. A solid product is obtained by contacting and reacting with the aromatic dicarboxylic acid diester having an alkyl group described above, and after washing the solid product with alkylbenzene, in the presence of an aromatic hydrocarbon, a tetravalent halogen-containing titanium compound and a hydroxyl group A method for obtaining a solid catalyst component (A) by contacting with a contained organic acid aluminum compound or aluminum hydroxide. At this time, the aromatic dicarboxylic acid diester having two or more alkyl groups having different carbon numbers can be brought into contact again with the second and subsequent contact with the titanium compound. Also, at some point,
A polysiloxane can also be contacted.

(16) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contact-reacted with a tetravalent halogen-containing titanium compound and a hydroxyl-containing organic aluminum compound or aluminum hydroxide, When the reaction contact with the titanium compound is repeated as necessary, the aromatic dicarboxylic acid diester and the general formula Al (OR ²² ) _r X _3-r (wherein R ²²
Is a method of preparing a solid catalyst component (A) by contacting an alkyl group or an aryl group having 1 to 4 carbon atoms, X is a halogen atom, and an aluminum compound represented by 0 ≦ r ≦ 3).
Also, at any point, the polysiloxane can be contacted.

(17) A solution is formed by contacting a dialkoxymagnesium such as diethoxymagnesium with a tetravalent halogen-containing titanium compound and an aromatic dicarboxylic acid diester in the presence of an aromatic hydrocarbon solvent. A method of preparing a solid catalyst component (A) by producing a solid product and then contacting it with a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic aluminum compound or aluminum hydroxide. At this time, the polysiloxane can be brought into contact at any point.

(18) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contact-reacted with a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic aluminum compound or aluminum hydroxide, A method of preparing a solid catalyst component (A) by contacting an aromatic dicarboxylic acid diester and a polycarbonyl compound at any time when repeating contact with a titanium compound as necessary. Also, at any point, the polysiloxane can be contacted.

(19) A dialkoxymagnesium such as diethoxymagnesium is suspended in an aromatic hydrocarbon, and then contact-reacted with a tetravalent halogen-containing titanium compound and a hydroxyl group-containing organic acid aluminum compound or aluminum hydroxide, A method of obtaining a solid catalyst component (A) by contacting an aromatic dicarboxylic acid diester and a monohydric or polyhydric alcohol at any point when repeating a contact reaction with a titanium compound as necessary. At any point, an aluminum compound such as aluminum chloride or a polysiloxane can be brought into contact.

(20) A method of mixing two or more of the solid catalyst components prepared by the methods (1) to (19) to obtain a solid catalyst component (A).

In the above-mentioned various preparation methods, particularly preferred methods for contacting component (e) include (i) component (a)
Is brought into contact with component (e) in the presence of component (b) or component (d): ・ (a) → (b) → (e) or ・ (a) → (d) → (e) (ii) contacting component (a) with component (e) in the presence of component (b) and component (d): (a) → (b) → (d) → (e), or (a) → (d) → (b) → (e) (iii) The solid reaction product X formed by contacting the components (a), (b), (c) and (d) Contacting component (e) in the presence of (b) and / or component (d): (a) → (b) → (c) → (d) → (solid reaction product X) →
(b ') → (e), ・ (a) → (b) → (c) → (d) → (solid reaction product X) →
(d ')->(b')-> (e), etc. (Here, component (b ') and component (d') may be the residue of component (b) and component (d) when , Component (b) and component (d) newly added). The temperature at which component (e) is brought into contact is-
20-130 degreeC, Preferably it is -10-100 degreeC, More preferably, it is 0-80 degreeC.

In the above preferred contacting method, the contact between the component (e) and the component (a) or the solid reaction product X is desirably performed in a suspended state. In this case, it is preferable that the contact is carried out by suspending the component (a) or the solid reaction product X in the component (b) or the component (d), and more preferably the component (a) or the solid reaction product The substance X is suspended and contact is made. After contacting the component (e) with the component (a) or the solid reaction product X in a suspended state,
It is particularly preferred that component (b) is further contacted. Compared to contact methods such as dry pulverization, contacting in a suspended state results in a particularly high catalytic activity and a low rate of generation of a polymer having low molecular weight or low stereoregularity that is soluble in a polymerization solvent. And is desirable in achieving the object of the present application.

Based on the above, a preferred contact sequence in the preparation of the solid catalyst component (A) is as follows. (1) (a) → (b) → (e) → (d) → (c) → (solid reaction product Y) → (b) → (solid catalyst component) (2) (a) → (b) → (e) → (d) → (c) → (solid reaction product Y) → (b) → (c) → (solid catalyst component) (3) [(a) + (d)] → (e) → (b) → (c) → (solid reaction product Y) → (d) → (b) → (solid catalyst component) (4) [(a) + (d)] → (e) → (b) → (c) → (solid reaction product Y) → (d) → (b) → (c) → (solid catalyst component) (5) [(a) + (e) + (d)] → (b) → (c) → (solid reaction product Y) → (d) → (b) → (solid catalyst component) (6) [(a) + (e) + (d)] → (b) → (c) → (solid reaction product Y) → (d) → (b) → (c) → (solid catalyst component) (7) [(a) + (d)] → (b) → (c) → (solid reaction (Product X) → (d ′) → (b ′) → (e) → (solid catalyst component) (8) [(a) + (d)] → (b) → (c) → (solid reaction product X) → (d ′) → (b ′) → (e) → (c) → (solid catalyst component) (9) [(a) + (d) + (c)] → (b) → (solid reaction Product X → (d ′) → (b ′) → (e) → (solid catalyst component) (10) [(a) + (d) + (c)] → (b) → (solid reaction product X) → ( (d ') → (b ′) → (e) → (c) → (solid catalyst component) (11) [(a) + (d) + (c)] → [(b) + (d)] → ( (Solid reaction product X) → (d ′) → (b ′) → (e) → (solid catalyst component) (12) [(a) + (d) + (c)] → [(b) + (d )] → (solid reaction product X) → (d ′) → (b ′) → (e) → (c) → (solid catalyst component) (where component (b ′) and component (d ′) are The solid reaction product X may be a residue of the components (b) and (d) at the time of the preparation of the solid component or a newly added component (b) and the component (d). )-(D), the solid reaction product Y is the reaction product of components (a)-(e).)

Further, particularly preferred methods for preparing the solid catalyst component (A) used in the present invention include the following methods: (1) A magnesium compound (a) such as diethoxymagnesium can be prepared by adding toluene compound such as toluene. And then contacting the suspension with component (b) such as titanium tetrachloride. Thereafter, at -20 to 50 ° C, preferably at 0 to 50 ° C, more preferably at 0 to 40 ° C,
It is desirable to carry out the aging reaction for 20 minutes, preferably 10 to 100 minutes, more preferably 20 to 80 minutes. Thereafter, the temperature is raised to 0 to 130 ° C, preferably 40 to 130 ° C.
C., more preferably 60-120 ° C., for 1-600 minutes, preferably 10-500 minutes, more preferably 30 minutes.
Incubate for ~ 400 minutes. At this time, before or after contacting the suspension with the component (b), one or more components (c) such as a phthalic acid diester are added.
The contact is performed at 0 to 130 ° C, preferably 10 to 100 ° C, particularly preferably 20 to 90 ° C. In that case, preferably, 2
One type of phthalic acid diester, one of which is 30-60
C. and the other at 60-80.degree. It is also desirable to contact the polysiloxane before or after the contact of the component (c). Thereafter, if necessary, the component (b) is further contact-reacted in the presence of the component (d) to obtain a solid reaction product. This solid reaction product may be washed with an aromatic hydrocarbon compound that is liquid at room temperature. The solid reaction product is then suspended in component (d),
The component (e) and the component (b) are added to the suspension at -20 to 1
30 ° C., preferably −10 to 100 ° C., more preferably 0 to 80 ° C., and 0 to 130 ° C., preferably 40
~ 130 ° C, more preferably 60 ~ 120 ° C, 1-6
The reaction is performed for 00 minutes, preferably for 10 to 500 minutes, more preferably for 30 to 400 minutes. At this time, before or after contacting the component (e) and the component (b) with the solid reaction product, one or more of the component (c) can be further contacted. Thereafter, if necessary, the component (b) may be further brought into contact in the presence of the component (d). Then, the solid catalyst component (A) is obtained by washing with a hydrocarbon compound which is liquid at normal temperature.

(2) Component (a) and component (e) are added to component (d) at -20 to 130 ° C., preferably -10 to -1.
Suspended at 00 ° C, more preferably 0-80 ° C.
30 ° C, preferably 50 to 130 ° C, particularly preferably 5 ° C
The reaction is carried out at 0 to 100 ° C. for 1 minute to 100 hours, preferably 30 minutes to 10 hours, particularly preferably 30 minutes to 5 hours. Next, the component (b) is added to the suspension at -20 to 100.
° C, preferably -10 to 90 ° C, particularly preferably -5 to
Contact at 80 ° C., 0-130 ° C., preferably 50-13
0 ° C., particularly preferably 60 to 120 ° C., for 1 to 600 minutes, preferably 10 to 500 minutes, more preferably 30 minutes
Incubate for ~ 400 minutes. Before or after contacting the suspension with the component (b), one or more of the components (c) is brought to -20 to 130 ° C, preferably -10 to -10 ° C.
120 ° C., particularly preferably at −5 to 110 ° C.,
A solid product is obtained. The solid product may be washed with a hydrocarbon compound that is liquid at room temperature. Thereafter, the component (b) is further added.
In the presence of component (d) at 0 to 130 ° C, preferably at 50 to 130 ° C, particularly preferably at 60 to 120 ° C.
It is desirable that the contact reaction is carried out for a period of up to 600 minutes, preferably 10 to 500 minutes, more preferably 30 to 400 minutes. At this time, it is also a preferable embodiment that one or more of the component (c) is further contacted before or after the component (b) is brought into contact with the solid product. Further, at any of the above points, a polysiloxane may be used, if necessary. Then, the solid catalyst component (A) is obtained by washing with a hydrocarbon compound which is liquid at normal temperature.

(3) One or more of component (a) and component (c) are suspended in component (d), and then component (b) is added to the suspension at -20 to 100 ° C. Preferably-
Contact at 10 to 90C, particularly preferably -5 to 80C,
0-130 ° C., preferably 50-130 ° C., particularly preferably 60-120 ° C., for 1-600 minutes, preferably 1
The reaction is carried out for 0 to 500 minutes, more preferably 30 to 400 minutes, to obtain a solid product. At this time, before or after the component (b) is brought into contact with the suspension, one or more components (c) are further added to the suspension at -20 to 130 ° C.
Preferably -10 to 120C, particularly preferably -5 to 1
Contact can also be made at 10 ° C. Further, the solid product may be washed with a hydrocarbon compound which is liquid at normal temperature. Next, after suspending the solid product in the component (d), the component (e) is added to the solid product at -20 to 130 ° C, preferably -10 to 100 ° C, and more preferably 0 to 80 ° C. Contact. After this, component (b) is further added to 0-130 ° C, preferably 50-130 ° C, particularly preferably 60-120 ° C.
It is desirable to carry out the contact reaction for 1 to 600 minutes, preferably 10 to 500 minutes, more preferably 30 to 400 minutes. At this time, it is also a preferable embodiment that one or more of the component (c) is further contacted before or after the component (b) is brought into contact with the solid product. Further, at any of the above points, a polysiloxane may be used, if necessary.

The ratio of each compound used in the preparation of the solid catalyst component (A) cannot be unequivocally specified because it varies depending on the preparation method. 5 to 100 mol, preferably 0.5 to 50
Moles, more preferably 1 to 10 moles, of component (c)
Is 0.001 to 10 mol, preferably 0.01 to 1 mol, more preferably 0.02 to 0.6 mol. Component (d) is used in an amount of 0.001 to 1 mole of component (a).
Mol or more, preferably 0.001 to 100 mol, more preferably 0.005 to 10 mol. The amount of component (e) used is 0.0005 to 0.1 mol, preferably 0.0008 to 0.08 mol, more preferably 0.0008 to 0.1 mol, per 1 mol of component (a), in the case of a hydroxyl group-containing organic aluminum acid. Is 0.001 to 0.06 mol, and 0.0005 to 0.1 mol, preferably 0.0007 to 0.05 mol, more preferably 0.001 to 0 mol, per 1 mol of the component (b). 0.03 mol. When the component (e) is aluminum hydroxide, 0.0 mol per 1 mol of the component (a)
0005-0.12 mol, preferably 0.00008-
0.1 mole, more preferably 0.0001 to 0.08 mole, and 0.0000 to 1 mole of component (b)
5 to 1 mol, preferably 0.00007 to 0.5 mol,
More preferably, it is 0.0001 to 0.1 mol. In the present invention, it is desirable to use the component (e) in the above range. When the amount is less than the above range, it is difficult to obtain the effect of high stereoregularity as in the present invention. It is easy to adversely affect stereoregularity. In particular, the ratio of the hydroxyl group in the component (e) to the component (a) or the component (b) is important. For example, with respect to 1 mol of the component (a),
The hydroxyl group is 0.00005 to 0.36 mol, preferably 0.00008 to 0.3 mol, particularly preferably 0.00
0.1 to 0.24 mol, and the hydroxyl group is contained in the component (b) in an amount of 0.00015 to 3 mol, preferably 0.000 to 3 mol.
21 to 1.5 mol, particularly preferably 0.00030 to
0.3 mol.

In the preparation methods exemplified above, component (a) is diethoxymagnesium or dipropoxymagnesium, component (b) is titanium tetrachloride, and component (c) is phthalic acid diester, preferably phthalic acid. Diethyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, di-isophthalate
-Butyl, di-n-octyl phthalate, bis (2-ethylhexyl) phthalate, di-iso-decyl phthalate or two or more thereof, and it is desirable to use toluene or xylene as the component (d). .

The most preferred components (a) to (d) in the present invention
The combinations of (e) are as follows: (1) Jie
Toxium magnesium, titanium tetrachloride, phthalate
Di-n-butyl acid, toluene, (C₁₇H₃₅CO_Two)_TwoAl
(OH) or Al (OH) _Three; (2) Diethoxymag
Nesium, titanium tetrachloride, diethyl phthalate
, Bis (2-ethylhexyl) phthalate, toluene,
(C₁₇H₃₅CO_Two)_TwoAl (OH) or Al (OH)_Three.

The organoaluminum compound (B) used for forming the olefin polymerization catalyst of the present invention includes a compound represented by the following general formula: R ² _p AlQ _3-p (wherein R ² has 1 to 1 carbon atoms)
4 represents an alkyl group, Q represents a hydrogen atom or a halogen atom, and p is a real number satisfying 0 <p ≦ 3. ) Can be used. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-i
Examples thereof include so-butylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more kinds can be used. Preferably,
Triethyl aluminum and tri-iso-butyl aluminum.

The organosilicon compound (C) used for forming the olefin polymerization catalyst of the present invention may be represented by the general formula R ³ _qSi (OR ⁴ ) _{4 -q} (wherein R ³ has 1 carbon atom)
To 12 alkyl groups, cycloalkyl groups, phenyl groups,
It represents a vinyl group, an allyl group, or an aralkyl group, and may be the same or different. R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different. q is an integer of 0 ≦ q ≦ 3. ) Is used. Such organosilicon compounds include:
Examples thereof include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

Specific examples of the above organosilicon compounds include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n
-Propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxysilane, tri-
t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di- -N-propyldiethoxysilane, di-iso-
Propyldiethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t
-Butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2
-Ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxy Silane, cyclohexyl (is
o-propyl) dimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl ( n-pentyl) diethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (i
(so-butyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethyl Ethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane , Iso-propyltrimethoxysilane, iso-propyltriethoxysilane, n
-Butyltrimethoxysilane, iso-butyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2
-Ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3 , 5
-Dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl)
Examples thereof include dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Among the above, di-n-propyldimethoxysilane, di-iso-
Propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t
-Butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxy Silane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4 -Methylcyclohexylsic Pentyl dimethoxy silane, 3,
5-dimethylcyclohexylcyclopentyldimethoxysilane is preferably used, and the organosilicon compound (C)
Can be used alone or in combination of two or more.

To polymerize olefins using the olefin polymerization catalyst of the present invention, an olefin is polymerized in the presence of a catalyst comprising the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C). Polymerization or copolymerization of olefins is carried out, and the amount ratio of each component is not limited as long as it does not affect the effects of the present invention, and is not particularly limited. ) Is 1 to 5000 mol, preferably 10 to 200 mol, per 1 mol of titanium atom in the solid catalyst component (A).
It is used in an amount of 0 mol, particularly preferably 50 to 1000 mol. The organosilicon compound (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 1 mol per mol of the component (B).
To 2 mol, particularly preferably 0.01 to 0.5 mol.

The order of contact of the components is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the organosilicon compound (C) is contacted, and the solid catalyst component (A) is further contacted. It is desirable to make it.

The polymerization method of the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in any of a gas and a liquid. It is also possible to use hydrogen as a molecular weight regulator during polymerization. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Further, any of a continuous polymerization method and a batch polymerization method can be used. Further, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

The olefins to be polymerized or copolymerized by the method of the present invention are olefins having 2 to 10 carbon atoms, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1
Long chain olefins such as -decene, branched olefins such as 3-methyl-1-butene and 4-methyl-1-pentene,
Dienes such as butadiene, or vinylcyclopentane, vinylcyclohexane, and the like, and one or more of these olefins can be used. In particular, ethylene and propylene are preferably used. Further, in the present invention, olefin polymerization (also referred to as main polymerization) performed using a catalyst comprising the solid catalyst component (A), the organoaluminum compound (B), and the organosilicon compound (C).
In this case, it is desirable to carry out preliminary polymerization prior to main polymerization in order to further improve the catalytic activity, stereoregularity, and particle properties of the produced polymer. As the olefins used in the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

In carrying out the prepolymerization, the order of contact of each component and the monomer is arbitrary, but preferably, the organoaluminum compound (B ) And then contacting the solid catalyst component (A), followed by contacting one or more olefins. When performing prepolymerization by combining an organosilicon compound, an organoaluminum compound (B) is first charged into a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere for polymerization, and then the organosilicon compound (C ), And further contacting the solid catalyst component (A), and then contacting one or more olefins. In addition, a molecular weight regulator such as hydrogen may be added during the prepolymerization.

[0083]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples. <Characteristic evaluation> The slurry polymerization of propylene and the slurry random copolymerization of propylene and ethylene were evaluated using the olefin polymerization catalyst of the present invention, and the total amount of polymer per 1 g of the solid catalyst component (polymerization activity: Yield),
The ratio of the amount of polymer insoluble in boiling n-heptane to the total amount of polymer (HI) and the rate of generation of a polymer soluble in the polymerization solvent (soluble matter generation rate) were measured. Yield, HI, and soluble matter generation rate were calculated by the following formulas. Further, the melt flow rate (MI) and bulk density (B
D) and the ethylene content (copolymer only) were measured. M
I and BD are measured according to JIS K 7210, respectively.
And JIS K6721. For the ethylene content, refer to FT-IR manufactured by JEOL Datum Co., Ltd.
(Fourier transform infrared spectrometer), JIR-RFX
3001.

Yield (g-PP / g-cat.) = ｛A (g)
+ C (g)} / solid catalyst component (g) HI (% by weight) =
{B (g) / a (g)} × 100 Soluble content generation rate (% by weight) = [c (g) / ｛a (g) + c
(G)｝] × 100 In the above formula, a is the weight of the polymer formed after the completion of the polymerization reaction, and b is the polymer formed after the completion of the polymerization reaction. 6
The weight of the insoluble portion of n-heptane at the time of extraction, c indicates the amount of the polymer dissolved in the polymerization solvent filtered after completion of the polymerization.

Example 1 <Preparation of solid catalyst component (A)> In a 2000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, 100 g of diethoxymagnesium and 8 parts of toluene were placed.
And then add titanium tetrachloride 20
0 ml was charged. The mixed solution was stirred for 1 hour while being kept at 30 ° C., and ripened. Then, 52 ml of bis (2-ethylhexyl) phthalate, 2.0 ml of diethyl phthalate and polysiloxane (TSF451-10
0: product made by Toshiba Silicone Co., Ltd.)
It was added at 0 ° C, 70 ° C, and 85 ° C. Next, the temperature was raised to 110 ° C., and the mixture was reacted for 1.5 hours while stirring. After the completion of the reaction, the supernatant was removed, and 800 ml of toluene and 200 ml of titanium tetrachloride were newly added, followed by a reaction at 110 ° C. for 15 minutes. After the completion of the reaction, the product was washed with toluene, and 800 ml of toluene, 200 ml of titanium tetrachloride and Alste (ditype) (trade name) (aluminum stearate manufactured by Shodo Chemical Co., Ltd .: (C ₁₇
H ₃₅ CO ₂ ) ₃ Al, (C ₁₇ H ₃₅ CO ₂ ) ₂ Al (OH),
_3. A mixture of (C ₁₇ H ₃₅ CO ₂ ) Al (OH) ₂ with a metal content of 4.
The ratio of free fatty acids is 18% for 0%. ) 18.5g
(1 mole of diethoxymagnesium contains 0.1% of arste.
034 mol and 0.017 mol with respect to 1 mol of titanium tetrachloride) were added thereto, and the mixture was heated to 100 ° C. and reacted for 2 hours with stirring. Next, the product was washed with heptane, filtered and dried to obtain a powdery solid catalyst component (A). The titanium content of the solid catalyst component (A) was 2.00% by weight.

<Polymerization> Inner volume 1 replaced by nitrogen gas
700 ml of n-heptane was charged into a 500 ml autoclave equipped with a stirrer, then 2.1 mmol of triethylaluminum, 0.21 mmol of cyclohexylmethyldimethoxysilane and the above solid catalyst component (A)
Was added in an amount equivalent to 0.0053 mmol as a titanium atom, followed by stirring to form a polymerization catalyst. Then, the pressure inside the system was increased to 0.1 MPa with propylene gas, and prepolymerization was performed at 20 ° C. for 30 minutes. Thereafter, 80 ml of hydrogen gas was charged, and the pressure inside the system was increased to 0.6 MPa with propylene gas.
The main polymerization was carried out at 70 ° C. for 2 hours. Table 1 shows the polymerization evaluation results.
Will be added to

Example 2 Example 1 was repeated except that the amount of Arste used was 9.3 g (0.017 mol of Arste per mol of diethoxymagnesium and 0.084 mol per mol of titanium tetrachloride). Preparation of solid catalyst component (A) and evaluation of polymerization were performed in the same manner as described above. When the titanium content of the obtained solid catalyst component (A) was measured, it was 1.99% by weight.
The results of the polymerization evaluation are also shown in Table 1.

Example 3 Example 1 was repeated except that the amount of Arste used was 4.6 g (0.0086 mol of Arste per mol of diethoxymagnesium and 0.0041 mol per mol of titanium tetrachloride). Preparation of solid catalyst component (A) and evaluation of polymerization were performed in the same manner as described above. When the titanium content of the obtained solid catalyst component (A) was measured, it was 1.92% by weight. The results of the polymerization evaluation are also shown in Table 1.

Example 4 Example 1 was repeated except that the amount of Arste used was 1.2 g (0.0022 mol of Arste per mol of diethoxymagnesium and 0.0011 mol per mol of titanium tetrachloride). Preparation of solid catalyst component (A) and evaluation of polymerization were performed in the same manner as described above. When the titanium content of the obtained solid catalyst component (A) was measured, it was 1.72% by weight. The results of the polymerization evaluation are also shown in Table 1.

Example 5 <Preparation of solid catalyst component (A)> In a 2000 ml round bottom flask equipped with a stirrer and sufficiently purged with nitrogen gas, 100 g of diethoxymagnesium and 8 parts of toluene were added.
And then add titanium tetrachloride 20
0 ml was charged. The mixed solution was stirred for 1 hour while being kept at 30 ° C., and ripened. Then, 52 ml of bis (2-ethylhexyl) phthalate, 2.0 ml of diethyl phthalate and polysiloxane (TSF451-10
0: product made by Toshiba Silicone Co., Ltd.)
It was added at 0 ° C, 70 ° C, and 85 ° C. Next, the temperature was raised to 110 ° C., and the mixture was reacted for 1.5 hours while stirring. After the completion of the reaction, the supernatant was removed, and 800 ml of toluene and 200 ml of titanium tetrachloride were newly added, followed by a reaction at 110 ° C. for 15 minutes. After the completion of the reaction, the product was washed with toluene. Then, a suspension obtained by suspending 4.6 g of Arste (0.0086 mol of Arste per mol of diethoxymagnesium and 0.0041 mol per mol of titanium tetrachloride) in 800 ml of toluene was added to the product. Add 200 ml of titanium tetrachloride and add 10
The temperature was raised to 0 ° C., and a contact reaction was performed for 2 hours while stirring.
The product is then washed with heptane, filtered and dried,
A powdery solid catalyst component (A) was obtained. The titanium content of this solid catalyst component (A) was 1.82% by weight. <Polymerization> The polymerization was evaluated in the same manner as in Example 1. The results of the polymerization evaluation are also shown in Table 1.

Example 6 A solid was prepared in the same manner as in Example 3 except that 4.6 g of Arste was suspended in 54 ml of n-heptane, then poured into 800 ml of toluene, and then contacted with 200 ml of titanium tetrachloride. Preparation of the catalyst component (A) and polymerization evaluation were performed. When the titanium content of the obtained solid catalyst component (A) was measured, it was 2.08% by weight. The results of the polymerization evaluation are also shown in Table 1.

Example 7 <Preparation of solid catalyst component> Instead of Arste, 0.2 g of aluminum hydroxide (0.0029 mol of aluminum hydroxide per 1 mol of diethoxymagnesium, and 0.1 g per 1 mol of titanium tetrachloride). 0014 mol) was used in the same manner as in Example 1. When the titanium content of this solid catalyst component (A) was measured, it was 1.6.
It was 5% by weight. <Polymerization> The polymerization was performed in the same manner as in Example 1. Table 1 shows the polymerization evaluation results.
Shown in

Example 8 The amount of aluminum hydroxide used was 0.02 g (0.0 mole of aluminum hydroxide was added to 1 mole of diethoxymagnesium).
A solid catalyst component was prepared in the same manner as in Example 7, except that 0029 mol and 0.00014 mol per 1 mol of titanium tetrachloride). At this time, the titanium content of (A) in the solid catalyst component was 1.77% by weight.
The polymerization was carried out in the same manner as in Example 7. The results of the polymerization evaluation are also shown in Table 1.

Example 9 <Preparation of solid catalyst component> In a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, 20 g of diethoxymagnesium, 160 ml of toluene and aluminum hydroxide were placed in a flask. After adding 4 g (0.10 mol of aluminum hydroxide to 1 mol of diethoxymagnesium) and performing a contact reaction at 90 ° C. for 2 hours with stirring,
Cooled to room temperature. Next, titanium tetrachloride 40
ml (1 mol of titanium tetrachloride, 0.05 mol of aluminum hydroxide) was charged and heated, and 5.7 ml of di-n-butyl phthalate was added at 80 ° C. Then 1
The temperature was raised to 10 ° C., and the reaction was performed for 2 hours while stirring. After the completion of the reaction, the supernatant was removed, and the solid product was washed with toluene. Then, 160 ml of toluene and 40 ml of titanium tetrachloride were added, and the mixture was reacted at 100 ° C. for 1.5 hours. After the completion of the reaction, the product was washed with toluene, filtered and dried to obtain a powdery solid catalyst component (A). When the titanium content of this solid catalyst component (A) was measured, it was 2.66% by weight. <Polymerization> The polymerization was performed in the same manner as in Example 1. Table 1 shows the polymerization evaluation results.
Will be added to

Comparative Example 1 <Preparation of Solid Catalyst Component (A)> In a 2000 ml round bottom flask equipped with a stirrer and sufficiently replaced with nitrogen gas, 100 g of diethoxymagnesium and toluene 8 were added.
And then add titanium tetrachloride 20
0 ml was charged. Thereafter, 27 ml of dibutyl phthalate was added, the temperature was raised to 110 ° C., and the reaction was carried out for 2 hours with stirring. After the completion of the reaction, the product was washed with toluene, and fresh 800 ml of toluene and titanium tetrachloride 200
Then, the temperature was increased to 110 ° C., and 1.
The contact reaction was performed for 5 hours. Next, the product was washed with heptane, filtered and dried to obtain a powdery solid catalyst component (A). The titanium content in the solid catalyst component (A) was measured and was 2.24% by weight. <Polymerization> Polymerization was carried out in the same manner as in Example 1. The results of the polymerization evaluation are also shown in Table 1.

Comparative Example 2 Except that 10 g of AlCl ₃ was used instead of Alste,
Preparation and polymerization evaluation of the solid catalyst component (A) were performed in the same manner as in Example 1. The titanium content in the obtained solid catalyst component (A) was measured and found to be 2.73% by weight. The results of the polymerization evaluation are also shown in Table 1.

Comparative Example 3 18.5 (C ₁₇ H ₃₅ CO ₂ ) ₃ Al was used instead of Alste.
Except for using g, the preparation and polymerization evaluation of the solid catalyst component (A) were performed in the same manner as in Example 1. When the titanium content in the obtained solid catalyst component (A) was measured, it was 1.9.
It was 2% by weight. The results of the polymerization evaluation are also shown in Table 1.

Comparative Example 4 The amount of aluminum hydroxide used was 20 g (0.29 mol of aluminum hydroxide per mol of diethoxymagnesium and 0.14 mol per mol of titanium tetrachloride).
(Mol), and the preparation and polymerization evaluation of the solid catalyst component were performed in the same manner as in Example 7. The titanium content in the solid catalyst component (A) was measured and was 1.50% by weight. The results of the polymerization evaluation are also shown in Table 1.

Comparative Example 5 <Preparation of solid catalyst component (A)> 5 g of aluminum hydroxide
And 45 g of diethoxymagnesium (0.16 mol of aluminum hydroxide per 1 mol of diethoxymagnesium) was placed in a vibrating mill pot having a capacity of 1000 ml filled with stainless steel balls having a diameter of 25 mm 4/5 of the total volume under a nitrogen gas atmosphere. Loaded, vibration frequency 1430 times / min,
The crushing process was performed at an amplitude of 3.5 mm for 1 hour at room temperature.
Equipped with a stirrer and fully purged with nitrogen gas, capacity 5
Into a 00 ml round bottom flask were charged 5.5 g of the above ground product and 15 ml of ortho-dichlorobenzene, and then 1.8 ml of dibutyl phthalate and 20 ml of titanium tetrachloride.
0 ml (0.035 mol of aluminum hydroxide per 1 mol of titanium tetrachloride) was charged. Then 11
The temperature was raised to 0 ° C., and the reaction was performed for 2 hours with stirring. After completion of the reaction, the product was washed with heptane, and further washed with 200 ml of titanium tetrachloride. Then, 200 ml of titanium tetrachloride was newly added, the temperature was raised to 110 ° C., and a contact reaction was performed for 2 hours with stirring. Next, the product was washed with heptane, filtered and dried to obtain a powdery solid catalyst component (A). The titanium content in the solid catalyst component (A) was measured and found to be 2.68% by weight. <Polymerization> Polymerization was carried out in the same manner as in Example 1. The results of the polymerization evaluation are also shown in Table 1.

[0100]

[Table 1]

Example 10 <Preparation of solid catalyst component> The same procedure as in Example 7 was carried out. <Polymerization> n-heptane 700 was placed in an autoclave having an internal volume of 2200 ml and having a stirrer replaced with nitrogen gas.
ml, then 2.1 m of triethylaluminum
mol, cyclohexylmethyldimethoxysilane 0.2
1 mmol and the above solid catalyst component (A) in an amount equivalent to 0.0035 mmol as a titanium atom were added and stirred to form a polymerization catalyst. Then, propylene gas was added to the hopper.
The pressure inside the system was increased to 0.1 MPa while continuously supplying at 0 Nl (liter) / min, and prepolymerization was performed at 30 ° C. for 30 minutes. Then, without stopping the supply of propylene, ethylene gas was supplied at 0.30 Nl / min and hydrogen gas was supplied at 0.15 N / min.
The pressure inside the system was increased to 0.4 MPa while continuously supplying at 1 / min, and main polymerization (copolymerization) was performed at 70 ° C. for 2 hours. Table 2 shows the results of the polymerization evaluation.

Example 11 <Preparation of solid catalyst component> A 2000 ml round bottom flask equipped with a stirrer and sufficiently purged with nitrogen gas was charged into a round bottom flask.
100 g of diethoxymagnesium and 800 m of toluene
and then 200 ml of titanium tetrachloride
Was charged. The mixed solution was stirred for 1 hour while being kept at 30 ° C., and ripened. Thereafter, 52 ml of bis (2-ethylhexyl) phthalate, 11 ml of diethyl phthalate and 40 ml of polysiloxane (TSF451-100: a product of Toshiba Silicone Co., Ltd.) were added at 50 ° C., 70 ° C., respectively.
Added at 85 ° C. Next, the temperature was raised to 110 ° C., and the mixture was reacted for 1.5 hours while stirring. After the completion of the reaction, the supernatant was removed, and 800 ml of toluene and 200 ml of titanium tetrachloride were newly added, followed by a reaction at 110 ° C. for 15 minutes. After completion of the reaction, the product was washed with toluene, and freshly 600 ml of toluene and a suspension of aluminum hydroxide in toluene (0.2 g of aluminum hydroxide per 20 g of toluene) were added.
0 ml) (0.0029 mol of aluminum hydroxide per 1 mol of diethoxymagnesium). Next, 200 ml of titanium tetrachloride (0.0014 mol of aluminum hydroxide per mol of titanium tetrachloride) and 2.5 ml of diethyl phthalate were added at 80 ° C., and the temperature was further raised to 100 ° C., and the mixture was stirred for 2 hours while stirring. Reacted. The product is then washed with heptane,
After filtration and drying, a powdery solid catalyst component (A) was obtained.
When the titanium content of (A) in this solid catalyst component was measured, it was 2.13% by weight. <Polymerization> The polymerization was carried out in the same manner as in Example 10. The results of the polymerization evaluation are also shown in Table 2.

Comparative Example 6 A solid catalyst component was prepared in the same manner as in Comparative Example 1.
The evaluation of polymerization was performed in the same manner as in Example 1. The results of the polymerization evaluation are also shown in Table 2.

Comparative Example 7 <Preparation of solid catalyst component> A solid catalyst component was prepared in the same manner as in Comparative Example 1, and the polymerization was evaluated in the same manner as in Example 10 except that the ethylene flow rate was changed to 0.2 Nl / min. . The results of the polymerization evaluation are also shown in Table 2.

[0105]

[Table 2]

[0106]

According to the present invention, when olefins are polymerized by the slurry method in the presence of the olefin polymerization catalyst of the present invention, the catalytic activity and the stereoregularity of the produced polymer are higher than when a conventional catalyst is used. While maintaining the bulk density at a high level, the rate of occurrence of the polymer soluble in the polymerization solvent is 2/3 to 1 /
It can be reduced to 10. Furthermore, in the copolymerization of olefins, it is possible to reduce the rate of occurrence of soluble components in the polymerization solvent to 以下 or less as compared with the case where a polymer having the same ethylene content is produced using a conventional catalyst. it can. This allows
It is possible to improve the process operability and the production cost during the production of polyolefin.

[Brief description of the drawings]

FIG. 1 is a flow chart showing steps for preparing a catalyst component and a polymerization catalyst of the present invention.

Claims (4)

[Claims] 1. A solid catalyst component for olefin polymerization, which is prepared using the following components (a) to (e). (A) a magnesium compound, (b) a tetravalent halogen-containing titanium compound, (c) an aromatic dicarboxylic acid diester,
(D) an aromatic hydrocarbon, and (e) at least one aluminum compound selected from a hydroxyl group-containing organic acid aluminum compound represented by the following general formula (1) and aluminum hydroxide. (R ¹ CO ₂ ) _m Al (OH) _3-m (1) (wherein m is 1 or 2, R ¹ is a hydrogen atom or a linear or branched saturated group having ^{1 to} 21 carbon atoms or It represents an unsaturated hydrocarbon group.) 2. The solid catalyst component for olefin polymerization according to claim 1, wherein the magnesium compound is a dialkoxy magnesium. 3. The tetravalent halogen-containing titanium compound,
Formula Ti in _{^{(OR 12) n X 4-}} n ( wherein, R ¹² is C 1 -C
And X represents a halogen atom such as chlorine, bromine or iodine, and n is an integer of 0 ≦ n ≦ 3. )
The solid catalyst component for olefin polymerization according to claim 1 or 2, which is a titanium compound represented by the following formula: 4. A solid catalyst for olefins polymerization, which is formed from the following components (A), (B) and (C). (A) the solid catalyst component for olefin polymerization according to claim 1, (B) a general formula R ² _p AlQ _3-p (wherein R ² represents an alkyl group having 1 to 4 carbon atoms, and Q represents a hydrogen atom Alternatively, it represents a halogen atom, and p is 0 <p ≦ 3
Is a real number. An organoaluminum compound represented by
And (C) the general formula R ³ _q Si (OR ⁴⁾ in _4-q (wherein, R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, any aralkyl group And may be the same or different.
⁴ represents an alkyl group having 1 to ⁴ carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, an aralkyl group,
They may be the same or different. q is an integer of 0 ≦ q ≦ 3. An organosilicon compound represented by the formula: