JP2003192718A - Catalyst and method for polymerizing olefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst for manufacturing, at a high polymerization activity, a polyolefin that has little amount of decane- soluble components and excellent stereoregularity, and to provide a method for polymerizing an olefin using this olefin polymerization catalyst. <P>SOLUTION: The olefin polymerization catalyst comprises (A) a solid titanium catalyst ingredient containing magnesium, titanium, a halogen and a polyether, (B) an organoaluminum compound, and (C) a monoalkoxysilane compound represented by R<SP>a</SP><SB>3</SB>Si(OR<SP>b</SP>) (wherein R<SP>a</SP>is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; and OR<SP>b</SP>is a methoxy group or an ethoxy group). An olefin may be prepolymerized with an olefin polymerization catalyst comprising the catalyst ingredient (A), (B) and optionally, (D) an electron donor. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst capable of producing a highly stereoregular polyolefin with high polymerization activity, and a method for olefin polymerization using this olefin polymerization catalyst.

[0002]

BACKGROUND OF THE INVENTION A Ziegler-Natta catalyst composed of a titanium catalyst component and an organoaluminum compound has been widely used as a catalyst for producing polyolefin, and contains a carrier-supported solid titanium catalyst component as the titanium catalyst component. It is known that catalysts show high polymerization activity. In particular, a catalyst containing a magnesium chloride-supported titanium catalyst component among solid titanium catalyst components exhibits high polymerization activity and can produce a highly stereoregular polyolefin when an olefin such as propylene is polymerized. Known as a catalyst.

Various studies have been conducted on a catalyst containing such a solid titanium catalyst component in order to improve the polymerization activity and obtain a polyolefin having desired characteristics.
For example, as a component (internal donor) when preparing a solid titanium catalyst component, or as a catalyst component (external donor) when forming a catalyst for olefin polymerization from a solid titanium catalyst component and an organoaluminum compound, various electron donors are provided. It has been proposed to use the body.

For example, as the internal donor, a monocarboxylic acid ester, a polycarboxylic acid ester, a polyhydric hydroxy compound ester, an aliphatic carboxylic acid, an acid anhydride, a ketone, an aliphatic ether, an aliphatic carbonate, an alkoxy group-containing alcohol, Aryloxy group-containing alcohol,
Organosilicon compound having Si-O-C bond, P-O-
Organic phosphorus compounds having a C bond are widely used, and in particular, polyvalent carboxylic acid esters such as phthalic acid esters are used. As the external donor, a nitrogen-containing electron donor, an oxygen-containing electron donor, an organic phosphorus compound having a P—O—C bond, an organic silicon compound having a Si—O—C bond, and the like are known.

The applicant of the present invention has previously disclosed in JP-A-58-83006 that a highly stereoregular polyolefin can be produced in a high yield and is excellent in particle size, particle size distribution, particle property and bulk specific gravity. As a polyolefin production catalyst, a solid titanium catalyst component containing at least a carboxylic acid ester as an internal donor (internal electron donor), an organoaluminum compound, and Si-O-C or Si as an external donor (external electron donor). An olefin polymerization catalyst comprising an organosilicon compound having a -NC bond has been proposed. As the organosilicon compound having a Si—O—C bond (external donor), an alkoxysilane compound such as tetraethoxysilane, phenyltriethoxysilane or diphenyldimethoxysilane is specifically used.

Among the alkoxysilane compounds,
A cyclopentyl group represented by dicyclopentyldimethoxysilane, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or a carbon adjacent to Si is a secondary carbon or A catalyst having a dimethoxysilane compound having two tertiary hydrocarbon groups and two methoxy groups as an external donor can produce a highly stereoregular polyolefin.

[0007] Further, in recent years, it has been attempted to further pursue the safety depending on the intended use of polyolefin, and the chemicals used in the production process of polyolefin are required to be produced with more attention. Has been. Therefore, the inventors of the present invention have thus prepared a solid titanium catalyst component using polyethers as an internal donor for an olefin polymerization comprising an organoaluminum compound and a monoalkoxy compound having one alkoxy group as an external donor. The present inventors have completed the present invention by finding that a high stereoregular polyolefin can be produced with high polymerization activity by using a catalyst.

[0008]

It is an object of the present invention to provide an olefin polymerization catalyst capable of producing a highly stereoregular polyolefin with a high polymerization activity, and an olefin polymerization method using the olefin polymerization catalyst. I am trying.

[0009]

SUMMARY OF THE INVENTION The catalyst for olefin polymerization according to the present invention is
(A) a solid titanium catalyst component containing magnesium, titanium, halogen and a polyether (excluding ester compounds), (B) an organoaluminum compound, and (C) R ^a ₃ SiOR ^b [wherein R ^a group is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and OR ^b is a methoxy group or an ethoxy group], and a monoalkoxysilane compound represented by the following: .

According to another embodiment, the catalyst for olefin polymerization according to the present invention is a solid titanium catalyst component containing [I] (A) magnesium, titanium, halogen and polyether (provided that the ester compounds are Not included), (B)
An olefin polymerization catalyst comprising an organoaluminum compound and, if necessary, an (D) electron donor, a prepolymerization catalyst prepared by prepolymerizing an olefin, and [II] R ^a ₃ SiOR ^b [in the formula, R ^a The group is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and OR ^b is a methoxy group or an ethoxy group], and optionally a [III] organoaluminum compound, It is characterized by consisting of.

Furthermore, according to a preferred embodiment of the present invention,
The above (D) electron donor is R ^a ₃ SiOR ^b (wherein R ^a is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and OR ^b is a methoxy group or an ethoxy group). It is a monoalkoxysilane compound shown. Further, the present invention relates to a method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of these polymerization catalysts.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and olefin polymerization method according to the present invention will be specifically described below.

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" refers to not only homopolymer but also copolymer. May also be used in the sense of including.

First, the solid titanium catalyst component (A) used when forming the olefin polymerization catalyst according to the present invention will be described. The solid titanium catalyst component used in the present invention contains at least magnesium, titanium, halogen and polyether as essential components. The solid titanium catalyst component is not limited in its preparation method as long as it contains these components, and the (a-1) magnesium compound,
It can be prepared by bringing the (a-2) titanium compound and (a-3) polyether into contact with each other by various methods. The components used when preparing the solid titanium catalyst component are shown below.

(A-1) Magnesium compound In the present invention, examples of the magnesium compound include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

Examples of the magnesium compound having a reducing ability include organomagnesium compounds represented by the following formula. X ^a _p MgR ^c _{2-p In the} formula, p is 0.
≦ p <2, R ^c is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group,
When p is 0, two R ^c may be the same or different. X ^a is a halogen or an alkoxy group.

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

Specific examples of the magnesium compound having no reducing ability are magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, magnesium methoxy chloride, magnesium ethoxy chloride, and isopropoxy magnesium chloride. , Butoxy magnesium chloride, alkoxy magnesium halides such as octoxy magnesium chloride, phenoxy magnesium chloride, allyloxy magnesium halides such as methylphenoxy magnesium chloride, diethoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, di n-octoxy magnesium, di
2-ethylhexoxy magnesium, alkoxy magnesium such as ethoxymethoxy magnesium, diphenoxy magnesium, allyloxy magnesium such as dimethylphenoxy magnesium, magnesium laurate,
Mention may be made of magnesium carboxylates such as magnesium stearate. In addition, magnesium metal and magnesium hydride can also be used.

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

The above-mentioned magnesium compound having a reducing ability and the magnesium compound having no reducing ability form a complex compound or a complex compound with another metal such as aluminum, zinc, boron, beryllium, sodium or potassium. Or may be a mixture with other metal compounds. Furthermore, the magnesium compound may be a single compound, or two or more of the above compounds may be combined.

As the magnesium compound used for preparing the solid titanium catalyst component, magnesium compounds other than those mentioned above can be used, but they are present in the form of halogen-containing magnesium compound in the finally obtained solid titanium catalyst component. Therefore, when a magnesium compound containing no halogen is used, it is preferable to react it with a halogen-containing compound during the preparation.

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

In the present invention, when the solid titanium catalyst component is prepared, the magnesium compound (a-1) as described above is used.
Is preferably used in a liquid state. When the magnesium compound is a solid among the above magnesium compounds, it can be made into a liquid state by using the electron donor (a-4).

Examples of the electron donor (a-4) include alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines, etc. which will be described later as the electron donor (a-6). Can be used.

It is also possible to use metal acid esters such as tetraethoxy titanium, tetra-n-propoxy titanium, tetra-i-propoxy titanium, tetrabutoxy titanium, tetrahexoxy titanium, tetrabutoxy zirconium, tetraethoxy zirconium and the like. .

Of these, alcohols and metal acid esters are particularly preferably used. The reaction between the solid magnesium compound and the electron donor (a-4) is carried out by bringing the solid magnesium compound and the electron donor (a-4) into contact with each other.
The method of heating as needed is common. This contact is usually carried out at a temperature of 0 to 200 ° C, preferably 20 to 180 ° C, more preferably 50 to 150 ° C.

The above reaction may be carried out in the coexistence of a hydrocarbon solvent (a-5). Specific examples of such a hydrocarbon solvent include pentane, hexane, heptane, octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, Alicyclic hydrocarbons such as cyclohexene, halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene and chlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene are used.

(A-2) Titanium Compound In the present invention, a liquid titanium compound is preferable as the titanium compound (a-2), and a tetravalent titanium compound is particularly preferably used. As such a tetravalent titanium compound,
The compound represented by the following formula can be mentioned.

Ti (OR^d)_gX^b _4-gWhere R^dIs a hydrocarbon
The group, X^bIs a halogen atom, and 0 ≦ g ≦ 4
It Specific examples of such a compound include TiC
l_Four, TiBr_Four, TiI_Four Titanium tetrahalide, such as
Ti (OCH₃) Cl₃, Ti (OC₂H_Five) Cl₃, Ti (O-n-C
_FourH₉) Cl₃, Ti (OC₂H_Five) Br₃, Ti (O-iso-C_FourH₉)
Br ₃Trihalogenated alkoxy titanium such as Ti (OC
H₃)₂Cl₂, Ti (OC₂H_Five)₂Cl₂, Ti (O-n-C_FourH₉)₂
Cl₂, Ti (OC₂H_Five)₂Br₂Dihalogenated dialco such as
Xytitanium, Ti (OCH₃)₃Cl, Ti (OC₂H_Five)₃ Cl
 , Ti (O-n-C_FourH₉)₃ Cl, Ti (OC₂H_Five)₃ Br
Which monohalogenated trialkoxy titanium, Ti (OCH
₃)_Four, Ti (OC₂H_Five)_Four , Ti (O-n-C_FourH₉)_Four , Ti
(O-iso-C_FourH₉)_Four , Ti (O-2-ethylhexyl)_FourNa
Examples include any tetraalkoxy titanium.

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

(A-3) Polyether When preparing a solid titanium catalyst component, a polyether is used as an electron donor. As the polyether, a compound having two or more ether bonds existing via a plurality of atoms can be used.

Specifically, as such a polyether, the atoms existing between the ether bonds are carbon, silicon,
Examples thereof include oxygen, nitrogen, phosphorus, boron, sulfur, and compounds of two or more selected from these. Of these, a compound in which a relatively bulky substituent is bonded to an atom between ether bonds, and a compound in which a plurality of carbon atoms are contained in atoms existing between two or more ether bonds is preferable,
For example, the polyether represented by the following formula is preferable.

[0033]

[Chemical 1]

(Where n is an integer of 2≤n≤10,
R ^{1 to} R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any R ^{1 to} R ²⁶ ,
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ) Specific examples of the above-mentioned polyether compound include 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxy. Propane, 2-s
-Butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2- (2-phenylethyl) ) -1,3-Dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3 -Dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3
-Dimethoxypropane, 2- (pt-butylphenyl)
-1,3-dimethoxypropane, 2,2-dicyclohexyl-
1,3-dimethoxypropane, 2,2-dicyclopentyl-1,
3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl- 1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxy Propane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-
Methyl-2-phenyl-1,3-dimethoxypropane, 2-
Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl)-
1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3 -Dimethoxypropane, 2,2-diphenyl-
1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-
1,3-diethoxypropane, 2,2-diisobutyl-1,3-
Dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl)
-2-isopropyl-1,3-dimethoxypropane, 2- (1
-Methylbutyl) -2-s-butyl-1,3-dimethoxypropane, 2,2-di-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane ,
2,2-Dineopentyl-1,3-dimethoxypropane, 2-
Isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-benzyl-2 -Isopropyl-1,3-
Dimethoxypropane, 2-benzyl-2-s-butyl-1,3
-Dimethoxypropane, 2-phenyl-2-benzyl-1,
3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxy Propane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxy Propane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-
1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3-bis (p-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p-fluorophenyl)-
1,4-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4- Diisobutyl-1,5-dimethoxypentane, 2,
4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3 −
Diisoamyloxypropane, 1,3-Diisoneopentyloxyethane, 1,3-Dineopentyloxypropane, 2,2-
Tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2 , 8-Dioxaspiro [5,
5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-
Diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2, 2,1] heptane, 1,1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3
-Dimethoxycyclohexane, 2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3
-Dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-
1,3-dimethoxycyclohexane, 2-isopropyl-2
-Ethoxymethyl-1,3-diethoxycyclohexane, 2
-Isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-
1,3-diethoxycyclohexane, 2-isobutyl-2-
Ethoxymethyl-1,3-dimethoxycyclohexane and the like can be mentioned. Also, as a polyether, Tris (p
-Methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis (methoxymethyl) silane, cyclohexyl-t-butylbis (methoxy) Methyl) silane, i-propyl-t-butylbis (methoxymethyl) silane and the like can also be mentioned.

Of these, 1,3-diethers are preferably used, particularly 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-
1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxy Propane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2-cyclopentyl 2-isopropyl-1,3-dimethoxypropane and the like are preferably used. These two
You may use it in combination of 2 or more types.

When preparing the solid titanium catalyst component,
In addition to the above-mentioned polyether (a-3), other electron donor (a-6) can be used if necessary. Specific examples of the other electron donor (a-6) include alcohols,
Phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, polyhydric alcohol esters, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds , An oxygen-containing cyclic compound and the like can be used.

Further, as the electron donor (a-6), an organosilicon compound as described below, water, or an anionic, cationic or nonionic surfactant may be used as a catalyst component.

Two or more kinds of these electron donors (a-6) can be used in combination. Preparation of Solid Titanium Catalyst Component (A) In preparing the solid titanium catalyst component, in addition to the above compounds, an organic compound or inorganic material containing silicon, phosphorus, aluminum, etc., used as a carrier, a reaction aid, etc. A compound or the like may be used.

Examples of such a carrier include Al₂O₃ , S_i
O₂ , B₂O₃ , M_gO, C_aO, T_iO ₂ , Z_nO, S_n
O₂ , B_aO, ThO, styrene-divinylbenzene co-weight
Examples include resins such as coalesced materials. Among these,
Al₂O₃ , S_iO₂ , Styrene-divinylbenzene copolymer
Coalescence is preferably used.

The solid titanium catalyst component (A) includes the magnesium compound (a-1) and the titanium compound (a) as described above.
-2) and polyether (a-3) can be prepared by contacting, and can be prepared by any method including known methods, the preparation method is not particularly limited, in the present invention, It is preferable to contact the liquid magnesium compound (a-1), the liquid titanium compound (a-2) and the polyether (a-3).

When the solid titanium catalyst component is prepared by bringing these compounds (a-1) to (a-3) into contact with each other, a hydrocarbon can be used if necessary, and the hydrocarbon can be magnesium. Examples thereof include the same hydrocarbon solvents as those used for liquefying the compound (a-1).

The specific preparation method of the solid titanium catalyst component will be briefly described below by giving some examples. In the following method, as the organoaluminum compound, those described below as the organoaluminum compound (B) are used.

(1) Magnesium compound, electron donor (a
-4) and a liquid state magnesium compound (a-1) consisting of a hydrocarbon solvent are contact-reacted with an organoaluminum compound to precipitate a solid, or while being precipitated, a titanium compound (a-2) is contact-reacted. Let

In this process, the polyether (a-3)
Is contacted with the contact product at least once. (2) The titanium compound (a-2) and the polyether (a-3) are contact-reacted with the contact product of the inorganic carrier and the organomagnesium compound (a-1).

At this time, the contact product of the inorganic carrier and the organomagnesium compound (a-1) may be previously reacted with the halogen-containing compound and / or the organoaluminum compound. (3) A magnesium compound, an electron donor (a-4), or a mixture of a magnesium compound (a-1) in a liquid state optionally containing a hydrocarbon solvent and an inorganic carrier or an organic carrier, A supported inorganic or organic carrier is prepared and then a titanium compound is added thereto.
Contact (a-2).

In this process, the polyether (a-3)
Is contacted with the contact product at least once. (4) Magnesium compound (a-1), titanium compound (a-2), electron donor (a-4) A solution containing a hydrocarbon solvent in some cases, an inorganic carrier or an organic carrier, and a polyether (a- 3)
Contact with.

(5) Liquid-state organomagnesium compound
(a-1) is contacted with a halogen-containing titanium compound (a-2) and a polyether (a-3). (6) The organomagnesium compound (a-1) in the liquid state is contact-reacted with the halogen-containing compound, and then the titanium compound (a-2) is contacted.

In this process, the polyether (a-3)
Is used at least once. (7) The alkoxy group-containing magnesium compound (a-1) is replaced with a halogen-containing titanium compound.
Catalytic reaction with (a-2) and polyether (a-3).

(8) A liquid magnesium compound (a-1) consisting of an alkoxy group-containing magnesium compound and an electron donor (a-4) was added to a titanium compound (a-2) and a polyester.
Contact reaction with ter (a-3).

(9) A liquid magnesium compound (a-1) consisting of an alkoxy group-containing magnesium compound and an electron donor (a-4) is brought into contact with an organoaluminum compound, and then a titanium compound (a-2). Contact with. In this process, the polyether (a-3) is contacted with the contact product at least once.

(10) A liquid magnesium compound (a-1) having no reducing ability and a titanium compound (a-2) were mixed with a polyester compound.
Contact is made in the presence or absence of ter (a-3). In this process, at least 1 part of polyether (a-3) was added.
Contact with the contact product.

(11) A titanium compound (a-2) is further brought into contact with the reaction products obtained in (1) to (10). (12)
The reaction products obtained in (1) to (11) are further contacted with polyether (a-3) and titanium compound (a-2).

The contact of each component as described above is usually -70.
C. to 200.degree. C., preferably -50.degree. C. to 150.degree. C., more preferably -30 to 130.degree.

The amount of each component used in preparing the solid titanium catalyst component varies depending on the preparation method and cannot be specified unconditionally, but, for example, per 1 mol of the magnesium compound,
The amount of the polyether (a-3) is 0.01 to 10 mol, preferably 0.1 to 5 mol, and the titanium compound (a-2) is in a liquid state.
Can be used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol.

In the present invention, the solid titanium catalyst component thus obtained is preferably washed with a hydrocarbon solvent at 0 to 150 ° C. As the hydrocarbon solvent, the hydrocarbon solvent (a-5) as shown above when liquefying the magnesium compound can be used, and among these, an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent can be used. Is preferably used.

When washing the solid titanium catalyst component,
The hydrocarbon solvent is usually 10 to 500 per 1 g of the solid matter.
It can be used in an amount of about ml. The solid titanium catalyst component (A) thus obtained is magnesium,
Contains titanium, halogen and polyether,
0.3 to 10% by weight of titanium, preferably 0.5 to 8% by weight
The total amount of magnesium and halogen is 10 to 95
It is desirable to include the polyether in an amount of 0.5% to 30% by weight.

(B) Organoaluminum Compound In the present invention, the organoaluminum compound used in forming the olefin polymerization catalyst is represented by the following formula, for example.

R ^e _q AlX ^c _3-q (wherein R ^e is a hydrocarbon group having 1 to 12 carbon atoms, X ^c is halogen or hydrogen, and q is 1 to 3) R ^e Has 1 to 1 carbon atoms
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, Examples include a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group. As such an organoaluminum compound,
Specifically, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri 2
-Trialkylaluminum such as ethylhexylaluminum, alkenylaluminum such as isoprenylaluminum, dimethylaluminium chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum. Sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride,
Alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, and alkyl aluminum hydrides such as diisobutyl aluminum hydride. .

Further, as the organic aluminum compound,
A compound represented by the formula may also be mentioned. R^f _r AlY
_3-rIn the above formula, R^f Is R above^eIs similar to
-OR ^g Group, -OS_iR^h ₃Group, -OAlRⁱ ₂ Group, -NR
^j ₂ Group, -S_iR^k ₃ Group or -N (R^l ) AlR^m ₂ On the basis
Yes, r is 1-2, R^g , R^h , Rⁱ And R^m
Is methyl group, ethyl group, isopropyl group, isobutyl
Group, cyclohexyl group, phenyl group, etc., R^j Is
Hydrogen, methyl group, ethyl group, isopropyl group, phenyl
Group, trimethylsilyl group, etc., R^k And R^l Is
Examples include a methyl group and an ethyl group.

Specific examples of such an organoaluminum compound include the following compounds.
_{^{(i) R f r Al (}} OR g) 3-r dimethyl aluminum methoxide, diethyl aluminum ethoxide, and diisobutyl aluminum methoxide, (ii) _R ^f _{r
^{Al (OSiR h) 3-r}} Et 2 Al (OS i Me 3), (iso-B
_{u) 2 Al (OS i Me} 3), (iso-Bu) 2 Al (OS i Et 3)
(Iii) R ^f _r Al (OAlR ⁱ ₂ ) _3-r Et ₂ AlO
AlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc.,
(iv) R ^f _r Al (NR ^j ₂ ) _3-r Me ₂ AlNEt ₂ , Et ₂
AlNHMe, Me ₂ AlNHEt, EtAlN (Me ₃ S
i) ₂ , (iso-Bu) ₂ AlN (Me ₃ Si) _2, etc., (v) R ^f _r
Al (SiR ^k ₃ ) _3-r (iso-Bu) ₂ AlSiMe ₃ etc., (vi)
R ^f _r Al [N (R ^l ) -Al R ^m ₂ ] _3-r Et ₂ Al N (M
_{e) -AlEt 2 (iso-Bu} ) 2 AlN (Et) Al (iso-Bu)
₂ and so on.

Further compounds similar to this, such as acids
Two or more aluminum atoms are bonded through elementary and nitrogen atoms
The organoaluminum compounds mentioned above can also be mentioned. Yo
Specifically, (C₂H_Five)₂AlOAl (C₂H_Five)₂ ,
(C_FourH₉)₂AlOAl (C_FourH₉) ₂ , (C₂H_Five)₂Al
N (C₂H_Five) Al (C₂H_Five)₂And more methylal
Aluminoxanes such as minoxane can be mentioned.
It

Among the above organoaluminum compounds, R ^f ₃ Al, R ^f _r Al (OR ^g ) _3-r , and R ^f _r Al
An organoaluminum compound represented by (OA1R ⁱ ₂ ) _3-r is preferably used.

As the organoaluminum compound, a complex alkyl compound represented by the following general formula can be used. M ¹ AlR ^s ₄ (M ¹ is Li, Na, K, R ^s
Is a hydrocarbon group having 1 to 15 carbon atoms) Specifically, L
Examples thereof include iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Two or more of these compounds can be used in combination. (C) Monoalkoxysilane compound In the present invention, the solid titanium catalyst component (A) as described above is used.
When forming an olefin polymerization catalyst from the above and the organoaluminum compound (B), a monoalkoxysilane compound represented by the following general formula (1) is used.

R ^a ₃ Si (OR ^b ) ... In the formula (1), O
The R ^b group is a methoxy group or an ethoxy group. The R ^a group is
An alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, specifically methyl, ethyl, (n-, i
-) Propyl, (n-, I-, t-) butyl, pentyl,
Hexyl, heptyl, (n-, I-) octyl, nonyl,
C1-C12 linear or branched alkyl groups such as decyl and thexyl (2,3-dimethyl-2-butyl), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. Is a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 21 carbon atoms such as phenyl, tolyl, biphenylyl and naphthyl, and an aralkyl group having 7 to 16 carbon atoms such as benzyl and α-methylbenzyl.

These groups may have a substituent such as halogen and amino group. Specific examples of such a monoalkoxysilane compound compound include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, tri (n-propyl) methoxysilane, tri (isopropyl) methoxysilane and tri (n). -Propyl) ethoxysilane, tri (n-butyl) methoxysilane, tri (isobutyl) methoxysilane, tri (isobutyl) ethoxysilane, dimethyl tert-butylmethoxysilane, dimethylisobutylmethoxysilane, dimethylcyclopentylmethoxysilane, dimethylcyclohexylethoxysilane And so on. Among these, trialkylmethoxysilane compounds are preferably used.

Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises the solid titanium catalyst component (A) containing a polyether as an internal donor as described above.
It is formed from (B) an organoaluminum compound and (C) a monoalkoxysilane compound represented by the formula (1).
FIG. 1 shows a process for preparing such an olefin polymerization catalyst.

In the present invention, the prepolymerized catalyst [I] can be formed by preliminarily (co) polymerizing the olefins with the above catalyst component. Specifically, [I] the solid state of (A) above. A prepolymerization catalyst in which an olefin is prepolymerized in a catalyst for olefin polymerization, which comprises a titanium catalyst component, (B) an organoaluminum compound, and (D) an electron donor as required, and [II] the above monoalkoxysilane An olefin polymerization catalyst can be formed from the compound and, if necessary, the [III] organoaluminum compound.

This monoalkoxysilane compound [II]
Is a monoalkoxysilane compound represented by the formula (1), and the organoaluminum compound [III] is exemplified as the organoaluminum compound (B).

An electron donor (D) can be used, if necessary, during the prepolymerization. This electron donor (D)
As the above, specifically, the above-mentioned monoalkoxysilane compounds can be used, and other electron donors can also be used. In the present invention, when the above-mentioned monoalkoxysilane compound is used as the electron donor (D) in the prepolymerization, the monoalkoxysilane [I
The use of [I] may be omitted.

Other electron donors include, for example, the above-mentioned polyether compounds, 2,6-substituted piperidines,
2,5-Substituted piperidines, substituted methylenediamines such as N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetraethylmethylenediamine, 1,3-
Dibenzyl imidazolidine, 1,3-dibenzyl-2-
Nitrogen-containing electron donors such as substituted imidazolidines such as phenylimidazolidine, triethylphosphite, tri
n-Propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, phosphorus-containing electron donors such as phosphorous acid esters such as diethyl phenyl phosphite, 2, It is also possible to use oxygen-containing electron donors such as 6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans, and further, as another electron donor, an organosilicon compound other than the above monoalkoxysilane compound (C). It can also be used. Specific examples of the other organic silicon compound include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysisilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane,
Phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-
m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxy Silane, di (3
-Methylcyclopentyl) dimethoxysilane, di-t-
Amyldimethoxysilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxysilane, methyltriallyloxy (allyloxy) silane,
Examples thereof include chlorotriethoxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, ethyl silicate and butyl silicate. Two or more of these may be used in combination.

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

The α-olefin used in the prepolymerization is
It may be the same as or different from the α-olefin used in the main polymerization described later. In the present invention, the method for carrying out the prepolymerization is not particularly limited, and for example, it can be carried out in a state where the olefins and polyene compounds are in a liquid state,
Further, it can be carried out in the coexistence of an inert solvent, and further it can be carried out under gas phase conditions. Of these, it is preferable to carry out prepolymerization under relatively mild conditions by adding olefins and respective catalyst components to the inert solvent in the presence of an inert solvent. At this time, it may be carried out under conditions in which the formed prepolymer is dissolved in the polymerization medium or may be dissolved therein, but it is preferably carried out under conditions in which it is not dissolved.

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

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. Although the concentration of the catalyst component in the prepolymerization varies depending on the type of the catalyst component, the concentration of the solid titanium catalyst component (A) is
It is usually about 0.001 to 5000 mmol, preferably about 0.01 to 1 in terms of titanium atom, per liter of polymerization volume.
000 millimole is particularly preferred, and 0.1 to 500 millimole is desirable.

The organoaluminum compound (B) is usually about 0.1 to 1000 mol, preferably about 0.5 to 500 mol, particularly preferably 1 to 100 mol, per mol of titanium in the solid titanium catalyst component (A). Can be used in any amount.

During the prepolymerization, the electron donor (D)
Is used in an amount of usually 0.01 to 50 mol, preferably 0.05 to 30 mol, and more preferably 0.1 to 10 mol, per 1 mol of titanium atom in the solid titanium catalyst component (A), if necessary. You can

At the time of prepolymerization, a molecular weight modifier such as hydrogen can be used. In the prepolymerization as described above, 0.01 to 2000 per 1 g of the solid titanium catalyst component (A).
g preferably 0.03 to 1000 g, more preferably 0.03 g.
05-200 g of preliminary (co) polymer can be produced.

When the prepolymerized catalyst is obtained in a suspended state, the prepolymerized catalyst can be used in the suspended state in the (main) polymerization of the next step, or the prepolymerized catalyst produced from the suspension can be used. The polymerization catalyst can also be used separately. The olefin polymerization catalyst according to the present invention may contain other components useful for olefin polymerization, in addition to the above components.

Method for Polymerizing Olefin In the method for polymerizing an olefin according to the present invention, a solid titanium catalyst component (A) containing a polyether as an internal donor as described above, (B)
Olefin polymerization catalyst comprising an organoaluminum compound and (C) monoalkoxysilane compound, or [I] prepolymerization catalyst, for olefin polymerization comprising a [II] monoalkoxysilane compound and optionally [III] organoaluminum compound The olefin is polymerized or copolymerized in the presence of a catalyst.

By polymerizing an olefin using such an olefin polymerization catalyst, a polyolefin having a wide molecular weight distribution and excellent moldability can be obtained. Specific examples of the olefin to be polymerized in the present invention include α-olefins having 2 or more carbon atoms as shown in the prepolymerization.

Further, cyclopentene, cycloheptene,
Norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,
Cycloolefins such as 4,4a, 5,8,8a-octahydronaphthalene, styrene, dimethylstyrenes, allylnaphthalene, allylnorbornane, vinylnaphthalene, allyltoluenes, allylbenzene, vinylcyclopentane, vinylcyclohexane, vinylcyclo Vinyl compounds such as heptane and allyltrialkylsilanes can also be used.

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

Particularly in the present invention, by polymerizing propylene, polypropylene having high stereoregularity can be obtained.
When the above olefin is copolymerized, an olefin copolymer having a narrow composition distribution can be obtained.

The decane-soluble component content of the polyolefin can be used as an index of such stereoregularity and composition distribution characteristics. Further, the boiling heptane extraction residual rate can be used as an index of stereoregularity.

It is also possible to copolymerize a small amount of a diene compound with an olefin. Specific examples of such a diene compound include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4- Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6- Propyl-1,6
-Octadiene, 6-butyl-1,6-octadiene, 6-
Methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7- Methyl-
1,6-decadiene, 6-methyl-1,6-undecadiene,
Examples thereof include 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene. You may use these in combination of 2 or more types.

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

In the polymerization, the solid titanium catalyst component (A) or the prepolymerization catalyst [I] is usually converted into titanium atom per 1 liter of the polymerization volume, usually about 0.001-1.
It can be used in an amount of 00 mmol, preferably about 0.005 to 20 mmol.

In the organoaluminum compound (B) (or [III]), the aluminum atom in the organoaluminum compound is usually about 1 to 2000 mol, preferably about 2 to 500 mol, per 1 mol of the titanium atom in the polymerization system. Can be used in an amount such that

The monoalkoxysilane compound (C) (or [II]) is generally used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, per 1 mol of aluminum atom of the organoaluminum compound. Can be used.

When the prepolymerization catalyst [I] is used, the organoaluminum compound [III] may not be used in some cases. Further, when forming an olefin polymerization catalyst containing a prepolymerization catalyst, an organoaluminum compound [III]
When [3] is used, the [III] and the organoaluminum compound (B) at the time of preparing the prepolymerization catalyst may be the same compound or different. When an olefin polymerization catalyst is formed from a prepolymerization catalyst prepared using a monoalkoxysilane compound (C), the monoalkoxysilane compound (C) and the monoalkoxysilane compound [II] are the same compound. Or may be different.

If hydrogen is used during the polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained. In the olefin polymerization method according to the present invention, the polymerization is usually carried out at a temperature of about 20 to 300 ° C., preferably about 50 to 150 ° C., and a normal pressure to 100 kg / cm 2, though it depends on the kind of olefin, the form of the polymerization and the like.
It is preferably carried out under a pressure of about 2 to 50 kg / cm @ 2.

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

In the present invention, an olefin homopolymer may be produced, or a random copolymer or a block copolymer may be produced from two or more kinds of olefins. According to the present invention, a highly stereoregular polyolefin, particularly polypropylene, can be obtained, and the polypropylene obtained in the present invention has a small amount of decane-soluble component at 23 ° C., for example, the decane-soluble component content at 23 ° C. is 1.1. It is preferably not more than 1.0% by weight, more preferably not more than 1.0% by weight, particularly preferably not more than 0.95% by weight.

[0095]

The olefin polymerization catalyst of the present invention formed from a solid titanium catalyst component containing a polyether as an internal donor, an organoaluminum compound, and a monoalkoxysilane compound as an external donor as described above,
A polyolefin having a low content of decane-soluble components and excellent stereoregularity can be obtained with high polymerization activity.

[0096]

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

[0097]

[Example 1] "Preparation of solid titanium catalyst component (A)" 7.14 g (75 mmol) of anhydrous magnesium chloride, 36.2 ml of decane and 2-ethylhexyl alcohol 3
4.7 ml (225 mmol) were mixed and the mixture was mixed at 130 ° C. for 4 minutes.
Heated for a period of time to give a homogeneous solution. In this homogeneous solution, 2-
1.90 g (9.38 mmol) of isopropyl-2-isobutyl-1,3-dimethoxypropane were added and 110
The mixture was stirred and mixed at 0 ° C. for another hour to dissolve it, and then cooled to room temperature. The homogeneous solution thus obtained is -20
The entire amount was dropped into 200 ml of titanium tetrachloride (TiCl ₄ ) kept at ℃ over 45 minutes. After dropping, the temperature of the obtained solution was raised to 110 ° C over 4 hours, and the temperature was changed to 110 ° C.
When the temperature reached, 1.37 g (6.75 mmol) of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was added. The mixture was stirred for another 2 hours at the above temperature. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration,
After resuspending this solid part with 250 ml of TiCl ₄ ,
It was heated again at 110 ° C. for 2 hours. After completion of the reaction, a solid part was collected by hot filtration and washed with decane and hexane at 90 ° C. This washing was performed until no titanium compound was detected in the washing liquid. A hexane slurry of the solid titanium catalyst component (A) was obtained as described above. A part of the solid titanium catalyst component (A) (hexane slurry) was collected and dried, and the composition of this catalyst component was analyzed. The solid titanium catalyst component (A) is composed of 2.8% by weight of Ti, 18.0% by weight of Mg, 57.0% by weight of C1, 0.8% by weight of 2-ethylhexoxy group and 2-isopropyl-
2-Isobutyl-1,3-dimethoxypropane 19.0% by weight
Contained.

"Main Polymerization" 400 ml of purified heptane was charged into an autoclave having an internal volume of 1 liter, and 0.4 mmol of triethylaluminum, 0.4 mmol of tri-n-propylmethoxysilane and the above-mentioned were added at 60 ° C in a propylene atmosphere. 0.004 mmol of the solid titanium catalyst component (A) obtained in the above was charged in terms of titanium atom, 75 ml of hydrogen was added, the temperature was raised to 70 ° C., and this was kept for 1 hour to polymerize propylene. Let During the polymerization, the pressure is 0.5
It was kept at MPa. After completion of the polymerization, the slurry containing the produced polymer was filtered to separate into a white powder and a liquid phase part. The yield of the white powdery polymer after drying was 91.8 g, the extraction residual rate (II) with boiling heptane was 98.6%, and the MFR was 5.1 g /
After 10 minutes, the apparent bulk specific gravity was 0.42 g / ml. On the other hand, concentration of the liquid phase portion gave 0.4 g of a solvent-soluble polymer. Therefore, the activity is 23000 g-PP / mmol-Ti,
It was 12800 g-PP / g-cat. II (t-II) in the whole obtained polymer was 98.2%. The results are shown in Table 1.

[0099]

Example 2 "Main Polymerization" The procedure of Example 1 was repeated except that 0.4 mmol of triethylmethoxysilane was used instead of 0.4 mmol of tri-n-propylmethoxysilane. The results are shown in Table 1.

[0100]

Example 3 "Main Polymerization" The procedure of Example 1 was repeated, except that 0.4 mmol of trimethylmethoxysilane was used instead of 0.4 mmol of tri-n-propylmethoxysilane. The results are shown in Table 1.

[0101]

Example 4 "Main Polymerization" The same procedure as in Example 1 was carried out except that 0.4 mmol of triisobutylethoxysilane was used instead of 0.4 mmol of tri-n-propylmethoxysilane. The results are shown in Table 1.

[0102]

Comparative Example 1 "Main Polymerization" The same procedure as in Example 1 was carried out except that 0.4 mmol of tri-n-propylmethoxysilane was not used. The results are shown in Table 1.

[0103]

Comparative Example 2 "Main Polymerization" The procedure of Example 1 was repeated except that 0.4 mmol of dimethyldimethoxysilane was used instead of 0.4 mmol of tri-n-propylmethoxysilane. The results are shown in Table 1.

[0104]

Comparative Example 3 "Main Polymerization" Example 1 except that 0.4 mmol of di-n-butyldimethoxysilane was used instead of 0.4 mmol of tri-n-propylmethoxysilane.
I went in the same way. The results are shown in Table 1.

[0105]

Comparative Example 4 "Main Polymerization" Example 1 except that 0.4 mmol of n-propyltrimethoxysilane was used instead of 0.4 mmol of tri-n-propylmethoxysilane.
I went in the same way. The results are shown in Table 1.

[0106]

Comparative Example 5 "Main Polymerization" The same procedure as in Example 1 was carried out except that 0.4 mmol of methyltriethoxysilane was used instead of 0.4 mmol of tri-n-propylmethoxysilane. The results are shown in Table 1.

[0107]

[Table 1]

[0108]

Example 5 "Preliminary Polymerization" 100 ml of purified hexane was placed in a 200 ml glass reactor which had been purged with nitrogen, and 0.6 mmol of triethylaluminum and the solid titanium catalyst component obtained in Example 1 were converted into titanium. After charging 0.2 mmol, propylene was fed for 1 hour at a rate of 1.0 liter / hour. After the completion of propylene supply, the solid portion obtained by filtration was washed twice with purified hexane,
The resulting prepolymerized catalyst was resuspended in decane. [Main Polymerization] The same operation as in Example 1 was carried out except that the prepolymerized catalyst obtained above was used. As a result, the activity was 12,4.
00g-PP / g-Cat, t-II is 98.4%, MFR is 4.8g / 10 minutes, and bulk specific gravity is 0.
It was 44 g / ml.

[Brief description of drawings]

FIG. 1 shows an example of a process for preparing an olefin polymerization catalyst according to the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J028 AA01A AB01A AC02A BA01A                       BA01B BB00A BB01B BC04A                       BC14B CB91C DA01 DA02                       DA03 DA04 DA06 EB01 EB21                       EC01 EC02 FA02 FA03 FA04                       GA07 GA09 GB02

Claims (4)

[Claims] 1. A solid titanium catalyst component comprising (A) magnesium, titanium, halogen and polyether (provided that
(Ester compounds are not included) (B) Organoaluminum compound, and (C) R ^a ₃ SiOR ^b [In the formula, R ^a is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and OR ^b is methoxy. A group or an ethoxy group], and a catalyst for olefin polymerization. 2. [I] (A) a solid titanium catalyst component containing magnesium, titanium, halogen and a polyether (excluding ester compounds) (B) an organoaluminum compound, and optionally (D ) A catalyst for olefin polymerization comprising an electron donor, a prepolymerization catalyst in which an olefin is prepolymerized, and [II] R ^a ₃ SiOR ^b [wherein R ^a is an alkyl group, a cycloalkyl group or an aryl group]. Or an aralkyl group, and OR ^b is a methoxy group or an ethoxy group], and, if necessary, [III] an organoaluminum compound. . 3. The (D) electron donor is R ^a ₃ SiOR ^b [wherein R ^a is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and OR ^b is a methoxy group or an ethoxy group]. The catalyst for olefin polymerization according to claim 2, which is a monoalkoxysilane compound represented by [1]. 4. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.