JPH1036430A - Production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low-fine-powder-content stereoregular polymer, especially a propylene polymer, having a density of 0.900-0.906 in high yields by performing the polymerization of an olefin in a specified manner by using a specified solid catalyst component, a specified organoaluminum compound and a specified organosilicon compound. SOLUTION: In a process for polymerizing an olefin in the presence of a catalyst comprising a solid catalyst component (A) containing Mg, Ti, an electron-donating compound, Al and a halogen, an organoaluminum compound (B) represented by formula I and an organosilicon compound (C) represented by formula II, components B and A are brought into contact with each other in the presence of an inert hydrocarbon solvent containing 0.01-1.0g, per g of component A, of a dissolved olefin (the amount of component B used is 0.5-50mol per Ti of component A), and the olefin is preliminary polymerized at 0-40 deg.C to form 1-20g, per g of component A, of a polymer, and the main polymerization is performed. In the formula, R<1> is a 1-4C alkyl; Y is H or the like; 0<q<=3; R<2> is a 1-12C alkyl or the like; R<3> is a 1-4C cycloalkyl or the like; and r is 0 or 1-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an olefin polymer. For more information,
The density of the olefin polymer, especially the propylene polymer, is 0.90
The present invention relates to a method for producing a stereoregular polymer having a content in the range of 0 to 0.906 g / ml in a high yield and having a low fine powder content.

[0002]

2. Description of the Related Art A method for producing an olefin polymer using a catalyst formed of a solid component containing magnesium, titanium, an electron-donating compound and a halogen, and a third component such as an organoaluminum compound and a silicon compound. Many proposals have been made and are well known.

[0003] For example, Japanese Patent Application Laid-Open No. 62-18406 discloses an olefin prepared by polymerizing 0.1 g or more of an olefin, using a specific catalyst comprising a combination of a solid catalyst component, an organoaluminum compound and a specific organosilicon compound. A method for making a polymer is disclosed.

JP-A-2-84404 discloses a solid titanium catalyst component containing magnesium, titanium and halogen as essential components, an organoaluminum compound and a cyclopentyl group, a cycloentenyl group, a cyclopentadienyl group or a mixture thereof. A method for polymerizing an olefin in the presence of an olefin polymerization catalyst formed from an organosilicon compound containing a derivative is disclosed.
It is also described that prepolymerization is performed before such polymerization is performed.

[0005] By the way, when each of the above-mentioned prior arts is used as a catalyst for olefin polymerization, the catalyst is so high that the catalyst residue such as chlorine or titanium remaining in the produced polymer is removed, that is, the so-called deashing step can be omitted. Starting with the development of active catalyst components,
At the same time, the present invention focuses on improving the yield of the stereoregular polymer and increasing the persistence of the polymerization activity during the polymerization, and has achieved excellent results for the purpose.

When olefins, especially propylene, are polymerized by the slurry method in the presence of the above-mentioned high-activity type catalyst, the conventional titanium trichloride-type solid catalyst component, the organoaluminum compound and the third component are used. Compared to using a catalyst formed from an electron-donating compound, the yield of the produced polymer is higher and its stereoregularity is better, but its density is higher than 0.906 g / ml There has been a problem that, when processed into a film or a sheet, problems such as breakage during high-speed molding and loss of transparency of the obtained molded product occur.

[0007] As means for solving such a problem, when the above-mentioned high activity type catalyst is used for the polymerization of olefins, especially propylene, a method of lowering the polymerization temperature or coexisting a small amount of ethylene as a comonomer has been tried. Thus, it is possible to control the density of the produced polymer to some extent.However, in the case of the slurry method, a low-molecular-weight polymer soluble in the polymerization solvent or, particularly, in the case of propylene polymerization, the stereoregularity is extremely low. An undesired phenomenon that the incidence of low attack polypropylene (hereinafter abbreviated as “attack incidence”) becomes high is induced.

[0008] When the rate of attack increases in the polymerization by the slurry method, a step of extracting the polymer particles after separation from the polymerization solvent is required, and in addition to the step of extracting the particles, the contamination of the reactor and the piping may be caused. In addition, there is a problem in the production cost of coalescing and stable operation, and when manufacturing multiple types of grades in one plant, there is a problem in controlling the product due to changes in operating conditions during continuous operation, and the operation of the process Had an unfavorable effect. In addition, when the amount of fine powder in the produced polymer, particularly fine powder having a particle diameter of 100 microns or less, increases, the clogging of the piping in the polymerization process, and the trouble in the polymer separation and drying steps may be caused. Met.

Accordingly, the present applicant has disclosed in Japanese Patent Application Laid-open No. Hei 8-3214.
JP-A-8-67711, in the polymerization of olefins, especially propylene by a slurry method using a solvent at the time of polymerization, while maintaining a high recovery of stereoregular polymer insoluble in the polymerization solvent, To propose a solid catalyst component and a catalyst for olefin polymerization which can easily produce a stereoregular polymer having a density of the produced polymer in the range of 0.900 to 0.906 g / ml, and to solve the above-mentioned problems of the prior art. Has an excellent effect on

[0010]

However, when the above-mentioned solid catalyst for olefin polymerization is subjected to olefin polymerization, particularly propylene polymerization, the heat of reaction at the beginning of the polymerization causes the catalyst to be degraded, whereby the catalyst activity is reduced. Decline,
A decrease in the stereoregularity of the resulting polymer and a polymer having a desired density cannot be obtained. Further, due to the destruction of particles of the solid catalyst component due to the heat of reaction, a large amount of fine powder is contained in the produced polymer, the particle size distribution tends to be broad, and the bulk specific gravity is further reduced. When the amount of the finely powdered polymer increases, it may hinder the continuation of the uniform reaction or cause a process obstruction such as blockage of the piping at the time of transferring the polymer. Have an unfavorable effect. Further, a decrease in the bulk specific gravity of the produced polymer directly leads to a decrease in productivity.

The present invention has been completed by conducting various studies in order to solve the problems left in the prior art as described above. The object of the present invention is to produce an attack when an olefin, particularly propylene, is subjected to polymerization. An olefin polymer which can produce a stereoregular polymer having a low yield and a density of the produced polymer in the range of 0.900 to 0.906 g / ml in a high yield, and which can produce a polymer having a small amount of fine powder. It is to provide a manufacturing method.

[0012]

The process for producing an olefin polymer according to the present invention for achieving the above object comprises the steps of (A)
A solid catalyst component containing magnesium, titanium, an electron donating compound, aluminum and halogen, (B) a general formula R
¹ _q AlY _{3-q wherein} R ¹ is an alkyl group having 1 to 4 carbon atoms, Y is hydrogen, chlorine, bromine, or iodine;
q is a real number satisfying 0 <q ≦ 3. ) And (C) a general formula R ² _r Si (OR ³ )
_4-r (wherein R ² is an alkyl group having 1 to 12 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.
³ is 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 may be the same or different. r is 0 or 1-3
Is an integer. In a method for polymerizing olefins using a catalyst comprising an organosilicon compound represented by the formula (1), one or more olefins are added to 1 g of the solid catalyst component (A).
The organic aluminum compound (B) and the solid catalyst component in the presence of 0.01 to 1.0 g of an inert hydrocarbon solvent
(A) and, per titanium atom in the solid catalyst component (A),
The organoaluminum compound (B) is contacted in the range of 0.5 to 50 mol, and then one or more olefins are added so that the amount of the produced polymer per 1 g of the solid catalyst component (A) is in the range of 1 to 20 g. The present invention is characterized in that main polymerization is performed after preliminary polymerization in the range of 0 to 40 ° C.

The solid catalyst component (A) [hereinafter sometimes referred to as “component (A)”] is an alkoxymagnesium,
It is obtained by bringing an aluminum halide compound, a titanium halide compound, an electron-donating compound and an organosilicon compound into contact with each other in suspension.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned alkoxymagnesium (hereinafter sometimes referred to as “component (a)”) used for the preparation of component (A) has the general formula Mg (OR ⁴ ) ₂ (where R ⁴ is And represents an alkyl group or an aryl group having 1 to 4 carbon atoms). Specifically, dimethoxymagnesium, diethoxymagnesium, di-n-propoxymagnesium, di-iso-propoxymagnesium, di-n-butoxymagnesium, di-iso-butoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxy- One or more of n-propoxymagnesium, n-butoxyethoxymagnesium, iso-butoxyethoxymagnesium and the like can be mentioned, and among them, diethoxymagnesium or di-n-propoxymagnesium is preferably used.

Further, the dialkoxymagnesium used for preparing the component (A) may be in the form of granules or powder, and the shape may be irregular or spherical. When spherical diethoxymagnesium 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 contained polymer powder is included. Troubles such as clogging caused by the fine powder are eliminated.

The above spherical diethoxymagnesium is
It is not necessarily required to be a true sphere, and an elliptical or potato-shaped one is used. Specifically, the degree of the spherical shape of the particles is represented by the ratio of the major axis diameter l to the minor axis diameter w, l / w,
3 or less, preferably from 1 to 2, and more preferably from 1 to 1.5.

The average particle diameter of the dialkoxymagnesium may be from 1 to 200 microns. Preferably, it is between 5 microns and 150 microns.

In the case of the above-mentioned spherical diethoxymagnesium, the average particle size is 1 micron to 100 microns, preferably 5 microns to 50 microns, more preferably 10 microns to 40 microns. Also,
As for the particle size, it is desirable to use a fine particle or coarse powder having a small particle size distribution. Specifically, particles of 5 microns or less are 20% or less, preferably 10% or less. 10% or less, preferably 5% or less of particles having a size of 100 microns or more. Further, the particle size distribution is expressed by ln (D90 / D10) (here, D90
Represents the particle size at an integrated particle size of 90%, and D10 represents the particle size at an integrated particle size of 10%.

The above dialkoxymagnesium does not necessarily have to be used as a starting material in the preparation of the component (A). For example, when preparing the component (A), the magnesium metal and the aliphatic monohydric alcohol having 1 to 4 carbon atoms may be used. May be used in the presence of a catalyst such as iodine.

The aluminum compound (hereinafter sometimes referred to as “component (b)”) used in the preparation of component (A) is at least one selected from the group consisting of aluminum compounds represented by the following general formulas I and II. Is a seed.

Al (OR ⁵ ) _m X _{3 -m} (general formula I) (wherein, R ⁵ is an alkyl group having 1 to 4 carbon atoms or a phenyl group or 1 to 2 alkyl groups having 1 to 3 carbon atoms) A substituted aralkyl group, when m is 2 or more, R ⁵ is the same or different, X represents a halogen element, and m is 0 ≦ m
≦ 3. )

R ⁶ _n AlX _3-n (general formula II) wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms, X is a hydrogen atom or a halogen element, and n is 0 <n ≦ 3. .)

Examples of the aluminum compound represented by the general formula I include aluminum trihalide, alkoxyaluminum dihalide, dialkoxyaluminum halide, and trialkoxyaluminum. Specific examples thereof include aluminum trichloride, aluminum tribromide, and aluminum tribromide. Triiodide, diethoxyaluminum chloride, di-iso-propoxyaluminum chloride, dibutoxyaluminum chloride, ethoxyaluminum dichloride, iso-propoxyaluminum dichloride, butoxyaluminum dichloride, trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, tri
-iso-propoxyaluminum, tributoxyaluminum, tri-iso-butoxyaluminum and the like, among which preferred substances are aluminum trichloride, di-iso-propoxyaluminum chloride, iso-
Propoxyaluminum dichloride, triethoxyaluminum, tri-iso-propoxyaluminum.

The aluminum compound represented by the general formula II includes trialkylaluminum, dialkylhydride, dialkylaluminum halide and alkylaluminum dihalide, and specific examples thereof include triethylaluminum, tri-iso-butylaluminum, diethyl Aluminum hydride, di-iso
-Butyl hydride, diethylaluminum chloride, di-iso-butylaluminum chloride, ethylaluminum dichloride, propylaluminum dichloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, etc., of which triethylaluminum and diethylaluminumchloride are preferred. , Ethyl aluminum dichloride and ethyl aluminum sesquichloride.

As the component (b), one or more compounds selected from the group of compounds of the above general formulas I and II can be used. The component (b) is used after being brought into direct contact with other components, or dissolved and diluted in an organic solvent such as an aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as hexane or heptane. You may.

The titanium halide compound (hereinafter sometimes referred to as “component (c)”) used in the preparation of component (A) of the present invention has the general formula Ti (OR ⁷ ) _p X _4-p (wherein , R ⁷
Is an alkyl group having 1 to 4 carbon atoms, X is a halogen element, and p is 0 or an integer of 1 to 3. ) Is a titanium halide or an alkoxy titanium halide. Specifically, as titanium tetrahalide, Ti
Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H) as Cl ₄ , TiBr ₄ , TiI ₄ , and alkoxytitanium halide
_{5) Cl 3, Ti (OC} 3 H 7) Cl 3, Ti (On-
C ₄ H ₉ ) Cl ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti
(OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) ₂ C
l ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ , Ti (OCH
₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC _{3
H 7) 3 Cl, Ti (} On-C 4 H 9) 3 Cl , and the like. Among these, titanium tetrahalide is preferable, and TiCl ₄ is particularly preferable. One or more of these titanium compounds may be used.
Furthermore, these components (c) may be used by dissolving and diluting them in an organic solvent such as an aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as hexane or heptane.

The electron-donating compound (hereinafter sometimes referred to as “component (d)”) used in the preparation of component (A) includes alcohols, ethers, esters, aldehydes, ketones, amines, Acid halides, nitriles and the like can be used, and among them, aromatic carboxylic acid diester is particularly preferably used.

As the aromatic carboxylic acid diester, a linear or branched alkyl diester of phthalic acid having 1 to 12 carbon atoms is particularly preferable. Specific examples of the diester include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso
-Butyl phthalate, ethyl methyl phthalate, butyl ethyl phthalate, methyl (iso-propyl) phthalate, ethyl-n-propyl phthalate, ethyl-n-
Butyl phthalate, di-n-pentyl phthalate, di-
iso-pentyl phthalate, dihexyl phthalate,
Di-n-heptyl phthalate, di-n-octyl phthalate, bis (2-methylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, di-isodecyl phthalate, bis ( Two, two
-Dimethylheptyl) phthalate, n-butyl (iso
-Hexyl) phthalate, ethyl (iso-octyl)
Phthalate, n-butyl (iso-octyl) phthalate
G, n-pentylhexyl phthalate, n-pentyl (iso-hexyl) phthalate, iso-pentyl (heptyl) phthalate, n-pentyl (iso-octyl) phthalate, n-pentyl (iso-nonyl) phthalate, iso-pentyl ( n-decyl) phthalate, n-pentyl (undecyl) phthalate, iso-
Pentyl (iso-hexyl) phthalate, n-hexyl (iso-octyl) phthalate, n-hexyl (i
(so-nonyl) phthalate, n-hexyl (n-decyl) phthalate, n-heptyl (iso-octyl) phthalate, n-heptyl (iso-nonyl) phthalate, n-heptyl (neo-decyl) phthalate, is
O-octyl (iso-nonyl) phthalate is exemplified, and one or more of these are used. Of these, diethyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate or bis (2
-Ethylhexyl) phthalate is preferably used.

When two or more of the above-mentioned components (d) are used, the combination thereof is not particularly limited. When phthalic diester is used, the total number of carbon atoms of the two alkyl groups of one phthalic diester is the same as that of component (d). It is preferable to select and combine them so that the difference in the total number of carbon atoms of the two alkyl groups of the other one phthalic acid diester is 4 or more. A specific example of the combination is as follows. (1) Diethyl phthalate and di-n-butyl phthalate (2) Diethyl phthalate and di-iso-butyl phthalate
(3) Diethyl phthalate and di-n-octyl phthalate (4) Diethyl phthalate and bis (2-ethylhexyl)
Phthalate (5) di-n-butyl phthalate and di-n-octyl phthalate (6) di-n-butyl phthalate and bis (2-ethylhexyl) phthalate (7) diethyl phthalate and di-n-butyl phthalate And bis (2-ethylhexyl) phthalate (8) diethyl phthalate, di-iso-butyl phthalate and bis (2-ethylhexyl) phthalate

[0030] (A) an organosilicon compound used in the preparation of component [sometimes referred to as the "component (e)"] represented by the general formula _{^{R 8 y Si (OR 9)}} 4-y ( wherein, R ⁸ Is an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and R ⁹ is 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, and y is an integer of 0 or 1 to 3). Alkylalkoxysilane, cycloalkylalkylalkoxysilane or alkoxysilane.

Specific examples of the component (e) 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, cyclohexylethyldimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexyl Ethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, Cyclopentyl (iso-butyl) dimethoxysila , Cyclohexyl (n- propyl) dimethoxysilane, cyclohexyl (n- propyl) diethoxy silane, cyclohexyl (an iso-propyl) diethoxysilane, cyclohexyl (n- butyl) dimethoxysilane, cyclohexyl (n- butyl)
Diethoxysilane, cyclohexyl (iso-butyl)
Dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyl Diethylethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane Silane,
iso-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxy Silane, cyclopentyltrimethoxysilane,
Cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxy Silane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis ( 3-methylcyclohexyl) di Toxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3,5 dimethoxycyclohexylcyclohexyldimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, tetramethoxysilane, tetraethoxysilane, Tetrapropoxysilane, tetrabutoxysilane and the like.

Among the above, di-iso-propyldimethoxysilane, di-iso-butyldimethoxysilane,
Di-t-butyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane,
Cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, phenyltriethoxysilane , Tetramethoxysilane and tetraethoxysilane are preferably used, and the component (e) can be used alone or in combination of two or more.

In addition to the above, polysiloxane may be used as the organosilicon compound of the component (e). As the polysiloxane, a compound represented by the general formula (Chemical Formula 1) (where x represents an average degree of polymerization and is 2 to 30,000, and a main component of R ¹⁰ to R ¹⁷ is a methyl group, and sometimes R ¹⁰ to R ¹⁷ Is substituted with a phenyl group, hydrogen, a higher fatty acid residue, an epoxy-containing group, or a polyoxyalkylene group, and the compound of the above general formula forms a cyclic polysiloxane in which R ¹³ and R ¹⁴ are methyl groups. 1) of a polysiloxane represented by the following formula (including component (e)):
Species or two or more species.

[0034]

Embedded image

The polysiloxane is also generically referred to as silicone oil and has a viscosity at 25 ° C. of 2 to 10,000 centistokes, preferably 2 to 1,000 centistokes.
More preferably, it is a liquid, viscous, linear, partially hydrogenated, cyclic or modified polysiloxane at room temperature having 3 to 500 centistokes.

As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used as partially hydrogenated polysiloxane, methylhydrogenpolysiloxane having a hydrogenation ratio of 10 to 80% is used, and cyclic polysiloxane is used as hexamethylcyclosiloxane. Trisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acids Examples include group-substituted dimethylsiloxane, epoxy-substituted dimethylsiloxane, and polyoxyalkylene-substituted dimethylsiloxane.

Specific examples of each polysiloxane include trade names TSF 400, TSF 401, TSF 404, TSF 405,
TSF 4045, TSF 410, TSF 411, TSF 433,
TSF437, TSF 4420, TSF 451-5A, TSF 4
51-10A, TSF 451-50A, TSF 451-10
0, TSF 483, TSF 484 (all are products manufactured by Toshiba Silicone Co., Ltd.), KF96, KF96L, KF96H, KF6
9, KF92, KF961, KF965, KF56, KF99, KF
94, KF995, KF105, KF351, HIVAC-F4, HIV
AC-F5 (both products manufactured by Shin-Etsu Chemical Co., Ltd.) are equivalent.

By subjecting one or more of the above polysiloxanes to a reaction in combination with other components (a) to (d),
Thus, a solid catalyst component which can produce a polymer having a very low content of fine powder while maintaining a predetermined polymer density with high activity can be obtained. These polysiloxanes can also be used by dissolving them in an organic solvent such as toluene, xylene, hexane or heptane.

The solid catalyst component (A) comprises component (a) and component (b)
, Component (c), component (d) and component (e) in suspension. This contact can be carried out in the absence of an inert organic solvent, but it is preferable to carry out the treatment in the presence of the solvent in view of the ease of operation. Examples of the inert organic solvent used include saturated hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and halogens such as ortho-dichlorobenzene, methylene chloride, carbon tetrachloride, and dichloroethane. Among them, aromatic hydrocarbons having a boiling point of about 90 to 150 ° C., specifically, toluene, xylene, and ethylbenzene are preferably used.

The amount ratio of each component is 0.01 to 10 g, preferably 0.05 to 2.0 g, and component (c) is 0.1 to 200 ml, preferably 0.5 to 2.0 g per 1 g of component (a). 100ml
And component (d) is 0.01 to 1.0 g, preferably 0.1 to 0.5 g.
And component (e) is 0.01 to 1 g, preferably 0.05 to 5.0 g. The amount of the inert organic solvent to be used is not particularly limited, but is preferably in the range of 0.1 to 10 in terms of the volume ratio to the component (c) in consideration of operational problems. In addition, these components can be added separately at the time of contact, or one or two or more can be selected and used.

The contact of each component is carried out in an inert gas atmosphere while removing water and the like, while stirring in a vessel equipped with a stirrer. The contact temperature may be in a relatively low temperature range around room temperature when the mixture is simply brought into contact and agitated or mixed or dispersed or suspended for denaturation, but when the reaction is carried out after contact to obtain a product. 40 to 1
A temperature range of 30 ° C. is preferred. When the temperature during the reaction is lower than 40 ° C., sufficient reaction does not proceed, and the performance of the solid catalyst component prepared as a result becomes insufficient. When the temperature exceeds 130 ° C., evaporation of the used solvent becomes remarkable. As a result, the control of the reaction becomes unstable. The reaction time is at least 1 minute, preferably at least 10 minutes, more preferably at least 30 minutes.

In preparing the solid catalyst component (A) of the present invention,
Component (a), component (b), component (c), component (d) and component (e)
The order of contact is not particularly limited and may be arbitrarily determined. The order of contact of each component is as follows. 1. Simultaneously contact components (a), (b), (c), (d) and (e). 2. The component (c) is repeatedly contacted with the solid product obtained by contacting the components (a), (b), (c), (d) and (e). 3. The components (d) and (e) are brought into contact with the solid product obtained by previously bringing the components (a), (b) and (c) into contact. 4. Components (d) and (e) are brought into contact with the solid product obtained by previously bringing components (a), (b) and (c) into contact, and then component (c) is repeatedly brought into contact. 5. Contact the component (b) with the solid product obtained by pre-contacting the components (a), (c), (d) and (e). 6. The component (b) is brought into contact with the solid product obtained by previously bringing the components (a), (c), (d) and (e) into contact, and then the component (c) is brought into contact repeatedly. 7.The component (b) is brought into contact with the solid product obtained by previously bringing the components (a), (c), (d) and (e) into contact, and then the components (b) and (c) are repeated. Make contact. 8. Repeatedly contact the components (b) and (c) with the solid product obtained by pre-contacting the components (a), (b), (c), (d) and (e).

In the order of contact of the above components, the contact order of the component (e) is arbitrary, but the component (a), (c) and (d) are brought into contact with a solid product obtained in advance. It is preferable to reduce the fine powder content of the polymer while maintaining a predetermined polymer density. In the above-mentioned contact, when the obtained solid product is brought into contact with the component (b) and / or the component (c) repeatedly, the contact condition is 1 minute or more in a temperature range of 40 to 130 ° C., preferably 10 minutes or more. Minutes or more, more preferably 3
Hold for at least 0 minutes. At this time, there is a method in which the components (b) and (c) are added as they are, or a method in which the components are appropriately diluted with the above-mentioned inert organic solvent, and the latter method is preferably used. It is also a preferable embodiment that the solid product obtained by the contacting / reaction in the first stage is washed with the above-mentioned inert organic solvent and then subjected to contact treatment with the component (b) and / or the component (c) repeatedly. .

Specific examples of the method for preparing the solid catalyst component (A) are shown below. 1. Suspension of diethoxymagnesium as the component (a) and aluminum trichloride as the component (b) in an aromatic hydrocarbon solvent such as toluene at a temperature range of -10 to 30 ° C. ) Is added as titanium tetrachloride. At this time, the amount of titanium tetrachloride is preferably 1/2 or less by volume ratio to the solvent in which the component (a) is suspended.
The suspension is heated, and the component (d) is heated in a temperature range of 40 to 100 ° C.
To the suspension, diethyl phthalate is further added in a temperature range of 60 to 80 ° C., and then dimethylpolysiloxane is added as the component (e). The temperature is further raised, and the temperature is kept in a temperature range of 100 to 120 ° C. for 30 minutes to 3 hours to react and obtain a solid product. The solid product is washed with titanium tetrachloride diluted in toluene and then with toluene. The temperature at this time is 40 to 130
It is 1 minute or more in the temperature range of ° C. Further, toluene and titanium tetrachloride are added to and brought into contact with the solid product, the temperature is raised, and the temperature is kept in a temperature range of 100 to 120 ° C. for 30 minutes to 3 hours to cause a reaction. At this time, aluminum trichloride can be added again as the component (b). Finally, the solid product is washed with heptane to obtain a solid catalyst component (A). 2. Diethoxymagnesium is suspended as a component (a) in an aromatic hydrocarbon solvent such as toluene in a temperature range of -10 to 30 ° C, and titanium tetrachloride is added as a component (c). At this time, the amount of titanium tetrachloride is preferably 1/2 or less by volume ratio to the solvent in which the component (a) is suspended. Then the ingredients
(d) Di-iso-octyl phthalate is used in a temperature range of 30 to
At 60 ° C., the suspension is added, and further diethyl phthalate is added in the temperature range of 60-80 ° C. Further, the temperature of the suspension was raised, and dimethylpolysiloxane was added as a component (e) in a temperature range of 80 to 100 ° C.
Hold at 保持 120 ° C. for 30 minutes to 3 hours and react to obtain a solid product. The solid product is washed with titanium tetrachloride diluted in toluene and then with toluene. The temperature at this time is 1 minute or more in a temperature range of 40 to 130 ° C. Next, aluminum trichloride is added as a component (b) to the solid product and brought into contact with the solid product.In order to bring the component (b) into uniform contact, the component (b) must be dissolved in an organic solvent such as toluene and added to and brought into contact with the solid product. Is preferred. Titanium tetrachloride is further added, and then the temperature is raised, and the temperature is kept in a temperature range of 100 to 120 ° C. for 30 minutes to 3 hours to cause a reaction. The solid product is washed with heptane to obtain a solid catalyst component (A).

The solid catalyst component (A) of the present invention prepared as described above is preferably washed with an inert organic solvent such as heptane in order to remove unreacted substances. Alternatively, after washing as it is, it is combined with an organoaluminum compound (B) [hereinafter sometimes referred to as “component (B)”] and an organosilicon compound (C) [hereinafter sometimes referred to as “component (C)” ”. The olefin polymerization catalyst of the present invention is formed.

The organoaluminum compound (B) used in the present invention includes a compound represented by the general formula R ¹ _q AlY _{3 -q} (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, Y is hydrogen, chlorine, bromine, Any of iodine, q is 0 <q
<3 is a real number. ) Is used. Examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide, and ethylaluminum hydride, and one or more of them can be used. Preferred are triethyl aluminum and tri-isobutyl aluminum.

The organosilicon compound (C) used in the present invention includes a compound represented by the following general formula: R ² _r Si (OR ³ ) _{4 -r} (wherein R ² is an alkyl group having 1 to 12 carbon atoms, cycloalkyl R ³ may be the same or different and may be any of a phenyl group, a vinyl group, an allyl group, and an aralkyl group, wherein R ³ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, The aralkyl group may be the same or different, and r is 0 or an integer of 1 to 3). Examples of such an organosilicon compound (C) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, and alkoxysilane.

Specific examples of the organosilicon compound (C) include a compound represented by the general formula used in the preparation of the solid catalyst component (A):
The same organosilicon compound represented by R ⁸ _y Si (OR ⁹ ) _4-y can be used. Among them,
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, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyl Dimethoxysilane, cyclopentylmethyldiethoxysilane,
Cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organic silicon Compound (C) is
One type or a combination of two or more types can be used.

In the polymerization method of the present invention, olefins are polymerized or copolymerized in the presence of the catalyst comprising the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C). The use ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound (B) is contained in the solid catalyst component (A). The molar ratio of the organosilicon compound (C) per mole of titanium atom is 1 to 1,000, preferably 50 to 500,
It is used in a molar ratio of 0.0020 to 2, preferably 0.01 to 0.5, per mole of the component (B).

Further, an organic compound containing oxygen or nitrogen may be used in combination with the above organosilicon compound (C). Specific examples thereof include alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, and the like.

More specifically, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl Ethers such as ether, butyl ether, amyl ether, diphenyl ether, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, Octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, P-methoxyethyl benzoate Monocarboxylic acid esters such as P-ethoxyethyl benzoate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dimethyl adipate, adipic acid Dicarboxylic acid esters such as diisodecyl, dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, didecyl phthalate Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone and benzophenone; acid halides such as phthalic dichloride and terephthalic dichloride; acetaldehyde; Examples thereof include aldehydes such as lopionaldehyde, octylaldehyde, and benzaldehyde; amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, and pyridine; and nitriles such as acetonitrile, benzonitrile, and tolunitrile.

In the process for producing an olefin polymer of the present invention, the olefin is polymerized in the presence of the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C) as described above. Prior to performing such polymerization (hereinafter sometimes referred to as “main polymerization”), preliminary polymerization as described below (hereinafter sometimes referred to as “preliminary polymerization”) is performed.

In the prepolymerization, the solid catalyst component
(A) is used in combination with a part of the organoaluminum compound (B). In this case, all or part of the organosilicon compound (C) can be used in combination with these components. The order of contact of each component when performing the prepolymerization is arbitrary, but preferably, the organoaluminum compound (B) is first charged into the prepolymerization system, and then the solid catalyst component (A)
And then contacting one or more olefins. When the combination is performed with the organosilicon compound (C), the organoaluminum compound (B) is first charged into the prepolymerization system, and then the organosilicon compound (C) is brought into contact with the organosilicon compound (C). , It is preferable to contact one or more olefins.

Preliminary polymerization of olefin is carried out using the above-mentioned combination catalyst, and in this case, the reaction is carried out in the presence of an inert hydrocarbon solvent. As the inert hydrocarbon solvent, propane,
Butane, pentane, hexane, heptane, octane, decane, dodecane, cyclohexane, benzene, toluene, xylene, or mineral oil are used,
Of these, aliphatic hydrocarbons such as hexane and heptane are preferably used.

The prepolymerization in the present invention is performed in an atmosphere of an inert gas such as nitrogen or argon, or an olefin to be polymerized. When pre-polymerization is performed in the presence of an inert hydrocarbon solvent as described above, a small amount of the olefin to be pre-polymerized is dissolved in the solvent in advance. Specifically, one or two or more prepolymerized olefins are used in an amount of 0.01 to 1.0 g, preferably 0.1 to 1.0 g per 1 g of the solid catalyst component (A).
03-0.5 g, more preferably 0.05-0.3 g, is dissolved in an inert hydrocarbon solvent. At this time, the amount of the olefin dissolved in the solvent is 1 to the amount of the polymer finally formed in the preliminary polymerization.
50%, preferably 3 to 30%, more preferably 5 to
15%. Thus, the olefin is first dissolved in the solvent, and the organoaluminum compound (B), and optionally the organosilicon compound (C),
After charging and contacting (A), a predetermined amount of olefin is brought into contact and prepolymerization is performed, thereby improving the catalytic activity in the subsequent main polymerization or the stereoregularity and bulk specific gravity of the produced polymer, Further, the amount of fine powder of the produced polymer can be reduced.

In the prepolymerization as described above, the organoaluminum compound (B) is used in an amount of 0.5 to 50 mol, preferably 1 to 25 mol, more preferably 2 to 10 mol, per titanium atom in the solid catalyst component (A). It is desirable to use an amount smaller than the amount of the organoaluminum compound (B) used in the main polymerization. Use of the above-mentioned amount of the organoaluminum compound (B) in the prepolymerization causes a decrease in the catalytic activity.

When the organosilicon compound (C) is used in the prepolymerization, the amount used is 0 to 10 mol, preferably 0 to 5 mol, more preferably 0 to 10 mol per titanium atom in the solid catalyst component (A). In the range of 1 mole.

In the prepolymerization, the concentration of the solid catalyst component (A) is set at 0.1 per liter of the above-mentioned inert hydrocarbon solvent.
01 to 50 g, preferably 0.05 to 30 g, more preferably 0.
It is desirable to set it in the range of 1 to 15 g. As described above, in the prepolymerization in the present invention, the prepolymerization can be performed at a concentration much higher than the catalyst concentration in the polymerization system in the main polymerization, and industrially, the prepolymerization is possible even in a polymerization tank having a relatively small volume. Becomes

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later, and examples thereof include ethylene, propylene, 1-butene, 4-methyl-1-pentene, and vinylcyclohexane. Ethylene or propylene. One of these olefins may be used,
A combination of more than one species may be used.

The temperature at the time of performing the prepolymerization is from 0 to
40 ° C., preferably 5-35 ° C., more preferably 10-30 ° C.
It is. If the temperature is lower than this range, polymerization of the olefin takes time, causing deterioration of the catalyst.If the temperature is higher than this range, the produced polymer is dissolved in the solvent, and as a result, during the main polymerization, Of the catalyst will be reduced. The reaction time for the prepolymerization may be such that a predetermined amount of the polymer can be produced, but is usually 0.1 to 10 hours, preferably 0.5 to 2 hours.

In the prepolymerization of the present invention, the solid catalyst component
(A) It is desirable that the polymerization is carried out so as to produce a polymer in the range of 1 to 20 g, preferably 1.5 to 15 g, more preferably 2 to 10 g per 1 g. When the amount of the produced polymer is smaller than this range, the catalytic activity in the main polymerization is reduced, the stereoregularity and the bulk specific gravity of the produced polymer are reduced, and the amount of the fine powder of the produced polymer is increased. When the amount of the produced polymer is larger than this range, it causes a decrease in the catalytic activity in the main polymerization and further causes a trouble when the produced polymer is processed.

After the prepolymerization as described above, the main polymerization, which will be described later, is performed. When the prepolymerized catalyst is stored for a certain period, the same inert carbon as that used as the solvent in the prepolymerization is used. It is preferable to wash the prepolymerized catalyst with hydrogen to such an extent that the organoaluminum compound liberated in the solvent is no longer detected. By this washing, deterioration of the performance of the prepolymerized catalyst can be suppressed.

After performing the prepolymerization as described above, the main polymerization of the olefin is carried out in the presence of the prepolymerization catalyst, the olefin polymerization catalyst formed from the organoaluminum compound (B) and the organosilicon compound (C). Do. This main polymerization is homopolymerization of olefin, random copolymerization of polymerizing two or more olefins, or block copolymerization.

The use ratio of each component is not particularly limited as long as it does not affect the effect of the present invention, and the organoaluminum compound (B) is usually used as the solid catalyst component (A). 1 to 50 per mole of titanium atom in
0 mol of the organosilicon compound (C) is used in the range of 0.001 to 0.5 per mol of the component (B).

The order of contact of each component is arbitrary,
In the same manner as in the contact sequence in the prepolymerization described above, 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. Preferably, olefin is polymerized.

The polymerization operation can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in either a gas or liquid state.
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, either a continuous polymerization method or a batch polymerization method is possible. Further, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

The olefins polymerized or copolymerized by the catalyst according to the present invention include ethylene, propylene, 1-
Butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane and the like.
Seeds may be used, or two or more kinds may be used in combination.

[0068]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples.

Example 1 <Preparation of solid catalyst component> In a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, 10 g of diethoxymagnesium, aluminum trichloride 1.
0 g and 90 ml of toluene were inserted into the suspension. Into this, 22 ml of room temperature titanium tetrachloride was charged, and the temperature was raised to 80 ° C. with stirring to cause a reaction. Next, 3.3 ml of di-n-butyl phthalate and 1.5 ml of tetrabutoxysilane were added as electron donating compounds, and the temperature in the system was further raised to 110.
The temperature was raised to ℃ and the reaction was carried out for 2 hours. After the completion of the reaction, the supernatant was removed and washed three times at 75 ° C. with 88 ml of toluene. Thereafter, 89 ml of toluene and 22 ml of titanium tetrachloride were newly added, the mixture was treated with stirring at 100 ° C. for 1.5 hours, and then washed eight times with 83 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. When the Ti content in this solid catalyst component was measured, it was 3.1 wt%. Also, the Al content is 0.8 wt%,
The content of the electron donating compound was 5.0% by weight.

<Preliminary polymerization> 300 ml of n-heptane was charged into a 1500 ml-volume stainless steel autoclave equipped with a stirrer which had been sufficiently dried with nitrogen gas and replaced with propylene gas, and 50 ml of propylene gas was introduced. Was dissolved in n-heptane. Next, 0.80 mmol of triethylaluminum was charged and stirred for 30 minutes. Thereafter, 0.12 mmol of the solid catalyst component as Ti was charged, then propylene was continuously introduced, and 3
Polymerization was carried out at 0 ° C. for 60 minutes. The amount of the produced polymer was 4.8 g per 1 g of the solid catalyst component.

<Main Polymerization> 700 ml of n-heptane was charged into a 1800 ml stainless steel autoclave equipped with a stirrer, which had been sufficiently dried with nitrogen gas and replaced with propylene gas, and kept under a propylene gas atmosphere. , 2.10 mmol of triethylaluminum, 0.21 mmol of cyclohexylmethyldimethoxysilane, and 0.0053 mmol of the above prepolymerized catalyst as Ti to form a catalyst for polymerization.
Then, 150 ml of hydrogen was charged, and the propylene pressure in the system was increased.
The polymerization was continued at 70 ° C. for 4 hours at 1.1 MPa. The pressure that decreases as the polymerization proceeds was supplemented by continuously supplying only propylene, and was maintained at a constant pressure during the polymerization. According to the above polymerization method, propylene was polymerized, and the produced polymer was separated by filtration and dried under reduced pressure to obtain a solid polymer.

On the other hand, the filtrate was condensed to obtain a polymer dissolved in the polymerization solvent, the amount of which was defined as (A), and the amount of the solid polymer was defined as (B)
And Further, the obtained solid polymer was extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane,
This amount is defined as (C).

The polymerization activity (Y) per solid catalyst component is represented by the following formula. (Y) = [(A) + (B)] (g) / Amount of solid catalyst component (g) Also, the attack occurrence rate (APP) is represented by the following formula: (APP) = (A) (g) / [(A) + (B)] (g) The yield (t-II) of the total crystalline polymer is determined by the following equation. (t-II) = (C) (g) / [(A) + (B)] (g) Further, the density (ρ), melt index (MI), bulk specific gravity (BD) and 100 When the amount of fine powder having a size of micron or less was measured, the results shown in Table 1 were obtained.

Example 2 <Preparation of solid catalyst component> In a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, 10 g of diethoxymagnesium, aluminum trichloride 1.
0 g and 90 ml of toluene were inserted into the suspension. 20 ml of titanium tetrachloride at room temperature was charged therein, and the temperature was raised to 50 ° C. with stirring to cause a reaction. Next, after adding 4.5 ml of di-iso-octyl phthalate, the temperature in the system was further reduced to 11
After heating to 0 ° C and adding 1.0 ml of tetraethoxysilane,
The reaction was performed for 2 hours. After the completion of the reaction, the supernatant was removed and washed three times at 75 ° C. with 88 ml of toluene. Thereafter, 80 ml of toluene, 1.0 g of aluminum trichloride and 30 ml of titanium tetrachloride were newly added, and the mixture was reacted at 105 ° C. with stirring for 2 hours. Then, n-heptane 8 at 40 ° C.
After washing 8 times with 0 ml, a solid catalyst component was obtained. When the Ti content in this solid catalyst component was measured, it was 2.6 wt%.
The Al content is 0.7 wt%, and the electron donating compound content is 1.
It was 6 wt%.

<Preliminary Polymerization and Main Polymerization> Using the solid catalyst component obtained as described above, the amount of triethylaluminum used in the preliminary polymerization was set to 0.20 mmol, and diphenyldimethoxysilane was used instead of cyclohexylmethyldimethoxysilane. Polymerization of propylene was carried out and evaluated in the same manner as in Example 1 except that the prepolymer was used and evaluated, and the results shown in Table 1 were obtained.

Example 3 <Preparation of solid catalyst component> A round bottom flask having a capacity of 500 ml and sufficiently replaced with nitrogen gas and equipped with a stirrer was charged with 10 g of diethoxymagnesium and 0.1 ml of aluminum trichloride.
8 g and 90 ml of toluene were inserted into the suspension. Into this, 22 ml of room temperature titanium tetrachloride was charged, and the temperature was raised to 80 ° C. with stirring to cause a reaction. Then, after adding 4.8 ml of di-iso-octyl phthalate, the temperature in the system was further reduced to 11
After the temperature was raised to 0 ° C. and 1.5 ml of vinyltriethoxysilane was added, the mixture was reacted for 2 hours. After the completion of the reaction, the supernatant was removed and washed three times at 75 ° C. with 88 ml of toluene. Then 89 ml of toluene, 0.8 g of aluminum trichloride
And 22 ml of titanium tetrachloride, and add 1.5 ml at 100 ° C.
The reaction was performed while stirring for an hour. Thereafter, the solid was washed eight times with 83 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. When the Ti content in this solid catalyst component was measured, it was 2.2 wt%. Further, the Al content was 1.0 wt%, and the electron donating compound content was 2.9 wt%.

<Preliminary Polymerization and Main Polymerization> Using the solid catalyst component obtained as described above, the amount of triethylaluminum used in the prepolymerization was 3.3 mmol, the amount of the solid catalyst component was 0.83 mmol as Ti, Propylene was polymerized and evaluated in the same manner as in Example 1 except that prepolymerization was performed using cyclohexylcyclopentyldimethoxysilane instead of cyclohexylmethyldimethoxysilane, and the results were evaluated. The results shown in Table 1 were obtained.

Example 4 <Preparation of a solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were put into a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and suspended. 20 ml of titanium tetrachloride at room temperature was charged therein, and the temperature was raised to 50 ° C. with stirring to cause a reaction. Then, after adding 5.2 ml of di-iso-octyl phthalate, the temperature was further raised, 0.2 ml of diethyl phthalate was added at 70 ° C., and then 1.0 ml of cyclohexylmethyldimethoxysilane was added.
After the addition of l, the temperature in the system was further increased to 112 ° C to
Allowed to react for hours. After completion of the reaction, the supernatant was removed, treated with 80 ml of toluene and 20 ml of titanium tetrachloride at 100 ° C. for 15 minutes, and washed three times with 100 ml of toluene. Thereafter, 0.6 g of aluminum trichloride, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added, and 10
The reaction was carried out with stirring at 0 ° C. for 2 hours. Then, at 40 ° C
Was washed eight times with 100 ml of n-heptane to obtain a solid catalyst component. When the Ti content in this solid catalyst component was measured, it was 2.1 wt%. In addition, the Al content was 0.6 wt%, and the electron donating compound content was 3.2 wt%.

<Preliminary Polymerization and Main Polymerization> Using the solid catalyst component obtained as described above, cyclohexylmethyldimethoxysilane was added to triethylaluminum at the time of prepolymerization, and then 0.048 mmol was added. A polymerization catalyst was formed in the same manner as in Example 1, and propylene was polymerized and evaluated. The results shown in Table 1 were obtained.

Comparative Example 1 The procedure of Example 1 was repeated except that aluminum trichloride and dimethylpolysiloxane were not used.
Preparation and polymerization of the solid catalyst component were performed. The obtained results are shown in Table 1.

COMPARATIVE EXAMPLE 2 Using the solid catalyst component prepared in Example 1, prior to the prepolymerization, triethylaluminum 30 was added under a nitrogen atmosphere without dissolving propylene in n-heptane in advance.
The polymerization was carried out and evaluated in the same manner as in Example 1 except that the preliminary polymerization was carried out using 0.12 mmol of solid catalyst component Ti and 0.12 mmol of Ti, and the results shown in Table 1 were obtained.

[0082]

[Table 1]

[0083]

As is clear from the examples and comparative examples, the propylene polymer produced by the method of the present invention has a density of 0.900 to 0.9 while maintaining high stereoregularity.
It is within the range of 0.906 g / ml, and the content of the finely divided polymer is very small. Furthermore, the polymer yield also shows a high value, which confirms the remarkable superiority of the method of the present invention.

[Brief description of the drawings]

FIG. 1 is a flowchart schematically illustrating the present invention.

Claims (2)

[Claims] 1. A solid catalyst component containing (A) magnesium, titanium, an electron-donating compound, aluminum and halogen, (B) a general formula R ¹ _q AlY _3-q (wherein R ¹ has 1 to 4 carbon atoms) Is an alkyl group, Y is hydrogen, chlorine, bromine, or iodine, and q is a real number satisfying 0 <q ≦ 3.)
And an organoaluminum compound represented by the general formula (C)
R ² _r Si (OR ³ ) _4-r (where R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which are the same or different. R ³ is 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, and r is 0 or 1-3. In a method for polymerizing olefins using a catalyst comprising an organosilicon compound represented by the formula: 0.01 to 1.0 g of one or more olefins is dissolved per 1 g of the solid catalyst component (A). In the presence of an inert hydrocarbon solvent, the organic aluminum compound (B) and the solid catalyst component (A), the solid catalyst component (A)
Per titanium atom in the organoaluminum compound (B)
In the range of 0.5 to 50 mol, and then the solid catalyst component
(A) one or two or more olefins are preliminarily polymerized in the range of 0 to 40 ° C. so that the amount of the produced polymer per 1 g is in the range of 1 to 20 g, and then main polymerization is performed. For producing an olefin polymer. 2. The olefin polymer according to claim 1, wherein the solid catalyst component is obtained by bringing an alkoxymagnesium, an aluminum compound, a titanium halide compound, an electron-donating compound and an organosilicon compound into contact with each other in suspension. Manufacturing method.