JPH1129611A - Solid catalyst component for olefin polymerization and catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst component capable of obtaining a polymer having high stereospecificity and excellent in particle properties in high yield by bringing a dialkoxymagnesium, a titanium halide and an aromatic dicarboxylic acid diester to mutually contact in the presence of a hydrocarbon solvent. SOLUTION: This catalyst component comprising magnesium, titanium, a halogen and an electron donor as essential ingredients is obtained by bringing (A) a dialkoxymagnesium (e.g. diethoxymagnesium, etc.), (B) a tetravalent titanium halide (e.g. TiCl4 , TiBr4 , etc.), and (C) an aromatic dicarboxylic acid diester (e.g.; di-n-heptyl phthalate, etc.), to contact in the presence of (D) a hydrocarbon solvent (e.g. toluene, xylene, etc.), preferably at -10-30 deg.C to form a hydrocarbon solution, reacting the solution at 60-90 deg.C for 0.5-5 hours to form a solid product and reacting the solid product with the compound B at 90-120 deg.C for 0.5-5 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid catalyst component and a catalyst for olefin polymerization, which can provide a polymer having high stereoregularity and excellent particle properties in a high yield. More specifically, the present invention relates to a solid catalyst for olefin polymerization and a catalyst capable of obtaining a polymer having a uniform particle size and particle size distribution and a good flowability in a high yield in the polymerization of olefins having 3 or more carbon atoms. It is.

[0002]

2. Description of the Related Art Conventionally, in the polymerization of olefins,
Magnesium, titanium, a solid catalyst component for olefin polymerization containing an electron-donating compound and a halogen as essential components, and the solid catalyst component and an organoaluminum compound;
Olefin polymerization catalyst comprising an organosilicon compound or the like,
Further, many olefin polymerization methods for polymerizing or copolymerizing olefins in the presence of the catalyst have been proposed (JP-A-57-63310 and JP-A-57-63310).
63311).

For example, in JP-A-63-3010, a product obtained by contacting a dialkoxymagnesium, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon and a titanium halide is heat-treated in a powder state. There has been proposed a catalyst for olefin polymerization comprising a solid catalyst component prepared as described above, an organoaluminum compound and an organosilicon compound, and a method for polymerizing olefins in the presence of the catalyst.

In Japanese Patent Application Laid-Open No. Hei 1-315406, titanium tetrachloride is brought into contact with a suspension formed of diethoxymagnesium and alkylbenzene, and then phthalic acid dichloride is added and reacted to form a solid. A solid catalyst component prepared by contacting the solid product with titanium tetrachloride in the presence of alkylbenzene, and a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound; Methods for polymerizing olefins in the presence have been proposed.

The above prior arts have a high activity enough to omit a so-called deashing step for removing catalyst residues such as chlorine and titanium remaining in a produced polymer, and also have a stereoregularity. It focuses on improving the yield of the polymer and increasing the sustainability of the catalyst activity during the polymerization, and has each produced excellent results.

However, when olefins are polymerized using a polymerization catalyst having a composition comprising such a highly active catalyst component and an electron donating compound represented by an organoaluminum compound and a silicon compound, a solid catalyst component is obtained. In addition to the fine powder itself, the resulting polymer contained a large amount of fine powder due to particle destruction due to the heat of reaction during polymerization, and the particle size distribution tended to be broad. When the amount of the finely divided polymer increases, it may hinder the continuation of a uniform reaction or cause process obstruction such as blockage of a pipe at the time of transferring the polymer. Undesirable effects up to. For this reason, the amount of the finely divided polymer was as small as possible, and this was a factor for seeking a polymer having a uniform particle size and a narrow particle size distribution.

As means for solving the problems of fluidity and particle size distribution of the formed polymer, JP-A-56-811 and JP-A-58-83006 disclose a hydrocarbon solution of a magnesium compound and a liquid titanium compound. To form a solid product, or after forming a hydrocarbon solution of a magnesium compound and a titanium compound, deposit a solid product, wherein the precipitation of the solid product is carried out in the presence of an electron donor. Disclosed below is a solid titanium catalyst component obtained by supporting an electron donor such as a polyvalent carboxylic acid ester on the solid product during or after the precipitation of the solid product.

However, the above method requires a step of dissolving a magnesium compound such as magnesium chloride in a solvent such as alcohol to form a uniform solution, and then depositing a solid product.
A lot of auxiliaries must be used, which is a very complicated process.

On the other hand, as means for solving the problems such as particle size distribution while simplifying the preparation process, JP-A-6-15
No. 7659, a spherical dialkoxymagnesium is added to a mixed solution of an aromatic hydrocarbon and titanium tetrachloride,
There has been proposed an olefin polymerization catalyst comprising a solid catalyst component obtained by adding and reacting a suspension of an aromatic hydrocarbon and a phthalic acid diester, and further reacting the suspension with titanium tetrachloride.

In JP-A-6-287225, a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon and phthalic acid diester is added to a mixed solution of aromatic hydrocarbon and titanium tetrachloride. And react
The obtained reaction product is washed with an aromatic hydrocarbon, and a solid component obtained by reacting with titanium tetrachloride again is dried.
A solid catalyst component for olefin polymerization obtained through a fine powder removal process has been proposed.

Further, in JP-A-6-287217, a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon and phthalic acid diester is added to a mixed solution of aromatic hydrocarbon and titanium tetrachloride. React
The obtained reaction product is washed with an aromatic hydrocarbon, and a solid component obtained by reacting with titanium tetrachloride again is dried.
There has been proposed a solid catalyst component for olefin polymerization obtained by subjecting a fine powder removal treatment to a treatment step of adding a powdered nonionic surfactant.

[0012]

The above technique has the effect of removing fine powder of the solid catalyst component itself and reducing the amount of fine powder of the resulting polymer. However, it has not been possible to control the generation of fine powder due to the particle destruction due to the heat of reaction at the time of polymerization as described above, and it has not yet solved the problem of fine powder contained in the produced polymer. In addition, the polymer produced in this technique is close to spherical and has a good morphology, but the particle shape or particle size depends on the dialkoxymagnesium used as the raw material, and therefore, the morphology of this dialkoxymagnesium Need to be controlled. Furthermore, the bulk specific gravity of the produced polymer is low, and in the production of polyolefin, the production amount per unit volume of the polymer in the polymerization tank is small, and the throughput of the polymer in the transportation or pelletizing process is limited, and as a result, the polyolefin is produced. The problem of reduced overall production productivity still remains.

The present inventors have conducted various studies to solve the above-mentioned problems remaining in the prior art, and as a result, have found that the solid catalyst component prepared by the present invention regardless of the form of the dialkoxymagnesium, Including a catalyst component, in the presence of a catalyst formed with a specific organosilicon compound and an organoaluminum compound, by performing the polymerization of olefin, confirmed that the above problem can be effectively solved,
The present invention has been completed.

Accordingly, an object of the present invention is to provide a solid catalyst component for the polymerization of olefins, which can obtain a granular or spherical polymer having a high stereoregularity, a narrow particle size distribution and a high bulk specific gravity in a high yield. It is to provide a catalyst.

[0015]

That is, the present invention relates to a solid catalyst component (A) for polymerizing olefins comprising magnesium, titanium, halogen and an electron donor as essential components, wherein (a) a dialkoxymagnesium. , (B)
Contacting a tetravalent titanium halide and (c) an aromatic dicarboxylic acid diester in the presence of (d) a hydrocarbon solvent to form a hydrocarbon solution, followed by solid product formation, and then (b) An object of the present invention is to provide a solid catalyst component for olefin polymerization, which is obtained by reacting with a tetravalent titanium halide.

Further, the present invention provides: (A) a solid catalyst component for the polymerization of olefins according to claim 1, (B) a general formula R ¹ _p AlY _3-p (wherein R ¹ has 1 to 4 carbon atoms) Y represents a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom, and p is a real number satisfying 0 <p ≦ 3.) (C) a general formula R ² _q Si (oR ³⁾ in _4-q (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, may be the same or different. R ³
Represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, which may be the same or different. q is 0 or 1
It is an integer of 3. The present invention provides a catalyst for polymerization of olefins, which is formed by an organosilicon compound represented by the formula (1).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The dialkoxymagnesium component (a) constituting the solid catalyst component (A) of the present invention (hereinafter referred to as "component
(a) ". ) Includes dimethoxy magnesium, diethoxy magnesium, di-n-propoxy magnesium, di-iso-propoxy magnesium, di-n
-Butoxymagnesium, di-iso-butoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxy-n-propoxymagnesium, n-butoxyethoxymagnesium, iso-butoxyethoxymagnesium and the like, and more preferably,
Diethoxymagnesium or di-n-propoxymagnesium. These can be used alone or in combination of two or more.

The above-mentioned component (a) is in the form of granules or powder, and its shape is not particularly limited, but irregular or spherical ones may be used. The average particle size of the component (a) is not particularly limited, but is preferably from 0.1 μm to 1000 μm, and is preferably from 0.5 μm to 500 μm from the viewpoint of easiness of operation in forming a hydrocarbon solution.
Particularly preferably, it is 1 μm to 100 μm. further,
Although the specific surface area of the dialkoxymagnesium is not particularly limited, it is usually 1 to 50 m ² / g, more preferably 5 m ² / g.
３０30 m ² / g.

Next, the tetravalent titanium halide (hereinafter sometimes referred to as “component (b)”) of component (b) used in preparing the solid catalyst component (A) of the present invention is titanium. Tetra halide or alkoxy titanium halide. Specifically, as titanium tetrahalide, TiC
l ₄ , TiBr ₄ , TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC
_{2 H 5) Cl 3, Ti} (OC 3 H 7) Cl 3, Ti (O
_{n-C 4 H 9) Cl} 3, Ti (OCH 3) 2 Cl 2, T
i (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) ₂ Cl
_{2, Ti (On-C 4} H 9) 2 Cl 2, Ti (OC
H 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. These titanium compounds can be used alone or in combination of two or more. These tetravalent titanium halides can be used after being diluted with a hydrocarbon solvent used for forming a hydrocarbon solution.

The tetravalent titanium halide is used in forming a hydrocarbon solution together with dialkoxymagnesium and an aromatic dicarboxylic acid diester in the presence of a hydrocarbon solvent, and is also used in forming a solid product thereafter. The tetravalent titanium halide used at this time may be the same or different.
When the tetravalent titanium halide in forming the initial hydrocarbon solution and the tetravalent titanium halide coexisting in forming the subsequent solid product are the same, dialkoxy magnesium and an aromatic dicarboxylic acid diester are used. When forming the hydrocarbon solution, it is added in excess, and then when the solid product is formed, the tetravalent titanium halide may not be newly added, or may be newly added.

In preparing the solid catalyst component (A) of the present invention, the component (c) used in forming a hydrocarbon solution of dialkoxymagnesium and tetravalent titanium halide in the presence of a hydrocarbon solvent is used. The aromatic carboxylic acid diester (hereinafter sometimes referred to as “component (c)”) includes:
Diesters of phthalic acid are preferred. Particularly preferred is a linear or branched alkyl diester of phthalic acid having 1 to 12 carbon atoms. 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, bis (2,2-dimethylhexyl) phthalate, di-n-nonyl phthalate, di-
-isodecyl phthalate, bis (2,2-dimethylheptyl) phthalate, n-butyl (iso-hexyl) phthalate, ethyl (2-ethylhexyl) phthalate, n-butyl (2-ethylhexyl) phthalate, n-pentylhexyl phthalate, n-pentyl (iso-hexyl) phthalate,
iso-pentyl (heptyl) phthalate, n-pentyl (is
o-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 (iso-nonyl) phthalate, n-hexyl (n-decyl) phthalate, n-heptyl (iso-octyl) phthalate, n-heptyl (iso- Nonyl) phthalate, n-heptyl (neo-decyl) phthalate, iso-octyl (iso-nonyl) phthalate, dibenzyl phthalate,
Examples thereof include n-butylbenzyl phthalate, ethylbenzyl phthalate, and dicyclohexyl phthalate, and one or more of these can be used in combination.

Of the above, diesters of phthalic acid having a straight or branched chain alkyl having 5 to 12 carbon atoms are preferred, and specifically, 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-iso-
Decyl phthalate is preferably used. Among them, diesters of linear or branched alkyl having 7 to 12 carbon atoms are particularly preferable, and di-n-heptyl phthalate, di-
-n- Octyl phthalate, bis (2-methylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n
-Nonyl phthalate and di-iso-decyl phthalate are preferably used.

A hydrocarbon solvent of component (d) used to form a hydrocarbon solution of dialkoxymagnesium, tetravalent titanium halide and aromatic dicarboxylic acid diester (hereinafter sometimes referred to as "component (d)") ) Is a hydrocarbon solvent which is liquid at normal temperature, and is an aliphatic hydrocarbon or an alicyclic hydrocarbon such as pentane, hexane, heptane, octane, decane, dodecane, cyclohexane, etc .; benzene, toluene, xylene, ethylbenzene, cumene , Aromatic hydrocarbons such as cymene; dichloroethane,
Dichloropropane, trichlorethylene, carbon tetrachloride,
Examples thereof include halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, and among them, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene and cymene are particularly preferable.

In the present invention, dialkoxymagnesium (a), tetravalent titanium halide (b) and aromatic dicarboxylic acid diester (c) are used in the presence of a hydrocarbon solvent (d).
When forming the hydrocarbon solution of the above, the order of contact of each component is not particularly limited and is arbitrary, but specific examples are as follows.

1) The component (a) is suspended in the component (d), and the components (b) and (c) are brought into contact with the suspension. 2) The component (a) is suspended in the component (d), and the component (b) and then the component (c) are brought into contact with the suspension. 3) The components (a) and (c) are added to and contacted with a mixture of the components (b) and (d). 4) The component (a) and then the component (c) are added and brought into contact with a mixture of the components (b) and (d). 5) A component (a) and a component (c) suspended in the component (d) are added to a mixture of the component (b) and the component (d) and brought into contact. 6) The component (a) suspended in the component (d) is added to a mixed solution of the component (b) and the component (d), followed by contact with the component (c). 7) In the mixture of component (b), component (c) and component (d),
The component (a) is added and brought into contact. 8) In the mixture of component (b), component (c) and component (d),
The component (a) suspended in the component (d) is added and brought into contact.

When the components are brought into contact with each other to form a hydrocarbon solution of dialkoxymagnesium and a tetravalent titanium halide and an aromatic dicarboxylic acid diester as described above, the contact temperature or the reaction temperature is not particularly limited and may be arbitrarily selected. However, it is preferably 50 ° C. or lower, more preferably -2.
The range is from 0 ° C to 40 ° C, particularly preferably from -10 ° C to 30 ° C.

After forming a hydrocarbon solution of dialkoxymagnesium, tetravalent titanium halide and aromatic dicarboxylic acid diester, a solid product is formed,
The component (b) and the component (c) may each be newly added before or after the production of the solid product, and the free component (b) and / or the component may be added when the hydrocarbon solution is formed.
You may add in excess so that (c) may remain.

When a solid product is formed in the hydrocarbon solution, the reaction system is heated, thereby precipitating the reaction product which is particularly dissolved in the hydrocarbon of the component (d) to produce solid particles. The conditions at this time are arbitrary, but are preferably 30 ° C. or higher, more preferably 50 ° C. or higher, particularly preferably in the range of 60 ° C. to 90 ° C., for 1 minute to 20 hours, preferably 5 minutes to 10 hours, The reaction is preferably performed for 30 minutes to 5 hours to produce a solid product.

After the solid product is formed, the temperature is raised and the reaction is carried out.
Preferably 60 ° C to 130 ° C or less, more preferably 90 ° C to 130 ° C.
C. to 120.degree. C. for 1 minute to 20 hours, preferably 5 minutes to 10 hours.
The reaction is carried out for a time, more preferably 30 minutes to 5 hours. Further, when the reaction system is subjected to the reaction from the time of solid product generation, the reaction system is heated and the temperature is raised.
20 ° C./min, more preferably 0.5 to 10 ° C./min to obtain a solid catalyst component having good particle properties.

When the component (c) is newly added to the reaction system during or after the production of the solid product and brought into contact with the reaction system, the conditions are not particularly limited, but are preferably 130 ° C. or lower, more preferably 100 ° C. or lower. It can be added and brought into contact with the above-mentioned solid product when it is generated, or during the course of temperature rise or reaction when it is subjected to the reaction thereafter. As described above, when using two or more aromatic dicarboxylic acid diesters having different alkyl groups, particularly a phthalic acid diester, a diester having a large carbon number of the alkyl group, preferably 5 or more carbon atoms is added at 60 ° C. or less, It is desirable to add a diester having a small number of carbon atoms, preferably 4 or less carbon atoms, at 60 ° C. or more.

The solid catalyst component (A) of the present invention is prepared as described above. After forming a hydrocarbon solution of dialkoxy magnesium, tetravalent titanium halide and aromatic dicarboxylic acid diester, the solid product is prepared. The solid product is then washed with an aromatic hydrocarbon solvent such as toluene, ethylbenzene, xylene, or an aliphatic hydrocarbon solvent such as hexane or heptane, and then washed with component (b) or component (d). Contacting the diluted component (b) with the solid product again at least once or more is a preferred embodiment for improving the performance of the obtained solid catalyst component.

Further, in the preparation of the solid catalyst component (A) of the present invention, in addition to the components (a), (b), (c) and (d), an organosilicon compound having a Si—O bond or an aluminum compound Can be used.

Specific examples of the organosilicon compound having a Si—O bond include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, and trimethylmethoxysilane.
-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-propyldi Ethoxysilane, 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, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n- Pentyl) diethoxysilane, cyclopentyl (is
o-butyl) dimethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (iso-propyl) diethoxysilane, cyclohexyl (n-butyl) dimethoxysilane, cyclohexyl (n-butyl) ) Diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxymethoxysilane, Cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane 2-ethylhexyl triethoxysilane, methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, n- propyltrimethoxysilane, n-
Propyltriethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane,
t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane , 2-ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane , 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-di Methylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3,5-dimethoxycyclohexylcyclohexyldimethoxy Silane, bis (3,
5-dimethylcyclohexyl) dimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like.

In addition to the above, polysiloxane may be used as the organosilicon compound. As the polysiloxane, general formula (1),

[0035]

Embedded image

(In the formula, 1 represents an average degree of polymerization;
000, the main component of R _{4 to} R ₁₁ is a methyl group, and a part of R _{4 to} R ₁₁ is substituted with a phenyl group, a hydrogen atom, a higher fatty acid residue, an epoxy-containing group, and a polyoxyalkylene group. It may be. In addition, the above general formula
In the compound (1), R ⁷ and R ⁸ may form a cyclic polysiloxane having a methyl group. ), Which can be used alone or in combination of two or more.

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.

Examples of the linear polysiloxane include dimethyl polysiloxane and methylphenyl polysiloxane, partially hydrogenated polysiloxane, methyl hydrogen polysiloxane having a hydrogenation rate of 10 to 80%, and cyclic polysiloxane as hexamethyl cyclopolysiloxane. 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.

These polysiloxanes can be used by dissolving them in an organic solvent such as toluene, xylene, hexane or heptane.

The aluminum compound is at least one selected from the group consisting of aluminum compounds represented by the following general formulas (2) and (3).

[0042] _{^{Al (OR 12) m X 1}} 3 -m (2) ( wherein, R ¹² represents an alkyl group having 1 to 4 carbon atoms, a phenyl group or an alkyl group having 1 to 3 carbon atoms 1-2 When m 2 is 2 or more, R ¹² is the same or different, X ¹ is a halogen atom, and m is 0 ≦ m ≦
3. )

[0043] ^{_{R 13 n AlX 2 3 -n (}} 3) ( wherein, R ¹³ represents an alkyl group having 1 to 4 carbon atoms, X ²
Represents a hydrogen atom or a halogen atom, and n represents 0 <n ≦ 3
It is. )

The aluminum compound represented by the general formula (2) includes aluminum trihalide, alkoxyaluminum dihalide, dialkoxyaluminum halide, and trialkoxyaluminum. Specific examples thereof include aluminum trichloride, aluminum tribromide. , Aluminum triiodide,
Diethoxyaluminum chloride, diisopropoxyaluminum chloride, dibutoxyaluminum chloride, ethoxyaluminum dichloride, isopropoxyaluminum dichloride, butoxyaluminum dichloride, trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, Examples thereof include aluminum triisobutoxy, and among them, preferred substances are aluminum trichloride, diisopropoxy aluminum chloride, isopropoxy aluminum dichloride, triethoxy aluminum, and triisopropoxy aluminum.

The aluminum compound represented by the general formula (3) includes trialkylaluminum, dialkylaluminum hydride, dialkylaluminum halide and alkylaluminum dihalide, and specific examples thereof include triethylaluminum, triisobutylaluminum, and diethylaluminum. Aluminum hydride, diisobutyl hydride, diethyl aluminum chloride, diisobutyl aluminum chloride,
Examples thereof include ethylaluminum dichloride, propylaluminum dichloride, ethylaluminum sesquichloride, and butylaluminum sesquichloride. Of these, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquichloride are preferable.

As the above-mentioned aluminum compound, one or more kinds selected from the compound group of the above-mentioned general formulas (2) and (3) can be used. The compound is
It may be used by bringing it into direct contact with other components or by dissolving and diluting it in an organic solvent such as an aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as hexane or heptane.

In the preparation of the solid catalyst component (A) of the present invention, the use ratio of each component is not particularly limited and is optional. Preferably, component (b) is used in an amount of 0.1 to 200 ml per 1 g of component (a).
, More preferably 0.5 to 100 ml, and component (c) is 0.01 to 2
g, more preferably 0.1 to 2 g, component (d) is 1 to 100 ml,
More preferably, it is 3 to 50 ml. In particular, the amount of the aromatic dicarboxylic acid diester (c) used in forming the hydrocarbon solution of dialkoxymagnesium, tetravalent titanium halide and aromatic dicarboxylic acid diester depends on the amount of the component (a) 1
It is 0.1 to 2 g, preferably 0.3 to 1 g per g.

When the above-mentioned optional organic silicon compound or aluminum compound is used,
The amount of the organosilicon compound is usually 0.01 to 1 g per 1 g of the component (a).
10 g, preferably 0.05 to 5 g, aluminum compound is 0.0
It is 1 to 10 g, preferably 0.05 to 2 g.

As described above, the solid catalyst component (A) of the present invention
As the prior art alcohol, without using a special solvent for dissolving a magnesium compound such as a tetraalkoxytitanium compound or carbon dioxide gas, and regardless of the particle size and shape of the raw material alkoxymagnesium, furthermore It can be prepared without pulverizing, sieving or spray-drying to control its particle size and shape, to obtain an olefin polymer or copolymer having a uniform particle size and particle size distribution and good flowability. be able to.

Next, as the organoaluminum compound (B) (hereinafter sometimes referred to as “component (B)”) used in the olefin polymerization catalyst of the present invention, the following formula R ¹ _p AlY _3-p ( In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, Y represents a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom, and p is a real number satisfying 0 <p ≦ 3. It is an aluminum compound.

Such an organoaluminum compound (B)
Examples thereof include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide, diethylaluminum hydride and the like, and one or more of these can be used in combination. Preferred are triethylaluminum and tri-iso-butylaluminum.

The organosilicon compound (C) (hereinafter sometimes referred to as “component (C)”) used in the catalyst of the present invention is represented by the following formula: R ² _qSi (OR ³ ) _4-q among, R ² represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or aralkyl group having 1 to 12 carbon atoms, the same or may be different .R ³
Represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, which may be the same or different. q is 0 or 1
It is an integer of 3. ).

Examples of such an organosilicon compound (C) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, and alkoxysilane.

Specific examples of the organosilicon compound (C) include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, and 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, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane,
Cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-
Pentyl) diethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (n-propyl)
Diethoxysilane, cyclohexyl (iso-propyl) diethoxysilane, cyclohexyl (n-butyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane,
Diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane,
Cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltri Ethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t-
Butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2 -Ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4 -Methylcyclohexylcyclopentyldimethoxysilane, 3,5-di Tylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3,5-dimethoxycyclohexylcyclohexyldimethoxy Silane, bis (3, 5-
Dimethylcyclohexyl) dimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane and the like.

Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n -Butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldimethoxysilane, Cyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethyl Kishishiran, cyclohexyl cyclopentyl distearate triethoxysilane, 3-methyl-cyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxysilane, 3, 5-
Dimethylcyclohexylcyclopentyldimethoxysilane is preferably used, and the organosilicon 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 organosilicon compound (C) has a molar ratio of 1 to 1,000, preferably 50 to 500, per mole of titanium atom.
It is used in a molar ratio of 0.0020 to 2, preferably 0.01 to 0.5 per mole of the component.

The olefin polymerization catalyst of the present invention comprises the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C) described above. As the external electron donor), an organic compound containing oxygen or nitrogen in addition to the organic silicon compound (C) can be used. Specific examples thereof include, for example, 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 and dodecanol; phenols such as phenol and cresol; methyl ether, ethyl ether and propyl Ethers such as ether, butyl ether, amyl ether and 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, P-ethoxyethyl benzoate,
Monocarboxylic acid esters such as methyl anisate and ethyl anisate; diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dimethyl adipate;
Dicarboxylic acids such as diisodecyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, and didecyl phthalate Acid esters; ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetone phenone and benzophenone; acid halides such as phthalic dichloride and terephthalic dichloride; aldehydes such as acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde; methyl amine, ethyl amine Amines such as tributylamine, tributylamine, piperidine, aniline and pyridine; nitriles such as acetonitrile, benzonitrile and tolunitrile Can Shimesuru.

Examples of the olefins homopolymerized or copolymerized using the catalyst of the present invention include ethylene, propylene, 1-butene and 4-methyl-1-pentene, and are particularly suitable for the polymerization of propylene. .

Further, in the present invention, in the polymerization of olefins (also referred to as main polymerization) using a catalyst comprising the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C), In order to further improve the activity, stereoregularity, and the particle properties of the produced polymer, it is preferable to carry out preliminary polymerization prior to polymerization. As monomers for the prepolymerization, not only ethylene and propylene but also monomers such as styrene and vinylcyclohexane can be used.

The polymerization is carried out by slurry polymerization, liquefaction polymerization or gas phase polymerization, and it is possible to use hydrogen as a molecular weight regulator during the polymerization. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower,
It is preferably at most 5 MPa, more preferably at most 2.5 MPa.

[0062]

By using the solid catalyst component and catalyst for olefin polymerization of the present invention, a granular or spherical polymer having high stereoregularity, narrow particle size distribution, and high bulk specific gravity can be obtained in high yield. Obtainable.

[0063]

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

Example 1 <Preparation of solid catalyst component (A)> In a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, 10 g of diethoxymagnesium, 50 ml of toluene and bis (2-ethylhexyl) phthalate were added. 5.2 ml of the mixture was charged, suspended and cooled to 1 ° C. This suspension is mixed with toluene 3
0 ml and a solution of 20 ml of titanium tetrachloride were added and stirred while maintaining the temperature at 3 ° C. to obtain a homogeneous solution. Then 80 ° C
The solid product was precipitated and 2.0 ml of di-n-butyl phthalate was added. Further, the temperature in the system was raised to 105 ° C., and the reaction was performed for 2 hours. After the completion of the reaction, the supernatant was removed and washed with 100 ml of toluene at 100 ° C. four times. Thereafter, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added, the mixture was treated with stirring at 100 ° C. for 2 hours, and then washed with 100 ml of n-heptane at 40 ° C. seven times to obtain a solid catalyst component. When the Ti content in this solid catalyst component was measured, it was 2.1 wt%.

<Formation and Polymerization of Polymerization Catalyst> In a 2-liter autoclave equipped with a stirrer completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and the solid catalyst component (A ) As titanium atom
033 mmol was charged to form a polymerization catalyst. Thereafter, 1.5 l of hydrogen gas and 1.4 l of liquefied propylene were charged,
The polymerization reaction was performed at 70 ° C. for 1 hour to obtain a solid polymer-1. Table 1 shows the obtained catalyst performance and properties of the polymer.

The properties of the polymer shown in Table 1 were obtained by taking the weight of the produced polymer as (I) after the completion of the polymerization reaction, and extracting the weight of the polymer insoluble when extracted with boiling n-heptane for 6 hours. The polymerization activity and the yield of the total crystalline polymer were determined by the following formula, where the weight of the combined product was defined as (II). Polymerization activity = (I) (g) / solid catalyst component (g) Yield of all crystalline polymer (wt%) = (II) × 100 / (I)

Further, MI, bulk specific gravity, average particle size, and particle size distribution of the formed polymer (ln (D90 / D10): where D 9
0 is the particle size of 90 wt% in the integrated particle size distribution, D 10 is the particle size of 10 wt% in the integrated particle size distribution) and the amount of the polymer of 105 μm or less is shown in Table 1.

Example 2 An experiment was carried out in the same manner as in Example 1 except that bis (2-ethylhexyl) phthalate was changed to di-iso-decylphthalate to prepare a solid catalyst component. The obtained results are shown in Table 1. It was also added. When the Ti content in the solid catalyst component was measured,
It was 2.2 wt%.

Example 3 An experiment was carried out in the same manner as in Example 1 except that di-n-butyl phthalate was replaced with diethyl phthalate to prepare a solid catalyst component. The results obtained are shown in Table 1. When the Ti content in the solid catalyst component was measured, it was 2.5 wt%.

Example 4 Bis (2-ethylhexyl) phthalate was used in an amount of 7.0 ml.
An experiment was conducted in the same manner as in Example 1 except that the results were set as described above, and the obtained results are also shown in Table 1. When the Ti content in the solid catalyst component was measured, it was 2.0 wt%.

Example 5 <Preparation of solid catalyst component> In a 500 ml round bottom flask equipped with a stirrer and sufficiently purged with nitrogen gas, 10 g of diethoxymagnesium, 50 ml of toluene and bis (2-
5.2 ml of ethylhexyl) phthalate was charged, suspended, and cooled to 1 ° C. This suspension was added to a solution of 30 ml of toluene and 20 ml of titanium tetrachloride, and stirred while maintaining the temperature at 3 ° C. to obtain a homogeneous solution. Thereafter, the temperature was raised to 80 ° C. to precipitate a solid product, and then 2.0 ml of di-n-butyl phthalate and decamethylcyclopentasiloxane 3
ml was added. Further, the temperature in the system was raised to 105 ° C., and the reaction was performed for 2 hours. After the reaction, remove the supernatant,
It was washed four times at 100 ° C. with 100 ml of toluene. Thereafter, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added, and the mixture was stirred and treated at 100 ° C. for 2 hours.
The solid catalyst component was obtained by washing 7 times with 100 ml of n-heptane at ° C. When the Ti content in this solid catalyst component was measured, it was 2.1 wt%.

<Formation and Polymerization of Polymerization Catalyst> A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component (A) obtained as described above was used. The results are shown in Table 1.

Comparative Example 1 <Preparation of a solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were charged into a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas to form a suspended state. 20 ml of titanium tetrachloride at room temperature was added thereto, and the temperature was raised to 50 ° C. while stirring, and 5.2 ml of bis (2-ethylhexyl) phthalate was added (at this time, the system remained suspended). .). Further raise the temperature to 70 ° C
Then, 1.0 ml of diethyl phthalate was added. Further, the temperature in the system was raised to 105 ° C., and the reaction was performed for 2 hours. After the reaction was completed, the supernatant was removed, and 10 ml of toluene was used.
Washed 4 times at 0 ° C. Thereafter, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added, and the mixture was treated with stirring at 100 ° C. for 2 hours, and then washed eight times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. Ti in this solid catalyst component
When the content was measured, it was 2.2 wt%.

<Formation and polymerization of polymerization catalyst> A polymerization catalyst was formed and polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component obtained as described above was used. 1

[0075]

[Table 1]

As is clear from Table 1, in the polymerization of olefins having 3 or more carbon atoms, when the solid catalyst component and the catalyst of the present invention are used, the polymerization activity per catalyst component and the yield of the whole crystalline polymer are reduced. It was confirmed that the polymer was extremely high and the bulk specific gravity of the produced polymer was also high. Furthermore, the average particle diameter is stably large, the particle size distribution is sharp, and the content of the finely divided polymer having a particle size of 105 μm or less is extremely low, and the excellent particle properties are clearly shown.

[Brief description of the drawings]

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

Claims (2)

[Claims] 1. A solid catalyst component (A) for olefin polymerization comprising magnesium, titanium, halogen and an electron donor as essential components, wherein (a) a dialkoxymagnesium, and (b) a tetravalent titanium halide. And (c) contacting the aromatic dicarboxylic diester in the presence of (d) a hydrocarbon solvent to form a hydrocarbon solution followed by the formation of a solid product, and then (b) a tetravalent titanium halide A solid catalyst component for olefin polymerization, which is obtained by reacting (A) a solid catalyst component for olefin polymerization according to claim 1, (B) a general formula R ¹ _p AlY _3-p (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) Y represents a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom, and p is a real number satisfying 0 <p ≦ 3.) (C) a general formula R ² _qSi (OR ³ ) in _4-q (wherein, R ² represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or aralkyl group having 1 to 12 carbon atoms, which may be the same or different .R ³
Represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, which may be the same or different. q is 0 or 1
It is an integer of 3. A catalyst for polymerization of olefins, which is formed by an organosilicon compound represented by the formula: