JP2002105121A - Catalyst for polymerizing olefins - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for polymerizing olefins excellent in activity against hydrogen and capable of producing a polymer having high stereoregularity in high yield. SOLUTION: This catalyst for polymerizing the olefins comprises (A) a solid catalyst component prepared by bringing (a) a dialkoxymagnesium into contact with (b) a tetravalent titanium halide and (c) a phthalic acid diester in (d) an aromatic hydrocarbon having 50-150 deg.C melting point, (B) an organoaluminum compound represented by general formula R1pAlQ3-p and (C) a halogen- containing organosilicon compound represented by general formula R2qSi(OR3)4-q.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for polymerization of olefins, which has high activity and good hydrogen activity, and can obtain a high stereoregular polymer in a high yield.

[0002]

2. Description of the Related Art Conventionally, in the polymerization of olefins such as propylene, a solid catalyst component containing magnesium, titanium, an electron donating compound and a halogen as essential components has been known. In addition, many olefin polymerization methods for polymerizing or copolymerizing propylene in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound and an organosilicon compound have been proposed. For example, JP-A-57-63310 and JP-A-57-63310
63311 discloses a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor;
A method has been proposed in which an olefin having 3 or more carbon atoms is polymerized using a catalyst comprising a combination of an organoaluminum compound and an organosilicon compound having a Si-OC bond. However, these methods
In order to obtain a highly stereoregular polymer in a high yield, it is not always satisfactory, and further improvement has been desired.

On the other hand, JP-A-63-3010 discloses that 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. Thus, a catalyst for olefin polymerization comprising an organic aluminum compound and an organosilicon compound, and a method for polymerizing olefins have been proposed.

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. And a solid catalyst component prepared by further contacting the solid product with titanium tetrachloride in the presence of alkylbenzene, a catalyst for polymerization of olefins comprising an organoaluminum compound and an organosilicon compound, and a catalyst for the catalyst. Methods for polymerizing olefins in the presence have been proposed.

The above prior arts have a high activity enough to omit a so-called demineralization 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.

[0006] By the way, polymers obtained by using the above-mentioned catalysts are used for various applications such as containers and films, in addition to molded products such as automobiles and home electric appliances. These are obtained by melting polymer powder produced by polymerization and molding by various molding machines. In particular, when manufacturing large molded products by injection molding, etc., the fluidity (melt flow rate) of the molten polymer is increased. Higher values may be required, and much work has been done to increase the melt flow rate of the polymer.

[0007] The melt flow rate is highly dependent on the molecular weight of the polymer. In the art, it is common practice to add hydrogen as a molecular weight regulator for the resulting polymer during the polymerization of propylene. At this time, when producing a polymer having a low molecular weight, that is, in order to produce a polymer having a high melt flow rate, usually a large amount of hydrogen is added. However, the pressure resistance of the reactor is limited due to its safety. There is also a limit on the amount. For this reason, in order to add more hydrogen, the partial pressure of the monomer to be polymerized must be reduced, and in this case, the productivity is reduced. In addition, the use of a large amount of hydrogen causes a problem of cost. Therefore, it has been desired to develop a catalyst capable of producing a polymer having a high melt flow rate with a smaller amount of hydrogen and having a high so-called hydrogen activity and a high stereoregularity polymer in a high yield. Technology was not enough to solve this problem.

[0008]

That is, an object of the present invention is to solve the problems left in the prior art and to provide a polymer having a higher hydrogen activity, a higher activity and a higher stereoregularity. An object of the present invention is to provide an olefin polymerization catalyst which can be obtained at a high yield.

[0009]

The inventor of the present invention has made intensive studies to solve the problems left in the prior art, and as a result,
The present inventors have found that a catalyst using a specific halogen-containing organosilicon compound as a third component (electron donor at the time of polymerization) at the time of polymerization of olefins has extremely high hydrogen activity and can solve the above-mentioned problems. The invention has been completed.

That is, the present invention relates to (A) a dialkoxymagnesium (a), a tetravalent titanium halide (b) and a phthalic acid diester (c) having a boiling point of 50 to 50.
A solid catalyst component prepared by contacting in an aromatic hydrocarbon (d) at 150 ° C., (B) the following general formula (1): R ¹ _p AlQ _3-p (1) (wherein, R ¹ is Represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p represents 0 <p ≦ 3.
Is a real number. An organoaluminum compound represented by
And (C) the following general formula (2): R ² _q Si (OR ³ ) _4-q (2) (wherein, R ² is one of a linear or branched alkyl group having 1 to 12 carbon atoms) One or two hydrogen atoms may be replaced by halogen atoms, which may be the same or different, and R ³ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, Represents an aralkyl group, which may be the same or different, and q is 1 ≦
It is an integer of q ≦ 3. The present invention provides an olefin polymerization catalyst characterized by being formed from the halogen-containing organosilicon compound represented by the formula (1).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Among the catalysts for olefins polymerization of the present invention, dialkoxymagnesium (a) (a) used for preparing a solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”). Hereinafter, the component (a) may be represented by the general formula Mg (OR ⁴ ) (OR ⁵ ) (wherein
R ⁴ and R ⁵ represent an alkyl group having 1 to 10 carbon atoms, and may be the same or different. Is preferred, more specifically, dimethoxymagnesium,
Diethoxymagnesium, dipropoxymagnesium,
Examples include dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, and the like, with diethoxymagnesium being particularly preferred. These dialkoxymagnesiums may be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound. The above dialkoxymagnesiums can be used alone or in combination of two or more.

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

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

The average particle size of the dialkoxymagnesium may be 1 to 200 μm. Preferably it is 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 μm, preferably 5 to 50 μm, more preferably 10 to 40 μm. Further, as for the particle size, it is desirable to use a fine particle and coarse powder having a small particle size distribution. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, 100μ
The number of particles of m or more is 10% or less, preferably 5% or less. Further, the particle size distribution is expressed as ln (D ₉₀ / D ₁₀ ) (where D ₉₀ is the particle size at 90% in the integrated particle size, and D ₁₀ is the particle size at 10% in the integrated particle size). Yes, preferably 2 or less.

The method for producing spherical dialkoxymagnesium as described above is disclosed in, for example, JP-A-58-41832, JP-A-62-51633, and JP-A-3-74341.
JP-A-4-368391, JP-A-8-73388
In Japanese Patent Publication No.

The tetravalent titanium halogen compound (b) (hereinafter sometimes referred to as “component (b)”) used for preparing the component (A) in the present invention has a general formula of Ti (OR ⁶ ).
_n X _{4- n} (wherein, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as chlorine, bromine, and iodine;
n is an integer of 0 ≦ n ≦ 4. ), One or more compounds selected from the group consisting of titanium halides and alkoxytitanium halides.

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

The phthalic acid diester (c) used in the preparation of the component (A) in the present invention (hereinafter sometimes referred to as “component (c)”) has an alkyl group contained in an alkoxycarbonyl group having a carbon number Is preferably a linear or branched alkyl group of 2 to 10, and specific examples thereof include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, and di-phthalate. n-butyl, diisobutyl phthalate, ethyl methyl phthalate, methyl phthalate (isopropyl), ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (isobutyl), di-phthalate
n-pentyl, diisopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-phthalate
Octyl, bis (2,2-dimethylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, diisodecyl phthalate, bis (2,2-dimethylheptyl) phthalate, n phthalate -Butyl (isohexyl), n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-phthalic acid
-Pentyl (isohexyl), isopentyl phthalate (heptyl), n-pentyl phthalate (2-ethylhexyl), n-pentyl phthalate (isononyl), isopentyl phthalate (n-decyl), n-pentyl undecyl phthalate, Isopentyl phthalate (isohexyl),
N-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate
Hexyl (isononyl), n-hexyl phthalate (n-
Decyl), n-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (isononyl), n-heptyl phthalate (neodecyl), and 2-ethylhexyl phthalate (isononyl). More than seeds are used.

Among the above-mentioned phthalic acid diesters, phthalic acid diesters in which two alkyl groups contained in the alkoxycarbonyl group are the same are preferable, and among them, diethyl phthalate, di-n-propyl phthalate and phthalate are particularly preferable. Diisopropyl acid, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, bis (2-ethylhexyl) phthalate, and diisodecyl phthalate are preferably used.

In the present invention, the above components (a), (b) and (c) may be referred to as an aromatic hydrocarbon (d) having a boiling point of 50 to 150 ° C. (hereinafter sometimes simply referred to as “component (d)”). )
Component (A) is prepared by contacting
Specifically, toluene, xylene and ethylbenzene are preferably used as the component (d). These may be used alone or in combination of two or more.

In the preparation of the solid catalyst component (A) in the present invention, an aluminum compound, a metal salt of an organic acid or polysiloxane can be used in addition to the components (a) to (d). These uses are effective in controlling the crystallinity of the resulting polymer.

Specific examples of the aluminum compound include aluminum trichloride, diethoxyaluminum chloride, diisopropoxyaluminum chloride,
Examples include ethoxyaluminum dichloride, isopropoxyaluminum dichloride, butoxyaluminum dichloride, and triethoxyaluminum.

Examples of the metal salts of organic acids include sodium stearate, magnesium stearate, aluminum stearate and the like.

Polysiloxane is also generically referred to as silicone oil and has a viscosity at 25 ° C. of 2 to 10,000 centistokes, more preferably 3 to 500 centistokes, and is a liquid or viscous chain or partially hydrogenated at room temperature. And cyclic or modified polysiloxanes.

Dimethyl polysiloxane and methylphenyl polysiloxane are used as the chain polysiloxane, and a hydrogenation ratio of 10 to 80% is used as the partially hydrogenated polysiloxane.
The methyl hydrogen polysiloxane of the following is a cyclic polysiloxane having hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8 -Tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane.

The method for preparing the component (A) of the present invention will be described below. Specifically, dialkoxymagnesium (a) is suspended in a tetravalent titanium halide (b) or an aromatic hydrocarbon (d), and a phthalic acid diester (c) and / or a tetravalent titanium halide ( b)
To obtain a solid component. In the method, by using a spherical magnesium compound, a solid catalyst component having a spherical and sharp particle size distribution can be obtained, and without using a spherical magnesium compound, a solution or suspension can be obtained using, for example, a spray device. By forming the particles by a so-called spray drying method in which the liquid is sprayed and dried, a solid catalyst component which is similarly spherical and has a sharp particle size distribution can be obtained.

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

Hereinafter, the contact sequence for preparing the solid catalyst component (A) of the present invention will be described more specifically. (1) (a) → (d) → (b) → (c) → << intermediate cleaning →
(D) → (b) >> → final cleaning → solid catalyst component (A) (2) (a) → (d) → (c) → (b) → << intermediate cleaning →
(D) → (b) >> → final washing → solid catalyst component (A) (3) (a) → (d) → (b) → (c) → << intermediate washing →
(D) → (b) → (c) >> → final cleaning → solid catalyst component (A) (4) (a) → (d) → (b) → (c) → << intermediate cleaning →
(D) → (c) → (b) >> → final washing → solid catalyst component (A) (5) (a) → (d) → (c) → (b) → << intermediate washing →
(D) → (b) → (c) >> → final washing → solid catalyst component (A) (6) (a) → (d) → (c) → (b) → << intermediate washing →
(D) → (c) → (b) >> → final washing → solid catalyst component (A)

In each of the above-mentioned contact methods, the steps in double parentheses (<<>>) are further repeated a plurality of times as necessary to further enhance the activity. And the component (b) or component (d) used in the steps in the brackets
May be a newly added one or a residue of a previous step. In each of the above-mentioned contact methods, an aluminum compound, a metal salt of an organic acid, or polysiloxane can be brought into contact at any time, if necessary. Further, in addition to the washing steps described in the above (1) to (6), the product obtained in each contacting step can be washed with a hydrocarbon compound which is liquid at normal temperature.

Based on the above, a particularly preferred method for preparing the solid catalyst component (A) in the present application is to suspend dialkoxymagnesium (a) in an aromatic hydrocarbon (d) having a boiling point of 50 to 150 ° C. After the tetravalent titanium halide (b) is brought into contact with the suspension, a reaction treatment is performed. At this time, before or after contacting the tetravalent titanium halide compound (b) with the suspension, one or two or more phthalic acid diesters (c) are added to the suspension at -20 to 13%.
Contact at 0 ° C. to obtain a solid reaction product (1). At this time, it is desirable to carry out an aging reaction at a low temperature before or after contacting one or more phthalic acid diesters. After washing the solid reaction product (1) at room temperature with a liquid hydrocarbon compound (intermediate washing), the tetravalent titanium halide compound (b) is again subjected to −20 to −20 in the presence of an aromatic hydrocarbon compound. The reaction is carried out by contacting at 100 ° C. to obtain a solid reaction product (2). In this case, it is also a preferable embodiment that one or more phthalic acid diesters (c) are further contacted before or after contacting the tetravalent titanium halide compound (b) with the solid reaction product. If necessary, the intermediate washing and the reaction treatment may be further repeated a plurality of times. Then the solid reaction product (2)
Is washed with a hydrocarbon compound that is liquid at room temperature (final washing)
Thus, a solid catalyst component (A) is obtained.

Preferred conditions for the above treatment or washing are as follows. -Low temperature aging reaction: -20 to 70 ° C, preferably -10 to 10
60 ° C., more preferably 0 to 30 ° C., for 1 minute to 6 hours,
Preferably 5 minutes to 4 hours, particularly preferably 10 minutes to 3 hours. Reaction treatment: 40 to 130 ° C, preferably 70 to 120
° C, particularly preferably 80 to 115 ° C, for 0.5 to 6 hours, preferably 0.5 to 5 hours, particularly preferably 1 to 4 hours.
time. Washing: 0 to 110 ° C, preferably 30 to 100 ° C, particularly preferably 30 to 90 ° C, 1 to 20 times, preferably 1 to 15 times, particularly preferably 1 to 10 times. In addition, the hydrocarbon compound used at the time of washing is preferably an aromatic or saturated hydrocarbon which is liquid at normal temperature, and specifically, toluene, xylene, ethylbenzene, etc. as the aromatic hydrocarbon.
As the saturated hydrocarbon, hexane, heptane, cyclohexane and the like can be mentioned. Preferably, aromatic hydrocarbons are used in the intermediate cleaning, and saturated hydrocarbons are used in the final cleaning.

The ratio of each component used in the preparation of the solid catalyst component (A) cannot be unequivocally defined because it varies depending on the preparation method. For example, tetravalent titanium halide per mole of dialkoxymagnesium (a) Compound (b) is 0.5
To 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the phthalic acid diester (c)
Is 0.01 to 10 mol, preferably 0.01 to 1 mol,
It is more preferably 0.02 to 0.6 mol, and the amount of the aromatic hydrocarbon (d) is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.005 to 500 mol.
10 moles.

The content of titanium, magnesium, halogen atom and maleic diester in the solid catalyst component (A) in the present invention is not particularly limited, but is preferably
1.0 to 8.0% by weight of titanium, preferably 2.0 to 8.0%
8.0% by weight, more preferably 3.0 to 8.0% by weight,
10 to 70% by weight of magnesium, more preferably 10% by weight
To 50% by weight, particularly preferably 15 to 40% by weight, more preferably 15 to 25% by weight, and halogen atoms of 20 to 8% by weight.
0% by weight, more preferably 30 to 80% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 75% by weight, and the total amount of phthalic acid diester is 0.5 to 30% by weight, more preferably 1 to To 25% by weight, particularly preferably 2 to 20% by weight in total.

The organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used in forming the propylene polymerization catalyst of the present invention is represented by the above general formula (1). As long as the compound is not particularly limited, R ¹ is preferably an ethyl group or an isobutyl group, Q is preferably a hydrogen atom, a chlorine atom, or a bromine atom, p is preferably 2 or 3, and 3 is preferably 3. Particularly preferred. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more kinds can be used. Preferably, they are triethyl aluminum and triisobutyl aluminum.

Halogen-containing organosilicon compound (C) used in forming the propylene polymerization catalyst of the present invention.
(Hereinafter, it may be simply referred to as “component (C)”.) Is not particularly limited as long as it is a compound represented by the above general formula (2), and R ² is 1 or 2 hydrogen atoms. A halogen-substituted alkyl group having 1 to 4 carbon atoms is preferable, and a ClCH ₂ — group, a Cl ₂ CH— group, a BrCH ₂ —
Group, Br ₂ CH— group, ClC ₂ H ₄ — group, Cl ₂ C ₂ H
₃ - group, BrC ₂ H ₄ - group, and Br ₂ C ₂ H ₃ - group is particularly preferable, when q is 2 or more, R ² is preferably the same. Further, as R ³ , a methyl group and an ethyl group are preferable. Examples of such halogen-containing organosilicon compounds include halogenated alkyl trialkoxy silanes, dihalogenated alkyl dialkoxy silanes, and trihalogenated alkyl alkoxy silanes. Among them, halogenated alkyl trialkoxy silanes and dihalogenated alkyl Dialkoxysilanes are preferred, and halogenated alkyltrialkoxysilanes are particularly preferred.

Specific examples of the halogen-containing organosilicon compound
For example, ClCH_TwoSi (OCH_Three)_Three, ClCH
_TwoSi (OC_TwoH_Five)_Three, Cl_TwoCHSi (OCH_Three)
_Three, Cl_TwoCHSi (OC_TwoH_Five)_Three, BrCH_TwoSi
(OCH_Three)_Three, BrCH_TwoSi (OC_TwoH_Five)_Three, B
r_TwoCHSi (OCH_Three)_Three, Br_TwoCHSi (OC _Two
H_Five)_Three, ClC_TwoH_FourSi (OCH_Three)_Three, ClC_Two
H_FourSi (OC_TwoH_Five)_Three, Cl_TwoC_TwoH_ThreeSi (OC
H_Three)_Three, Cl_TwoC_TwoH_ThreeSi (OC_TwoH_Five) _Three, Br
C_TwoH_FourSi (OCH_Three)_Three, BrC_TwoH_FourSi (OC
_TwoH_Five)_Three, Br_TwoC_TwoH_ThreeSi (OCH_Three)_Three, Br
_TwoC_TwoH_ThreeSi (OC_TwoH_Five)_Three, (ClCH_Two)_TwoS
i (OCH_Three)_Two, (ClCH_Two)_TwoSi (OC
_TwoH_Five)_Two, (Cl_TwoCH)_TwoSi (OCH_Three)_Two,
(Cl_TwoCH)_TwoSi (OC_TwoH_Five)_Two, (BrC
H_Two)_TwoSi (OCH_Three)_Two, (BrCH_Two)_TwoSi
(OC_TwoH_Five)_Two, (Br_TwoCH)_TwoSi (OCH_Three)
_Two, (Br_TwoCH)_TwoSi (OC_TwoH_Five) _Two, (ClC
_TwoH_Four)_TwoSi (OCH_Three)_Two, (ClC_TwoH_Four)_TwoS
i (OC_TwoH_Five)_Two, (Cl_TwoC_TwoH_Three)_TwoSi (OC
H_Three)_Two, (Cl_TwoC_TwoH_Three)_TwoSi (OC
_TwoH_Five)_Two, (BrC_TwoH_Four)_TwoSi (OCH_Three)_Two,
(BrC_TwoH_Four)_TwoSi (OC_TwoH_Five)_Two, (Br_TwoC
_TwoH_Three)_TwoSi (OCH_Three)_Two, (Br _TwoC_TwoH_Three)_Two
Si (OC_TwoH_Five)_Two, (ClCH_Two)_ThreeSi (OCH
_Three), (ClCH_Two)_ThreeSi (OC_TwoH_Five), (Cl_Two
CH)_ThreeSi (OCH_Three), (Cl_TwoCH)_ThreeSi (O
C_TwoH_Five), (BrCH_Two)_ThreeSi (OCH_Three), (B
rCH_Two)_ThreeSi (OC_TwoH_Five), (Br_TwoCH)_ThreeS
i (OCH_Three), (Br_TwoCH)_ThreeSi (OC
_TwoH_Five), (ClC_TwoH_Four)_ThreeSi (OCH_Three), (C
1C _TwoH_Four)_ThreeSi (OC_TwoH_Five), (Cl_TwoC
_TwoH_Three)_ThreeSi (OCH_Three), (Cl_TwoC_TwoH_Three)_ThreeS
i (OC_TwoH_Five), (BrC_TwoH_Four)_ThreeSi (OC
H_Three), (BrC_TwoH_Four)_ThreeSi (OC_TwoH_Five), (B
r_TwoC_TwoH_Three)_ThreeSi (OCH_Three), (Br_TwoC
_TwoH_Three)_ThreeSi (OC_TwoH_Five), And among them
ClCH _TwoSi (OCH_Three)_Three, ClCH_TwoSi (OC
_TwoH_Five)_Three, BrCH_TwoSi (OCH_Three)_Three, BrCH
_TwoSi (OC_TwoH_Five)_Three, (ClCH_Two)_TwoSi (OC
H _Three)_Two, (ClCH_Two)_TwoSi (OC_TwoH_Five)_Two,
(BrC_TwoH_Four)_TwoSi (OCH_Three)_Two, (BrC_TwoH
_Four)_TwoSi (OC_TwoH_Five)_TwoIs preferably used, and Cl is
CH_TwoSi (OC_TwoH_Five)_ThreeIs particularly preferably used
You. These halogen-containing organosilicon compounds may be used alone.
They can be used alone or in combination of two or more.

The olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst of the present invention. The olefins include ethylene, propylene, 1-butene, 1
-Pentene, 4-methyl-1-pentene, vinylcyclohexane and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed.
The olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane and the like.
Species or two or more of them can be used in combination. Above all,
Ethylene and 1-butene are preferably used.

The amount 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 component (B) is a titanium atom in the component (A). 1 to 2000 mol, preferably 50, per mol
It is used in the range of ~ 1000 mol. Component (C) is
0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 2 mol, per 1 mol of the component (B).
It is used in a range of 0.5 mol.

The order of contact of the components is arbitrary, but first, the organoaluminum compound (B) is charged into the polymerization system, then the organosilicon compound (C) is contacted, and the solid catalyst component (A) is further contacted. It is desirable to make it. Alternatively, the catalyst is formed by first charging the organoaluminum compound (B) into the polymerization system, and then charging the previously contacted component (A) and the component (C) into the polymerization system. Is also a preferred embodiment. Thus, the component (A) and the component (C)
By contacting and treating, it is possible to further improve the hydrogen activity of the catalyst.

The polymerization method of the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene 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, any of a continuous polymerization method and a batch polymerization method can be used. Further, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

Further, in the present invention, when the olefin is polymerized using a catalyst comprising the components (A), (B) and (C) (also referred to as main polymerization), the catalytic activity, stereoregularity and formation In order to further improve the particle properties and the like of the resulting polymer, it is desirable to carry out preliminary polymerization prior to the main polymerization. In the prepolymerization, the same monomers as olefins or styrene used in the main polymerization can be used. Specifically, the component (A), the component (B) and the component (C) are brought into contact with each other in the presence of an olefin, and 0.1 to 100 g of a polyolefin is preliminarily polymerized per 1 g of the component (A). The component (B) is contacted to form a catalyst.

In carrying out the prepolymerization, the order of contact of each component and monomer is arbitrary, but preferably, the component (B) is first placed in a prepolymerization system set in an inert gas atmosphere or a gas atmosphere for carrying out polymerization such as propylene. )
Next, after contacting the component (A), an olefin such as propylene and / or one or more other olefins are contacted. When prepolymerization is performed by combining component (C), component (B) is first charged into a prepolymerization system set in an inert gas atmosphere or a gas atmosphere for performing polymerization such as propylene, and then component (C) And then contacting the solid catalyst component (A) with an olefin such as propylene and / or one or more other olefins.
First, the component (B) is charged into a prepolymerization system set in a method of contacting at least one kind of olefins or in an inert gas atmosphere or a gas atmosphere for performing polymerization such as propylene, and then the components (A) and ( (C) is preferably brought into contact and charged into a prepolymerization system.

When the polymerization of olefins is carried out in the presence of the catalyst for olefin polymerization of the present invention, the melt flow rate (MI) of the produced polymer is smaller than that of the conventional catalyst when the amount of hydrogen is the same. It is ten times improved, and furthermore, the catalytic activity and the stereoregularity of the produced polymer show the same performance as the conventional catalyst. That is, it was confirmed that when the catalyst of the present invention was used for the polymerization of olefins, the activity and the stereoregularity of the polymer were maintained at a high level, and the activity against hydrogen was remarkably improved.

[0044]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but this is merely an example and does not limit the present invention.

<Evaluation of Polymerization> Bulk polymerization of propylene was evaluated using the olefin polymerization catalyst of the present invention, and the amount of polymer produced per solid catalyst component (polymerization activity: Yiel
d) When the resulting polymer was extracted with boiling n-heptane for 6 hours using a high temperature Soxhlet extractor, the proportion (HI) of the polymer insoluble in n-heptane was measured. Yiel
d and HI were calculated from the following equations (4) and (5). Furthermore, the melt flow rate (MI) of the produced polymer,
The bulk density (BD) was measured. The measuring methods of MI and BD are JIS K 7210 and JIS K 672, respectively.
1. Yield (g-PP / g-cat.) = A (g) / solid catalyst component (g) (4) HI (wt%) = {b (g) / a (g)} × 100 (5) The above ( In the formulas 4) and (5), a indicates the weight of the polymer formed after the completion of the polymerization reaction, and b indicates n-heptane obtained by extracting the polymer formed after the polymerization reaction with boiling n-heptane for 6 hours. Indicates the weight of the insoluble matter.

Example 1 <Preparation of Solid Catalyst Component> A 2000 ml round bottom flask equipped with a stirrer and sufficiently purged with nitrogen gas was placed in a flask.
150 g of diethoxymagnesium and 750 m of toluene
1 was put into a suspended state. The suspension was then equipped with a stirrer and fully purged with nitrogen gas, volume 20
Toluene 45 previously charged in a 00 ml round bottom flask
0 ml and a solution of titanium tetrachloride 300 ml were added. Next, the suspension was reacted at 5 ° C. for 1 hour (low temperature aging treatment). Thereafter, 22.5 ml of di-n-butyl phthalate was added, the temperature was raised to 90 ° C., and a reaction treatment (first treatment) was performed for 2 hours with stirring. After the completion of the reaction, the product was washed four times with 1300 ml of toluene at 80 ° C. (intermediate washing), and 1200 ml of toluene and 300 ml of titanium tetrachloride were newly added, followed by a reaction treatment at 112 ° C. for 2 hours with stirring (second treatment). ) Was done.
Thereafter, the intermediate washing and the second treatment were repeated once more. The product is then treated with 1300 ml of heptane at 40 ° C.
, And the mixture was filtered and dried to obtain a powdery solid catalyst component (A). The titanium content of the solid catalyst component was measured and found to be 3.74% by weight.

<Formation and polymerization of polymerization catalyst>
Replaced auto with a stirrer of 2,200 ml internal volume
First, 1.3 m of triethylaluminum was placed in the clave.
mol and then 0.0026 as titanium atoms
mmol of the above solid catalyst component and ClCH_TwoSi
(OC _TwoH_Five)_Three0.13 mmol is charged and stirred
Thus, a polymerization catalyst was formed. Then, 2000m of hydrogen gas
, 1400 ml of liquefied propylene, and
Prepolymerization for 1 minute and then main polymerization at 70 ° C for 1 hour.
Was. Table 1 shows the results of the polymerization evaluation.

COMPARATIVE EXAMPLE 1 0.13 mmol of cyclohexylmethyldimethoxysilane was used instead of 0.13 mmol of ClCH ₂ Si (OC ₂ H ₅ ) _3.
The experiment was performed in the same manner as in Example 1 except that mmol was used. The results obtained are also shown in Table 1.

[0049]

[Table 1]

From the above results, it can be seen that when a halogen-containing silicon compound is used as an electron donor during polymerization, the activity against hydrogen is dramatically improved.

[0051]

As described above, the catalyst of the present invention has an extremely good activity for hydrogen. By polymerizing olefins using the polymerization catalyst of the present invention, an extremely high melt flow rate can be obtained.
An olefin polymer having high stereoregularity can be obtained in a high yield. This can solve problems such as an increase in cost due to equipment improvement and an increase in the amount of hydrogen used, or a decrease in productivity.

[Brief description of the drawings]

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

Continuing on the front page F-term (reference) 4J028 AA01A AB01A AC04A AC05A AC06A BA00A BA02B BB00A BB01B BC14B BC16B BC17B BC24B BC34B CA15A CB04A CB44A DA01 DA02 DA03 DA05 DA06 EB02 EB03 EB04 FA01 GA01 FA02 FA03 AB01 AC04 AC05 AC06 BA00A BA02B BB00A BB01B BC14B BC16B BC17B BC24B BC34B CA15A CB04A CB44A DA01 DA02 DA03 DA05 DA06 EB02 EB03 EB04 EB05 EB08 EB10 EC01 EC02 FA01 FA02 FA04 FA07 GA05 GA09 GA21 GB01

Claims (3)

[Claims] (A) A dialkoxymagnesium (a), a tetravalent titanium halide (b) and a phthalic acid diester (c) are contacted in an aromatic hydrocarbon (d) having a boiling point of 50 to 150 ° C. (B) the following general formula (1): R ¹ _p AlQ _{3 -p} (1) (wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, and Q represents hydrogen Represents an atom or a halogen atom, and p is 0 <p ≦ 3
Is a real number. An organoaluminum compound represented by
And (C) the following general formula (2): R ² _q Si (OR ³ ) _4-q (2) (wherein, R ² is one of a linear or branched alkyl group having 1 to 12 carbon atoms) One or two hydrogen atoms may be replaced by halogen atoms, which may be the same or different, and R ³ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, Represents an aralkyl group, which may be the same or different, and q is 1 ≦
It is an integer of q ≦ 3. A catalyst for polymerization of olefins, which is formed from the halogen-containing organosilicon compound represented by the formula (1). 2. The catalyst for olefin polymerization according to claim 1, wherein the dialkoxymagnesium is diethoxymagnesium. 3. The olefin polymerization catalyst according to claim 1, wherein the halogen-containing organosilicon compound is an alkyltrialkoxysilane halide or an alkyldialkoxysilane dihalide.