JP2003313221A - Polymerization catalyst for olefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerization catalyst for an olefin giving an olefin polymers in a very high yield, particularly for a propylene polymer maintaining high stereospecificity in a very high yield and further having high activity to hydrogen. <P>SOLUTION: The polymerization catalyst for the olefin composed of an organic silicone compound comprises (A) a solid catalytic component prepared by contacting (a) a magnesium compound, (b) a tetravalent titanium halide compound and (c) an ester of a monocarboxylic acid, (B) an organic aluminum compound of the formula: R<SP>3</SP><SB>p</SB>AlQ<SB>3-p</SB>and (C) the organic silicone compound of the formula: R<SP>2</SP><SB>q</SB>Si(OR<SP>3</SP>)<SB>4-q</SB>. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst capable of obtaining an olefin polymer in an extremely high yield while maintaining a high degree of stereoregularity and having a high hydrogen activity. is there.

[0002]

2. Description of the Related Art Conventionally, solid catalyst components containing magnesium, titanium, an electron-donating compound and halogen as essential components have been known in the polymerization of olefins.
Also, many olefin polymerization methods have been proposed in which olefins are polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound and an organosilicon compound. For example, JP-A-5
No. 9-142206, alkoxymagnesium is suspended in an aromatic hydrocarbon compound in the presence of a carboxylic acid monoester such as ethyl benzoate or methyl acetate,
Then, a catalyst component for olefin polymerization, which is formed by contacting titanium halide such as titanium tetrachloride, is disclosed.

Further, in JP-A-62-158704, a titanium halide is further contacted with a composition obtained by suspending alkoxymagnesium in an aromatic hydrocarbon compound and then contacting it with titanium halide. At this time, a catalyst for olefin polymerization comprising a solid catalyst component obtained by contacting with a diester of an aromatic dicarboxylic acid such as phthalic acid diester at any time, an organoaluminum compound and an organosilicon compound is disclosed.

Further, JP-A-9-169808 discloses a catalyst component for olefin polymerization prepared by using alkoxy magnesium, titanium compound, diester of aromatic dicarboxylic acid such as phthalic acid diester, and cyclic or chain polysiloxane. Is disclosed.

The above-mentioned prior art has a high activity for the purpose of omitting a so-called deashing step of removing catalyst residues such as chlorine and titanium remaining in the produced polymer, and also a stereoregular polymer. It has been focused on improving the yield of the product and improving the sustainability of the catalytic activity during polymerization, and each has produced excellent results.

The electron-donating compound (so-called internal donor) contained in the solid catalyst component for olefin polymerization, particularly the solid catalyst component for propylene polymerization, is initially a carboxylic acid monoester such as ethyl benzoate as in the above-mentioned prior art. Esters were the mainstream. After that, aromatic dicarboxylic acid diesters such as phthalic acid diesters have become the mainstream as internal donors due to problems such as catalyst activity sustainability and odor of produced polymers.

However, the solid catalyst component using the aromatic dicarboxylic acid diester as an internal donor has excellent activity durability, but this characteristic may cause troubles in the polymerization process. That is, after the polymerization is completed, the catalyst is discharged from the polymerization tank together with the produced polymer, but since the activity is still continuing at that time, the polymerization reaction occurs in the discharge pipe, and the polymer is generated in the pipe. This adheres to the inner wall of the pipe, resulting in trouble such as blockage. Due to such problems or quality requirements of polymers to be produced, solid catalyst components using a conventional monocarboxylic acid ester such as ethyl benzoate as an internal donor are still used as olefins, especially for propylene polymerization and copolymerization. It is used in a considerable amount industrially.

However, although the solid catalyst component using the above-mentioned carboxylic acid monoester as an internal donor has high activity,
In recent years, cost reduction of olefin polymers, process improvement, and in order to produce polymers having high functions such as copolymers with high efficiency, it is strongly desired to further activate the catalyst. Is not always sufficient to satisfy the above requirement, and further improvement has been desired.

By the way, the polymer obtained by using the above-mentioned catalyst is used in various applications such as molded articles such as automobiles and home electric appliances, containers and films. These melt the polymer powder generated by polymerization and are molded by various molding machines. However, when manufacturing large moldings such as injection molding, the fluidity of the molten polymer (melt flow rate) It may be required to be high, and so much research has been done to increase the melt flow rate of polymers. Melt flow rate is highly dependent on the molecular weight of the polymer. It is a common practice in the art to add hydrogen as a molecular weight modifier for the polymer produced 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, a large amount of hydrogen is usually added, but the pressure resistance of the reactor is limited due to its safety, and hydrogen that can be added is limited. There is a limit to the amount. Therefore, in order to add more hydrogen, the partial pressure of the monomer to be polymerized must be lowered, and in this case, the productivity is lowered. Further, since a large amount of hydrogen is used, there is a cost problem. Therefore, it has been desired to develop a catalyst having a high activity against hydrogen, which can produce a polymer having a high melt flow rate with a smaller amount of hydrogen. When the stereoregularity or crystallinity of the polymer is improved as in the above-mentioned conventional technique, the activity against hydrogen is extremely lowered, and a polymer having a high melt flow rate cannot be produced. Further, when a polymer having a high melt flow rate is produced by improving the activity of the catalyst against hydrogen, there is a problem that the stereoregularity or crystallinity of the polymer is deteriorated. Was not enough.

[0010]

Therefore, an object of the present invention is to obtain an olefin polymer in a very high yield by using a solid catalyst component for olefin polymerization using a monocarboxylic acid ester as an internal donor. In particular, it is to provide a catalyst for olefin polymerization capable of obtaining a propylene polymer in a high yield while maintaining a high stereoregularity, and having a high hydrogen activity.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the problems remaining in the above-mentioned prior art, and as a result, as a result of the conventional organic catalysts of monocarboxylic acid type, When combined with silicon compounds to form a catalyst, it shows extremely high activity, and when it is subjected to propylene polymerization, it has extremely high activity and yield while maintaining high stereoregularity, and also has extremely high activity against hydrogen. The present invention has been completed and the present invention has been completed.

That is, the present invention provides (A) a magnesium compound, (b) a tetravalent titanium halogen compound and (c) a solid catalyst component obtained by contacting with a monocarboxylic acid ester, and (B) the following general catalyst components. Formula (1); R ¹ _p AlQ _3-p
(1) (In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is 0 <p ≦ 3.
Is a real number. ) An organoaluminum compound represented by
And (C) the following general formula (2); R ² _q Si (OR ³ ) _4-q
(2) (In the formula, R ² represents a chain or branched alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms,
R ³ 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, and may be the same or different, and q is 0. It is an integer of ≦ q ≦ 3. The present invention provides a catalyst for olefin polymerization formed from an organosilicon compound represented by

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION A magnesium compound (hereinafter simply referred to as "component") used for preparing a solid catalyst component (A) (hereinafter sometimes referred to as "component (A)") of the olefin polymerization catalyst of the present invention. "(A)." Includes dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, fatty acid magnesium, etc. Among these magnesium compounds, Dialkoxy magnesium is preferable, and specifically, dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, ethoxymethoxy magnesium, ethoxy propoxy magnesium, butoxy. Butoxy magnesium, and the like,
Diethoxy magnesium is particularly preferred. In addition, these dialkoxy magnesium, metal magnesium,
It may be obtained by reacting with an alcohol in the presence of halogen or a halogen-containing metal compound. The dialkoxymagnesium may be used alone or in combination of two or more.

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

The above spherical dialkoxymagnesium is
The shape does not necessarily have to be a true sphere, and an elliptical shape or a potato shape can be used. Specifically, the shape of the particles is such that the ratio (l / w) of the major axis diameter l and the minor axis diameter w is 3
It is the following, preferably 1 to 2, and more preferably 1 to 1.5.

The dialkoxymagnesium having an average particle size of 1 to 200 μm can be used. It is preferably 5 to 150 μm. In the case of spherical dialkoxymagnesium, its average particle size is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. Regarding the particle size, it is desirable to use one having a small particle size distribution with a small amount of fine powder and coarse powder. Specifically, the proportion of particles having a size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, 100μ
The proportion of particles of m or more is 10% or less, preferably 5% or less. Furthermore, the particle size distribution is ln (D90 / D10)
(Where D90 is the cumulative particle size at 90% particle size, D
10 is an integrated particle size and is a particle size at 10%. ), It is 3 or less, preferably 2 or less.

The method for producing spherical dialkoxymagnesium as described above is described in, for example, JP-A-58-41832, JP-A-62-51633, and JP-A-3-743.
41, JP 4-368391 A, JP 8
No. 73388, for example.

It is used in the preparation of the component (A) in the present invention.
Tetravalent titanium halogen compound (b) (hereinafter referred to as “component
(B) ”. ) Is the general formula Ti (O
R⁶)_nCl _4-n(In the formula, R⁶Is alkyl having 1 to 4 carbon atoms
Represents a group, and n is 0 or an integer of 1 to 3. )
Titanium Halide or Alkoxy Titanium Halide
One or more compounds selected from the group
It

Specifically, titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide are used as titanium halides, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride and n- are used as alkoxytitanium halides. Butoxy titanium trichloride,
Dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-
Examples thereof include butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride and tri-n-butoxy titanium chloride. Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more.

The monocarboxylic acid ester (c) (hereinafter sometimes referred to as "component (c)") used for preparing the component (A) in the present invention is an aliphatic monocarboxylic acid ester or an aromatic monocarboxylic acid. An ester, specifically, 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, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl anisate, methyl anisate and the following general formulas ^{(3); (R 4)} 3 CCOOR 5 (3) ( wherein, R ⁴ is 1 to 3 carbon atoms Al Shows the group, may be the same or different, R ⁵ is and compounds of the monocarboxylic acid ester represented by the show.) An alkyl group having 1 to 12 carbon atoms.

In the above general formula (3), R ⁴ is a methyl group, an ethyl group, a propyl group or an isopropyl group, preferably a methyl group, specifically, an ester of pivalic acid (or an ester of trimethylacetic acid). is there. R ⁵ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a t-butyl group, and particularly preferably a methyl group or an ethyl group. Specific compounds include methyl trimethyl acetate (methyl pivalate), ethyl trimethyl acetate (ethyl pivalate), propyl trimethyl acetate (propyl pivalate), isopropyl trimethyl acetate (isopropyl pivalate), butyl trimethyl acetate (butyl pivalate). ), Isobutyl trimethyl acetate (isobutyl pivalate), t-butyl trimethyl acetate (t-butyl pivalate), methyl triethyl acetate, ethyl triethyl acetate, propyl triethyl acetate, isopropyl triethyl acetate, butyl triethyl acetate, isobutyl triethyl acetate, triethyl acetate t-butyl, methyl tripropyl acetate, ethyl tripropyl acetate, propyl tripropyl acetate, isopropyl tripropyl acetate, butyl tripropyl acetate, isobutyl tripropyl acetate, tri Propyl acetate t- butyl, triisopropyl methyl acetate, triisopropyl ethyl acetate, triisopropyl propyl acetate, triisopropyl isopropyl acetate, butyl triisopropyl acid, triisopropyl isobutyl acetate, triisopropyl acid t
-Butyl and the like.

Among the above monocarboxylic acid esters, ethyl benzoate, ethyl p-ethoxybenzoate, ethyl anisate, methyl trimethylacetate (methyl pivalate) and ethyl trimethylacetate (ethyl pivalate) are preferred. These monocarboxylic acid esters may be used alone or in combination of two or more.

In the present invention, the above component (a),
A method for preparing the component (A) by contacting the components (b) and (c) in the presence of the aromatic hydrocarbon compound (d) (hereinafter sometimes simply referred to as “component (d)”) is prepared. Although it is a preferred embodiment of the method, as the component (d), specifically, an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C., such as toluene, xylene, or ethylbenzene is preferably used. These may be used alone or in combination of two or more.

The method for preparing the component (A) of the present invention will be described below. Specifically, the dialkoxy magnesium (a) is suspended in an alcohol, a halogenated hydrocarbon solvent, a tetravalent titanium halogen compound (b) or an aromatic hydrocarbon compound (d) to prepare a monocarboxylic acid such as a pivalate ester. Examples thereof include a method of contacting the carboxylic acid ester (c) and / or the tetravalent titanium halogen compound (b) to obtain a solid component. In the method, by using a spherical magnesium compound, a solid catalyst component having a spherical shape and a sharp particle size distribution can be obtained, and even if the spherical magnesium compound is not used, for example, a solution or a suspension is prepared by using a spraying device. By forming particles by a so-called spray drying method in which the liquid is sprayed and dried, it is possible to similarly obtain a solid catalyst component having a spherical shape and a sharp particle size distribution.

The components are contacted with each other in a container equipped with a stirrer under an inert gas atmosphere and under the condition that water and the like are removed.
It is carried out with stirring. The contact temperature is a temperature at the time of contacting each component, and may be the same as or different from the reaction temperature. The contact temperature is, in the case of simply bringing them into contact with stirring and mixing, or in the case of carrying out a modification treatment by dispersing or suspending them,
The temperature may be in a relatively low temperature range near room temperature, but when the reaction is performed after the contact to obtain a product, it is 40 to 130.
The temperature range of ℃ is preferred. If the temperature during the reaction is lower than 40 ° C, the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid component, and if the temperature exceeds 130 ° C, the evaporation of the solvent used becomes remarkable. , It becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

The preferred method for preparing the solid catalyst component (A) of the present invention is to suspend the component (a) in the component (d),
Next, a method of preparing the solid catalyst component (A) by contacting the component (b) and then the component (c) and reacting them, or alternatively, suspending the component (a) in the component (d), A method of preparing the solid catalyst component (A) by bringing the component (b) into contact with the component (c) and then causing the reaction to occur.

The preferred contacting sequence for preparing the solid catalyst component (A) of the present invention will be described below in more detail. (1) (a) → (d) → (b) → (c) → << intermediate cleaning →
(D) → (b) >> → final washing → solid catalyst component (A) (2) (a) → (d) → (c) → (b) → << intermediate washing →
(D) → (b) >> → final washing → solid catalyst component (A) (3) (a) → (d) → (b) → (c) → << intermediate washing →
(D) → (b) → (c) >> → final washing → solid catalyst component (A) (4) (a) → (d) → (b) → (c) → << intermediate washing →
(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 contact methods, the step in the double brackets (<<>>) can be repeated a plurality of times as necessary to further improve the activity. In addition, the component (b) used in the step in <<>> may be newly added or may be the residue of the previous step. In addition to the washing steps shown in (1) to (6) above, the product obtained at each contacting step can be washed with a hydrocarbon compound that is liquid at room temperature.

Based on the above, as a particularly preferred method for preparing the solid catalyst component (A) in the present application, dialkoxymagnesium (a) is suspended in an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. After bringing the tetravalent titanium halogen compound (b) into contact with this suspension, a reaction treatment is performed. At this time, before or after contacting the tetravalent titanium halogen compound (b) with the suspension, one or more monocarboxylic acid ester (c) such as ethyl benzoate is added at -20 to -20. A solid reaction product (1) is obtained by contacting at 130 ° C., further contacting the monocarboxylic acid ester (c), and performing a reaction treatment. At this time, it is desirable to perform an aging reaction at a low temperature before or after contacting one or more monocarboxylic acid esters.
The solid reaction product (1) is washed (intermediate washing) with a liquid hydrocarbon compound at room temperature, and then the tetravalent titanium halogen compound (b) is added again in the presence of an aromatic hydrocarbon compound.
A solid reaction product (2) is obtained by contacting at −20 to 100 ° C. for reaction treatment. If necessary, the intermediate washing and the reaction treatment may be repeated a plurality of times. Next, the solid reaction product (2) is washed (final washing) with a liquid hydrocarbon compound at room temperature to obtain a solid catalyst component (A).

The preferred conditions for the above treatment or cleaning are as follows. -Low temperature aging reaction: -20 to 70 ° C, preferably -10
60 ° C., more preferably 0 to 30 ° C., 1 minute to 6 hours,
It is 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.degree. C., 0.5 to 6 hours, preferably 0.5 to 5 hours, particularly preferably 1 to 4
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. The hydrocarbon compound used for washing is preferably an aromatic or saturated hydrocarbon compound which is liquid at room temperature, and specifically, the aromatic hydrocarbon compound is toluene, xylene, ethylbenzene or the like, and the saturated hydrocarbon compound is hexane. , Heptane, cyclohexane and the like.
Preferably, it is desirable to use an aromatic hydrocarbon compound in the intermediate cleaning and a saturated hydrocarbon compound in the final cleaning.

The ratio of the amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method and cannot be specified unconditionally. For example, a tetravalent titanium halogen compound per mol of the magnesium compound (a). (B) is 0.5-10
0 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the monocarboxylic acid ester (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol, more preferably 0. 0.02 to 0.6 mol, the aromatic hydrocarbon compound (d) is 0.001 to 500 mol, preferably 0.001 to 100 mol, and more preferably 0.005.
10 to 10 mol.

The contents of titanium, magnesium, halogen atoms and monocarboxylic acid ester in the solid catalyst component (A) in the present invention are not particularly limited, but preferably titanium is 1.0 to 8.0% by weight, Preferably 2.0
-8.0 wt%, more preferably 3.0-8.0 wt%, magnesium 10-70 wt%, more preferably 10-50 wt%, particularly preferably 15-40 wt%,
More preferably, it is 15 to 25% by weight and the halogen atom is 20
-85% by weight, more preferably 30-85% by weight, particularly preferably 40-80% by weight, still more preferably 45-7%.
5% by weight, and the total amount of monocarboxylic acid diester is 0.5
-30% by weight, more preferably 1-25% by weight in total, and particularly preferably 2-20% by weight in total.

The organoaluminum compound (B) (hereinafter sometimes simply referred to as "component (B)") used when forming the olefin polymerization catalyst of the present invention is represented by the above general formula (1). Is not particularly limited as long as it is a compound represented by the formula ( ¹⁾ , R ¹ is preferably an ethyl group or an isobutyl group, Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, and p is preferably 2 or 3 and 3 Is particularly preferable. Specific examples of the organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide and diethylaluminum hydride, and one or more of them can be used. Preferred are triethyl aluminum and triisobutyl aluminum.

The organosilicon compound (C) (hereinafter sometimes simply referred to as "component (C)") used when forming the olefin polymerization catalyst of the present invention is represented by the above general formula (2). R ² is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a cyclohexyl group and a cyclopentyl group, and R ³ is a methyl group or an ethyl group. Is preferred.

Examples of such organosilicon compounds include alkylalkoxysilanes, cycloalkylalkoxysilanes, and cycloalkylalkylalkoxysilanes. Specific examples include trimethylmethoxysilane, trimethylethoxysilane, and tri-n-. Propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylmethoxysilane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane , Cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di n- propyl dimethoxy silane, diisopropyl dimethoxysilane, di -n- propyl diethoxy silane, diisopropyl diethoxysilane, di -
n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane,
Bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, Bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethyl Cyclohexylcyclopentyldimethoxysilane, 3-
Methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (isopropyl) dimethoxysilane, cyclopentyl ( Isobutyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (isopropyl) dimethoxysilane, cyclohexyl (n-propyl) di Ethoxysilane , Cyclohexyl (isobutyl) dimethoxysilane, cyclohexyl (n
-Butyl) diethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, methyltrimethoxysilane,
Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane , T-butyltrimethoxysilane, n
-Butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane,
Examples thereof include cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

Among the above, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-
Butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxy Silane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane,
Cyclohexylcyclopentyldiethoxysilane, 3-
Methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and particularly preferably diisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane and dicyclopentyldimethoxysilane. The organosilicon compound (C) may be used alone or in combination of two or more.

Further, in the catalyst of the present invention, in addition to the above-mentioned components (A), (B) and (C), an electron donating compound of an organic compound containing an oxygen atom or a nitrogen atom can be used in combination. Examples of such compounds include alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates and the like.

Specifically, methanol, ethanol, n
Alcohols such as propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether,
Ethers such as 9,9-bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionic acid Ethyl, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, p-methoxybenzoate Monocarboxylic acid esters such as ethyl, ethyl p-ethoxybenzoate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate , Dicarboxylic acid esters such as dioctyl dipin, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate and didecyl phthalate, Acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone and other ketones, phthalic acid dichloride, terephthalic acid dichloride and other acid halides, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde and other aldehydes, methylamine, ethylamine, tributylamine , Amines such as piperidine, aniline and pyridine, amides such as oleic acid amide and stearic acid amide, acetonitrile, benzonitrile and toluene Nitriles tolyl, methyl isocyanate, and an isocyanate compound such as ethyl isocyanate.

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

The ratio of the amount of each component used is arbitrary as long as it does not affect the effects of the present invention and is not particularly limited. Usually, the component (B) is the titanium atom in the component (A). 1 to 2000 mol, preferably 50 per mol
It is used in the range of up to 1000 mol. Component (C) is
0.002 to 10 mols, preferably 0.01 to 2 mols, and particularly preferably 0.01 to 10 mols per mol of the component (B).
It is used in the range of 0.5 mol.

The order of contacting each component is arbitrary. First, the organoaluminum compound (B) is charged into the polymerization system, then the organosilicon compound (C) is contacted, and then the solid catalyst component (A) is contacted. It is desirable to let Further or alternatively, the organoaluminum compound (B) is first charged into the polymerization system, while the components (A) and (C) are preliminarily contacted with each other,
It is also a preferred embodiment that the catalyst is formed by charging and contacting the contacted component (A) and component (C) into the polymerization system. By thus treating the components (A) and (C) in contact with each other in advance, it is possible to further improve the hydrogen activity of the catalyst and the crystallinity of the produced polymer.

The polymerization method in 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 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 carried out in one step or in two or more steps.

Further, in the present invention, when the olefin is polymerized using the catalyst containing the component (A) and the component (B) or the component (C) (also referred to as main polymerization), the catalytic activity, stereoregularity and In order to further improve the particle properties of the resulting polymer, it is desirable to carry out preliminary polymerization prior to the main polymerization. In the preliminary polymerization, the same olefins as in the main polymerization or monomers such as styrene can be used. Specifically, the component (A), the component (B) or the component (C) is contacted in the presence of olefins to preliminarily polymerize 0.1 to 100 g of polyolefin per 1 g of the component (A), and Component (B) or component (C)
To form a catalyst.

In carrying out the prepolymerization, the order of contacting each component and the monomer is arbitrary, but preferably, the component (B) is first added to the prepolymerization system set in an inert gas atmosphere or a gas atmosphere in which propylene or the like is polymerized. ),
Then, after contacting the component (A), an olefin such as propylene and / or one or more other olefins are contacted.

When the olefins are polymerized in the presence of the olefin polymerization catalyst of the present invention, the melt flow rate (MI) of the produced polymer is improved with the same hydrogen content as compared with the case where the conventional catalyst is used. In addition, 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 is used for the polymerization of olefins, the activity against hydrogen is improved while maintaining the activity and the crystallinity of the polymer at a high level.

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which are merely illustrative and do not limit the present invention. Example 1 <Preparation of Solid Catalyst Component> A round bottom flask equipped with a stirrer and sufficiently replaced with nitrogen gas and having a capacity of 200 ml was charged with 10 g of diethoxymagnesium and 40 ml of toluene to prepare a suspension state. . The suspension was then equipped with a stirrer and thoroughly replaced with nitrogen gas, volume 500 ml.
Was added to a solution of 10 ml of toluene and 50 ml of titanium tetrachloride previously charged in the round-bottomed flask.
Then, the suspension was reacted at −5 ° C. for 2 hours (low temperature aging treatment). Thereafter, 4.5 g of ethyl pivalate was added, the temperature was further raised to 90 ° C., and then a reaction treatment (first treatment) was carried out for 2 hours while stirring. After the reaction was completed, the product was washed once with 100 ml of toluene at 70 ° C.
Wash 4 times with 100 ml of n-heptane at 0 ° C (intermediate wash)
Then, add 50 ml of titanium tetrachloride newly,
Reaction treatment at 100 ° C for 1 hour with stirring (second treatment)
I went. Further, 50 ml of titanium tetrachloride was added, and the reaction treatment was performed for 1 hour at 100 ° C. with stirring (3rd
Processing). The product is then treated with heptane 1 at 40 ° C.
The solid catalyst component (A) in the form of powder was obtained by washing 7 times with 00 ml, filtering and drying. The titanium content in this solid catalyst component was measured and found to be 4.98% by weight.

[Formation and Polymerization of Polymerization Catalyst] In an autoclave equipped with a stirrer and having an internal volume of 2.0 liters, which was completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum,
0.13 mmol of cyclohexylmethyldimethoxysilane and 0.0026 of the solid catalyst component as titanium atom
mmol was charged to form a polymerization catalyst. Then, 2.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, prepolymerization was carried out at 20 ° C. for 5 minutes, and then the temperature was raised to 7
The polymerization reaction was carried out at 0 ° C. for 1 hour. Polymerization activity per 1 g of the solid catalyst component at this time, the proportion (HI) of the boiling n-heptane insoluble matter in the produced polymer, and the bulk specific gravity (BD) and melt index value (MI) of the produced polymer (a). Table 1
It was shown to.

The melt index value (MI) of the produced polymer (a) is shown in Table 1. The polymerization activity per solid catalyst component used here was calculated by the following formula. Polymerization activity = produced polymer (g) / solid catalyst component (g) Further, the ratio (HI) of boiling n-heptane insoluble matter in the produced polymer was obtained by extracting the produced polymer with boiling n-heptane for 6 hours. The ratio (% by weight) of the polymer insoluble in n-heptane was used. Further, the melt index value (MI) of the produced polymer (a) is ASTM D1238 and JIS K7.
According to 210, bulk specific gravity (BD) was measured according to JIS K6721.

Example 2 Ethyl benzoate was used in place of 4.5 g of ethyl pivalate.
An experiment was conducted in the same manner as in Example 1 except that 1 g was used. The results are shown in Table 1.

Example 3 0.53 mm of dicyclopentyldimethoxysilane instead of 0.13 mmol of cyclohexylmethyldimethoxysilane
An experiment was conducted in the same manner as in Example 1 except that ol was used. The results are shown in Table 1.

Example 4 0.53 mmol of diisopropyldimethoxysilane instead of 0.13 mmol of cyclohexylmethyldimethoxysilane
An experiment was conducted in the same manner as in Example 1 except that was used. The results are shown in Table 1.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that 0.53 mmol of ethyl benzoate was used instead of 0.13 mmol of cyclohexylmethyldimethoxysilane. The results obtained are shown in Table 1.

Comparative Example 2 An experiment was conducted in the same manner as in Example 1 except that 0.53 mmol of ethyl P-ethoxybenzoate was used instead of 0.13 mmol of cyclohexylmethyldimethoxysilane. The results obtained are shown in Table 1.

[0054]

[Table 1]

From the above results, it can be seen that when a specific organosilicon compound is used during the polymerization, the activity of the catalyst is improved and the activity against hydrogen is further improved while maintaining a high degree of stereoregularity of the produced polymer. .

[0056]

The olefin polymerization catalyst of the present invention can obtain an olefin polymer in an extremely high yield while maintaining a high degree of stereoregularity. Further, the olefin polymerization catalyst of the present invention shows extremely high body hydrogen activity while exhibiting high stereoregularity equal to or higher than that of conventional catalysts. Therefore, a general-purpose polyolefin can be provided at low cost, and it is expected to be useful in the production of a copolymer of olefins having high functionality.

[Brief description of drawings]

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

Continued front page    F term (reference) 4J128 AA01 AB01 AC04 AC05 AC06                       BA00A BA01A BA02B BB00A                       BB01B BC05A BC06A BC15B                       BC16B BC34B CA16A CB22C                       CB25C CB42A CB56A CB62C                       CB66C EB02 EB04 EB05                       EB08 EB10

Claims (6)

[Claims] 1. A magnesium compound (A) (a),
(B) a solid catalyst component obtained by contacting a tetravalent titanium halogen compound and (c) a monocarboxylic acid ester,
(B) General formula (1) below; R ¹ _p AlQ _3-p (1) (In the formula, R ¹ 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) (In the formula, R ² is a chain or branched chain alkyl group having 1 to 12 carbon atoms, or a carbon number. 3 to 6 cycloalkyl groups are shown,
R ³ 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, and may be the same or different, and q is 0. It is an integer of ≦ q ≦ 3. ) A catalyst for olefin polymerization, which is formed from an organosilicon compound represented by 2. The catalyst for olefin polymerization according to claim 1, wherein the magnesium compound is alkoxy magnesium. 3. A catalyst for olefin polymerization, wherein the monocarboxylic acid ester is a compound represented by the following general formula (3). (R ⁴ ) ₃ CCOOR ⁵ (3) (In the formula, R ⁴ represents an alkyl group having 1 to 3 carbon atoms and may be the same or different. R ⁵ represents an alkyl group having 1 to 12 carbon atoms. Show.) 4. The catalyst for olefin polymerization according to claim 1, wherein the monocarboxylic acid ester is a pivalic acid ester. 5. The catalyst for olefin polymerization according to claim 1, wherein the monocarboxylic acid ester is ethyl pivalate. 6. The catalyst for olefin polymerization according to claim 1, wherein the organosilicon compound is cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane or diisopropyldimethoxysilane.