JP2582192B2 - Olefin polymerization catalyst component and method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst component for olefin polymerization and a method for producing a polyolefin, and more particularly, to a solid product used for preparing a solid catalyst component for olefin polymerization, and a solid catalyst using the solid product. And a method for producing a polyolefin using the solid catalyst component.

[0002]

2. Description of the Related Art An olefin polymerization catalyst generally called a Ziegler catalyst generally comprises a transition metal compound component and an organometallic compound component. Among these two components, in the former preparation of the transition metal compound component, a technique using magnesium chloride or magnesium dialkoxide as a carrier raw material has been more widely practiced than before, and there are extremely many related techniques. doing.

[0003] However, when these magnesium compounds are used as a carrier material for a catalyst for olefin polymerization, it is necessary to use those having an optimum particle size in order to improve the activity as a catalyst and control the particle size of the produced polymer. In this case, the magnesium compound alone may be pulverized as a particle size adjusting means, or may be co-pulverized when an unpulverized magnesium compound is treated with an ester or the like, but in any case, mechanical pulverization, classification and the like Processing is an indispensable operation.

When a material not subjected to such a pulverization treatment or the like is used as a carrier material, the polymerization activity of the catalyst becomes low, and the amount of the supported transition metal (for example, titanium) itself is low. Lower. This causes problems such as an increase in the amount of residual chlorine in the polymer. In addition, problems occur in the shape and particle size distribution of the obtained polymer particles, which may cause a trouble in the process of producing a polyolefin (for example, blockage of a transfer line for a large number of finely divided polymers). Therefore, it is recognized that the grinding process of magnesium compound is very important. However, this mechanical grinding process requires setting of conditions (grinding method such as wet or dry grinding, grinding which affects the shape of the grinding product). Machine, crushing strength, crushing time, etc.), it took considerable labor and cost.

Further, in order to improve the so-called morphology such as the particle size and shape of the produced polymer, a method of supporting magnesium on an inorganic oxide such as silica (Japanese Patent Laid-Open No.
1-291604, 61-291105, 62
-119203, 62-119204)
Alternatively, a method is used in which a magnesium compound is once dissolved in a solvent such as alcohol and then precipitated again (Japanese Patent Laid-Open No.
Although these methods can omit the pulverizing step, they require a supporting treatment, a dissolution, and a precipitation treatment, so that the process becomes extremely complicated and the performance of the catalyst is reduced. There is a disadvantage that stability is deteriorated. Therefore, there is a demand for a method of controlling the particle size, particle size distribution and morphology of the catalyst carrier for olefin polymerization without performing complicated operations such as mechanical pulverization and classification.

Further, (A) reacting a compound formed from metal magnesium, a halogenated hydrocarbon and an alcohol, wherein halogen / metal magnesium satisfies a predetermined range, an electron-donating compound and a halogen-containing tetravalent titanium compound. A method for polymerizing olefins, comprising using a catalyst comprising the obtained solid catalyst component and (B) an organoaluminum compound (JP-A-57-151).
601) has been proposed, but it has not always been satisfactory in terms of the morphology of the solid product and the polymer powder.

In view of this situation, the present inventors have conducted intensive studies on producing a catalyst carrier material having a spherical shape and a controlled particle size and particle size distribution by a one-step reaction. When alcohol and a specific amount of a halogen-containing metal compound are reacted, the particle size distribution is narrow,
It is possible to obtain a solid product that can be used as a carrier material for an olefin polymerization catalyst without performing a particle size adjustment treatment such as pulverization and classification, and to use an olefin polymerization catalyst component using the solid product as a carrier. It has been found that when an olefin is polymerized, a polymer with significantly improved morphology can be obtained while exhibiting a titanium carrying amount, polymerization activity and stereoregularity equal to or higher than those of the conventional one. Further, the present inventors can freely control the particle size of the obtained solid product by appropriately selecting the reaction conditions of the metal magnesium, alcohol and the halogen-containing metal compound, and thus control the morphology of the resulting polymer. Can also be done freely.

By the way, the solid product obtained by reacting the metal magnesium, alcohol and a specific amount of the halogen-containing metal compound according to the present invention is a material completely different from any conventionally known magnesium-based carrier raw materials.
In fact, it has been known that a small amount of iodine, ethyl orthoformate, or the like is added when reacting metallic magnesium with alcohol (Japanese Patent Publication No. 46-7093, U.S. Pat. No. 4,412,132). However, in these reactions, iodine or the like is merely used as a reaction initiator, and the amount is very small. On the contrary, the solid products according to the present invention are completely different from those shown in these prior arts, because the amount of halogen used in the present invention is much larger than that used as a reaction initiator. You can see that. That is, an object of the present invention is to provide an entirely new carrier material for an olefin polymerization catalyst which has not been known, and to provide a solid catalyst composition and a method for producing a polyolefin using the same.

[0009]

According to the present invention, there is provided, according to the present invention, a solid product used for preparing a solid catalyst component for olefin polymerization, comprising a metal magnesium, an alcohol, and the metal magnesium. It is obtained by reacting a halogen-containing metal compound containing a halogen atom in an amount of 0.0001 gram atom or more per gram atom, and has a sphericity (S) represented by the following formula (1).
Is S <1.60, and the particle size distribution index (P) represented by the following formula (2) is P <5.0. S = (E1 / E2) ² (1) (where E1 indicates the contour length of the projection of the particle, and E2 indicates the circumference of a circle equal to the projection area of the particle.) P = D90 / D10. (2) (Here, D90 indicates a particle diameter corresponding to a cumulative weight fraction of 90%, and D10 indicates a particle diameter corresponding to a cumulative weight fraction of 10%.)

[0010] Also provided is a solid catalyst composition obtained by using (a) the solid product and (b) a tetravalent titanium compound.

In a preferred embodiment, (a) the solid product; (b) a tetravalent tetravalent titanium compound;
(C) A solid catalyst composition obtained by using the electron donating compound is provided.

(A) (a) the solid product;
There is provided a method for producing a polyolefin, characterized by using (b) a solid catalyst component obtained using a tetravalent titanium compound, and (B) an organometallic compound.

In a preferred embodiment, (A)
(A) a solid catalyst component obtained by using the solid product, (b) a tetravalent titanium compound, and (c) an electron donating compound, (B) an organometallic compound, and (C) electron donating. And a method for producing a polyolefin characterized by using a hydrophilic compound.

Further, as a preferred embodiment, the obtained polyolefin powder has a sphericity (S) represented by the above formula (1) that is S <1.60, and the above formula (2)
The method for producing a polyolefin having a particle size distribution index (P) represented by the formula: P <5.0 is provided.

Hereinafter, the present invention will be described in more detail. The solid product (a) of the present invention is obtained from magnesium metal, an alcohol, and a halogen-containing metal compound. In this case, the shape of the metallic magnesium is not particularly limited. Therefore,
Metallic magnesium having an arbitrary particle size, for example, granular, ribbon-shaped, powdered, etc. metallic magnesium can be used. In addition, the surface state of the metallic magnesium is not particularly limited, but those in which a coating such as magnesium oxide is not formed on the surface are preferable.

Although any alcohol can be used, it is preferable to use a lower alcohol having 1 to 6 carbon atoms. In particular, the use of ethanol is preferable because a solid product that significantly improves the expression of catalytic performance can be obtained. The purity and water content of the alcohol are not limited, but if an alcohol having a high water content is used, magnesium hydroxide [Mg (OH) ₂ ] is formed on the surface of the magnesium metal, so that the water content is 1% or less, particularly 2000 ppm.
It is preferable to use the following alcohols. Further, in order to obtain a solid product (a) having a better morphology, it is preferable that the water content is as small as possible.

The type of the halogen-containing metal compound is not limited, and any metal compound containing a halogen atom in its chemical formula can be used. In this case, the type of the halogen atom is not particularly limited, but is preferably chlorine, bromine or iodine. As the halogen-containing metal compound, specifically, MgCl ₂ , MgI ₂ , Mg
(OEt) Cl, Mg (OEt) I, MgBr ₂ , Ca
Cl ₂ , NaCl, KBr and the like can be suitably used. Of these, MgCl ₂ and MgI ₂ are particularly preferred. The state, shape, particle size, and the like of the halogen-containing metal compound are not particularly limited, and may be any one.

The amount of alcohol is not limited, but is preferably from 2 to 100 mol, particularly preferably from 5 to 50 mol, per mol of metallic magnesium. If the amount of alcohol is too large, the yield of the solid product (a) having a good morphology may be reduced. If the amount is too small, stirring in the reaction tank may not be performed smoothly. However, it is not limited to the molar ratio.

In the halogen-containing metal compound, the halogen atom in the halogen-containing metal compound is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.1 gram atom per 1 gram atom of metal magnesium.
Used to have 001 gram atoms or more. When the halogen atom is less than 0.0001 gram atom, the amount of the halogen used is not much different from the amount used as the reaction initiator, and when the obtained solid product (a) is used without pulverization, the supported amount, the activity, the stereoregularity , And the morphology of the produced polymer becomes poor. Therefore, the pulverization of the solid product (a) is indispensable. The upper limit of the amount of the halogen-containing metal compound to be used is not particularly limited, and may be appropriately selected within a range where the solid product (a) of the present invention is obtained. Preferably it is less than 0.06 gram atom per atom. Further, by appropriately selecting the amount of the halogen-containing metal compound to be used, the particle size of the solid product (a) can be freely controlled.

The reaction itself between the metal magnesium, the alcohol and the halogen-containing metal compound can be carried out in the same manner as in a known method. That is, the metal magnesium, the alcohol, and the halogen-containing metal compound are refluxed (about 7
At 9 ° C.) until no further generation of hydrogen gas is observed (usually about 20 to 30 hours) to obtain a solid product. Specifically, for example, when using an iodine-containing metal compound as a halogen-containing metal compound, metal magnesium, a method of charging a solid iodine-containing metal compound into an alcohol, and then heating and refluxing, metal magnesium, in the alcohol A method in which an alcohol solution of an iodine-containing metal compound is dropped and then heated and refluxed, a method in which an alcohol solution of an iodine-containing metal compound is added dropwise while heating the metal magnesium and alcohol solution, and the like. Both methods are preferably performed in an inert gas (for example, nitrogen gas, argon gas) atmosphere and optionally using an inert organic solvent (for example, saturated hydrocarbon such as n-hexane).

Regarding the charging of the metal magnesium, the alcohol and the halogen-containing metal compound, it is not necessary to put the whole amount into the reaction tank from the beginning, and they may be divided and charged. A particularly preferred form is a method in which the alcohol is charged in its entirety from the beginning, and the magnesium metal is divided and charged several times. In this case, a temporary large amount of hydrogen gas can be prevented, which is very desirable from the viewpoint of safety. Also, the size of the reaction tank can be reduced. Furthermore, it is also possible to prevent entrainment of alcohol or a halogen-containing metal compound caused by temporary mass generation of hydrogen gas. The number of divisions may be determined in consideration of the scale of the reaction tank, and is not particularly limited, but usually 5 to 10 times is preferable in view of the complexity of the operation.

The reaction itself may be of a batch type or a continuous type. Furthermore, as a variant, an operation in which a small amount of metallic magnesium is firstly introduced into the alcohol which is entirely introduced from the beginning, the product generated by the reaction is separated and removed in another tank, and then a small amount of metallic magnesium is again introduced. It is also possible to repeat. When the solid product thus obtained is used in the next synthesis of a solid catalyst component, a dried product may be used, or a product washed with an inert solvent such as heptane after filtration may be used. In any case, the obtained solid product (a) can be used in the following steps without pulverization or classification operation for adjusting the particle size distribution.

The solid product (a) is nearly spherical and has a sharp particle size distribution. Furthermore, even if each particle is taken, the sphericity variation is very small.
In this case, the sphericity (S) represented by the formula (1) is less than 1.60, particularly less than 1.40, and the particle size distribution index (P) represented by the formula (2) is 5.0. Preferably, it is less than 4.0, especially less than 4.0. Where D
90 refers to a particle size corresponding to a cumulative weight fraction of 90%. In other words, it indicates that the weight sum of the particles smaller than the particle diameter represented by D90 is 90% of the total weight of all the particles. D10 is the same.

In the present invention, a tetravalent titanium compound (b) can be used. Those tetravalent titanium compounds are
For example, the general formula TiX ¹ n (OR ¹ ) _4-n (where X ¹ is a halogen atom, especially a chlorine atom, and R ¹
Is a hydrocarbon group having 1 to 10 carbon atoms, particularly a linear or branched alkyl group, and when a plurality of groups R ¹ are present, they may be the same or different from each other. n is 0 to 4
Is an integer. ) Is a tetravalent titanium compound. Specifically, Ti (O-i-C 3 H 7) 4, Ti (O-C 4 H 9) 4, T
_{iCl (O-C 2 H 5} ) 3, TiCl (O-i-C 3 H 7) 3, TiCl (O-C
_{4 H 9) 3, TiCl 2} (O-C 4 H 9) 2, TiCl 2 (O-i-C 3 H
₇ ) ₂ , TiCl _{4 and the} like.

In the solid catalyst component of the present invention, an optional electron donating compound (c) can be used, if necessary.
These electron donating compounds (c) are usually organic compounds containing oxygen, nitrogen, phosphorus or sulfur. Specifically, amines, amides, ketones, nitriles, phosphines, phosphylamides, esters, ethers, thioethers, alcohols, thioesters, acid anhydrides, acid halides, aldehydes, Examples thereof include organic acids, organic silicon compounds having a Si—O—C bond, and more specifically, the following compounds.

Aromatic carboxylic acids such as benzoic acid, p
-Oxybenzoic acid; acid anhydrides such as succinic anhydride,
Benzoic anhydride, p-toluic anhydride; 3-1 carbon atoms
5 ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone; aldehydes having 2 to 15 carbon atoms, for example, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, naphthaldehyde; 2 carbon atoms ~ 18 esters, for example,
Methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, Ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, toluyl Methyl acrylate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate,
Ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate;

Preference is given to mono- and diesters of aromatic dicarboxylic acids, for example monoesters and diesters of phthalic acid, for example monomethyl phthalate, dimethyl phthalate, monomethyl terephthalate, dimethyl terephthalate, monoethyl phthalate, diethyl phthalate,
Monoethyl terephthalate, diethyl terephthalate,
Monopropyl phthalate, dipropyl phthalate, monopropyl terephthalate, dipropyl terephthalate,
Monobutyl phthalate, dibutyl phthalate, monobutyl terephthalate, dibutyl terephthalate, monoisobutyl phthalate, diisobutyl phthalate, monoamyl phthalate, diamyl phthalate, monoisoamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, ethyl propyl phthalate;

Acid halides having 2 to 20 carbon atoms,
As the acid moiety (acyl group moiety) of the acid halide, an aliphatic (including an alicyclic or other ring-containing) monobasic, dibasic or tribasic group having about 2 to 20 carbon atoms is used. A mono- to tri-valent acyl acid obtained by extracting each hydroxyl group from an acid, or an aromatic (alkali-
And aralkyl types. And the like. Monovalent to trivalent acyl groups obtained by extracting respective hydroxyl groups from a monobasic, dibasic or tribasic acid of the system are preferred. Further, as the halogen atom in the acid halide, a chlorine atom, a bromine atom and the like are preferable, and a chlorine atom is particularly preferable.

In the present invention, acid halides that can be suitably used include, for example, acetyl chloride, acetyl bromide, propionyl chloride, butyryl chloride, isobutyryl chloride, 2-methylpropionyl chloride, valeryl chloride, and the like. Isovaleryl chloride, hexanoyl chloride, methylhexanoyl chloride, 2-ethylhexanoyl chloride, octanoyl chloride, decanoyl chloride, undecanoyl chloride, hexadecanoyl chloride, octadecanoyl chloride, benzylcarbonyl chloride, cyclohexanecarbonyl Chloride, malonyl dichloride, succinyl dichloride, pentanedioyl dichloride, hexanedioil dichloride, cyclohexanedicarbonyl dichloride, benzoylc Chloride, benzoyl bromide, methylbenzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, benzene -
1,2,4-tricarbonyl trichloride and the like can be mentioned. Among these, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride and the like are particularly preferable, and phthaloyl chloride is particularly preferable.
These acid halides may be used alone or in a combination of two or more.

Ethers having 2 to 20 carbon atoms, for example, methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether; acid amides such as acetate amide, benzoate Acid amide, toluic acid amide; amines such as tributylamine, N, N′-dimethylpiperazine, tribenzylamine, aniline, pyridine,
Pyrroline, tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile, tolunitrile; tetramethylurea, nitrobenzene, lithium butyrate;

Organic silicon compounds having a Si--O--C bond, for example, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane Methoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyl Triisopropoxysilane,
Vinyl tributoxy silane, ethyl silicate, butyl silicate, trimethylphenoxy silane, methyl triaryloxy silane, vinyl tris (β-methoxyethoxy) silane, vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane and the like can be mentioned. Of these, preferred are esters, ethers, ketones, acid anhydrides and the like.

The solid catalyst component (A) is prepared by a known method using the solid product (a), the tetravalent titanium compound (b) and, if necessary, the electron-donating compound (c). Can be prepared. For example, it is preferable that the solid product (a) is brought into contact with the electron donating compound (c) and then brought into contact with the tetravalent titanium compound (b). The conditions for bringing the electron donating compound (c) into contact with the solid product (a) are not particularly limited, and may be appropriately determined according to various circumstances. Usually, 0.01 to 10 mol of the electron donating compound (c) per 1 mol of the solid product (a) in terms of magnesium atom,
Preferably, 0.05 to 5 mol is added, and the contact reaction may be performed at 0 to 200 ° C. for 5 minutes to 10 hours, preferably at 30 to 150 ° C. for 30 minutes to 3 hours. In addition, an inert hydrocarbon such as pentane, hexane, heptane or octane can be added to the reaction system as a solvent.

The conditions for contacting the tetravalent titanium compound (b) with the solid product (a) or the contact product thereof with the electron-donating compound (c) are not particularly limited, but are usually not limited. Represents 1 to 50 mol, preferably 2 to 20 mol of the tetravalent titanium compound (b) per 1 mol of magnesium in the product.
5 minutes to 10 hours at 0 to 200 ° C.
The reaction is preferably performed at 30 to 150 ° C. for 30 minutes to 5 hours. The contact with the tetravalent titanium compound (b) is carried out by using a liquid tetravalent titanium compound (for example, titanium tetrachloride) by itself and other tetravalent titanium compounds by using any inert hydrocarbon solvent ( For example, it can be carried out in a state of being dissolved in hexane, heptane, kerosene). Before the contact between the solid product (a), the tetravalent titanium compound (b) and, if necessary, the electron-donating compound (c), for example, a halogenated hydrocarbon or a halogen-containing compound may be used. Silicon compounds,
Halogen gas, hydrogen chloride, hydrogen iodide and the like can be brought into contact with the solid product (a). After the completion of the reaction, the product is preferably washed with an inert hydrocarbon (for example, n-hexane or n-heptane).

The solid catalyst component has a pore volume of 0.4 cc /
g or more, and the specific surface area is preferably 300 m ² / g or more. If either the pore volume or the specific surface area deviates from the above range, the catalytic activity may decrease. In addition,
The pore volume and the specific surface area can be determined from the volume of the adsorbed nitrogen gas according to, for example, the BET method [“Journal of American Chemical Society”.
(J. Am. Chem. Soc.), Vol. 60, p. 309 (1983
Year)].

In the method for producing a polyolefin of the present invention,
As the organometallic compound (B), any organic compound containing a metal belonging to Groups 1 to 3 of the periodic table can be suitably used. Examples of the metals of Groups 1 to 3 of the periodic table include lithium, sodium, potassium, zinc, cadmium, aluminum, and the like, with aluminum being particularly preferred. Specific examples of the organometallic compound (B) include alkyl lithiums, for example, methyl lithium, ethyl lithium, propyl lithium or butyl lithium;
Examples include dialkyl zinc, such as dimethyl zinc, diethyl zinc, dipropyl zinc or dibutyl zinc.

Further, as the organoaluminum compound,
In the general formula ^{_{AlR 2 m X 2 3-m}} ( wherein, R ² is an alkyl group, a cycloalkyl group or an aryl group having 1 to 10 carbon atoms, m is an integer of 1 to 3, X ² is a halogen A compound represented by an atom such as a chlorine atom or a bromine atom) is widely used. Specifically, trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum or trioctylaluminum; or dialkylaluminum monohalide compounds such as diethylaluminum monochloride and dipropylaluminum monochloride Or dioctyl aluminum monochloride and the like can be mentioned.

In the production method of the present invention, an electron donating compound (C) can be used in combination, if necessary. In this case, as the electron donating compound (C), the same one as the electron donating compound (c) used in preparing the solid catalyst component (A) can be used. At this time, the electron donating compound (C) may be the same as or different from the electron donating compound (c) used in the preparation of the solid catalyst component (A).

The olefin that can be polymerized by the production method of the present invention is usually represented by the general formula R ³ —CH ＝ CH ₂ (where R ³ is a hydrogen atom or an alkyl or cycloalkyl group having 1 to 20 carbon atoms). A), for example, linear monoolefins such as ethylene,
Propylene, butene-1, hexene-1 or octene-
1; branched monoolefins such as 4-methyl-pentene-1; and dienes such as butadiene. The method of the present invention can be effectively used for homopolymerization or copolymerization of various olefins.

As the polymerization conditions, the same conditions as those used in known methods can be used. For example, under a partial pressure of an olefin higher than the atmospheric pressure, at a temperature of -80 ° C. to + 150 ° C., if necessary, an inert hydrocarbon may be used. It can be carried out in the liquid or gas phase in the presence of a diluent. The polyolefin powder thus obtained is nearly spherical and has a sharp particle size distribution. That is, the sphericity (S) is less than 1.60 and the particle size distribution index (P) is less than 5.0.

As is apparent from the above description, the method of the present invention is a method for producing a polyolefin using a so-called Ziegler-type catalyst, wherein the solid produced by reacting metallic magnesium with an alcohol and a specific amount of a halogen-containing metal compound. The product (a) is used as a carrier. Therefore, the constituent components other than the solid product (a), that is, the tetravalent titanium compound (b), the organometallic compound (B) and other desired components (for example, an electron donating compound), and the solid catalyst component ( A) Preparation method,
Alternatively, conventional techniques can be directly applied to the olefin polymerization conditions and the like. These conventional methods are described, for example, in JP-B-46-34098 and JP-A-52-34098.
98076, JP-A-53-2580, JP-A-53-2580
No. 43,094, JP-A-61-181807, JP-A-6181
2-127305, JP-A-60-63207 and JP-A-60-139706.

[0041]

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. The following reagents were used in the following Examples and Comparative Examples. Magnesium metal: Granular (average particle size: 350 μm) Ethanol: Wako Pure Chemical Industries, Ltd., reagent grade iodine: Wako Pure Chemical Co., Ltd., reagent grade magnesium chloride: Wako Pure Chemical Co., Ltd., reagent grade magnesium iodide : Wako Pure Chemical Industries, Ltd., special grade reagent

The X-ray diffraction measurement was performed as follows. The solid product was pulverized to an average particle size of 10 μm. The pulverized material was vacuum-dried at room temperature, and the obtained dry powder was filled in a mylar film cell under an inert gas atmosphere. The thickness of the mylar film was 6 μm, and the thickness of the cell including the mylar film and the dry powder was 1 mm. This cell was attached to a powder X-ray diffractometer [manufactured by Rigaku Denki Kogyo Co., Ltd.], and an X-ray diffraction spectrum was measured by a transmission method. Copper (Cu) is used for the opposite cathode and the voltage is 50
kv, current 120 mA, and wavelength (λkα) 1.543
Angstrom conditions were used.

Example 1 (1) Preparation of solid product (a) Glass reactor equipped with a stirrer (internal volume 0.5 liter)
Is sufficiently replaced with argon gas, 200 g of ethanol and 0.45 g of magnesium chloride (anhydrous) are added and dissolved. Then, 12 g of metallic magnesium is added, and hydrogen gas is generated from the inside of the system under reflux under stirring. The reaction was continued until it disappeared to obtain a solid reaction product. The reaction solution containing the solid reaction product was dried under reduced pressure to obtain a solid product (a). The obtained solid product was confirmed to be spherical by electron microscope observation. The solid product was subjected to X-ray diffraction analysis using CuKα radiation. As a result, three diffraction peaks appeared in the range of 2θ = 5 to 20 °. When these peaks are referred to as a peak a, a peak b, and a peak c in order from the low angle side, the peak intensity ratio b / c
Was 0.69.

(2) Preparation of Solid Catalyst Component (A) The solid product (a) was placed in a glass three-necked flask (internal volume 0.5 liter) sufficiently purged with argon gas.
(Not crushed) 16 g and dehydrated heptane 8
0 ml was added, and 2.4 ml of silicon tetrachloride was added under stirring. Further, 2.5 ml of diethyl phthalate was added, and the inside of the system was maintained at 60 ° C. Next, 80 ml of titanium tetrachloride was charged and maintained at 110 ° C. for 2 hours, and then washed with heptane at 80 ° C. Further, after 100 ml of titanium tetrachloride was added and maintained at 110 ° C. for 2 hours, the solid catalyst component (A) was obtained by washing with heptane. The specific surface area of this solid catalyst component was 382 m ² / g, and the pore volume was 0.61 cc / g.

(3) Polymerization A SUS autoclave (with an internal volume of about 1.0 liter) sufficiently purged with argon gas was charged with 400 m of purified heptane.
l, 1 mmol of triethylaluminum, 0.25 mmol of cyclohexylmethyldimethoxysilane and 0.005 mmol of the solid catalyst component (A) in terms of titanium atom, and hydrogen up to 0.5 kg / cm ² .
Polymerization of propylene was performed at 70 ° C. for 2 hours at a total pressure of 8 kg / cm ² . Table 1 shows the above results.

The term "stereoregularity" in the table refers to the insoluble matter after extraction with boiling heptane for 6 hours. The sphericity (S) was measured as follows. In the case of the solid product (a) A sample of the solid product (a) after drying is photographed with a scanning electron microscope (JSM-25SIII, manufactured by JEOL Ltd.) at an acceleration voltage of 5 KV and a magnification of 150 times. I got next,
This negative was subjected to image analysis processing by a transmission method. The image analysis process was performed on an image analysis apparatus (manufactured by Nexus Corp.) by cutting particles of 20 pixels or less (one pixel was 1.389 μ × 1.389 μ) and about 2,000 remaining particles. By the image analysis processing, the contour length E1 and the circumference E2 of the circle equal to the projected area of the particle were obtained, and were calculated by the above equation (1). In the case of polyolefin powder A sample of polyolefin powder was subjected to image analysis processing by a direct reflection method. In the image analysis processing, one pixel is set to 0.08
Except that it was set to 13 mm x 0.0813 mm, the same procedure was performed as for the solid product (a), and the calculation was carried out according to the formula (1). Similarly, the particle size distribution index (P) is obtained by determining the particle size distribution of the particles with a sieve, plotting the distribution on a logarithmic distribution paper,
% Particle diameter (D90) and 10% particle diameter (D10) were calculated by the above formula (2). Further, the bulk density of the polyolefin powder was measured according to JIS K6721. The same applies to the following examples and comparative examples.

Example 2 (1) Preparation of solid product (a) The procedure of Example 1 (1) was repeated except that the amount of magnesium chloride was changed to 0.3 g. The obtained solid product was confirmed to be spherical by electron microscope observation. (2) Preparation of solid catalyst component (A) Using the obtained solid product, a solid catalyst component (A) was prepared in the same manner as in Example 1 (2). (3) Polymerization Using the obtained solid product (a), propylene was polymerized in the same manner as in Example 1 (3). Table 1 shows the above results.

Example 3 (1) Preparation of solid product (a) The same procedure as in Example 1 (1) was carried out. (2) Preparation of solid catalyst component (A) The amounts of Zr (On-Bu) ₄ and Ti (O-
50 ml of hexane in which n-Bu) ₄ is dissolved is mixed with 150 g of a hexane slurry containing 10 g of the obtained solid product (a).
The mixture was added dropwise at a temperature of 20 ° C. for 15 minutes with stirring to the mixture, and 92 ml of a 50% by weight hexane dilution of EtAlCl ₂ was added thereto at a temperature of 35 ° C. with stirring.
It was added dropwise over a period of 0 minutes, and further reacted for 120 minutes under reflux. Next, the column was washed with dry hexane until no chlorine was detected in the liquid.
l. (3) Polymerization 400 ml of n-hexane was added to a 1 liter autoclave equipped with a stirrer, the temperature was raised to 80 ° C., and the internal atmosphere was sufficiently replaced with hydrogen gas.
g / cm ² · G, and further 5.4k of ethylene
g / cm ² · G. Then add 0.01
The solid catalyst component (A) obtained in the above (2) containing 0 mmol of Ti and 0.50 mm of triisobutylaluminum
The polymerization of ethylene was carried out for 1 hour while supplying ethylene so as to maintain the total pressure at 5.4 kg / cm ² · G. Table 1 shows the above results.

Example 4 (1) Preparation of solid product (a) Magnesium chloride 0.4 as a halogen-containing metal compound
Example 1 (1) was repeated except that 1.35 g of magnesium iodide was used instead of 5 g. (2) Preparation of solid catalyst component (A) Using the obtained solid product, a solid catalyst component (A) was prepared in the same manner as in Example 1 (2). (3) Polymerization Using the obtained solid product (a), propylene was polymerized in the same manner as in Example 1 (3). Table 1 shows the above results.

Comparative Example 1 (1) Preparation of solid product (a) Example 1 (1) except that magnesium chloride was not used.
A solid product was prepared as described above. This solid product was ground in a 1 liter stainless steel ball mill for 24 hours. (2) Preparation of solid catalyst component (A) Using the obtained solid product, a solid catalyst component (A) was prepared in the same manner as in Example 1 (2). (3) Polymerization Using the obtained solid product (a), propylene was polymerized in the same manner as in Example 1 (3). Table 1 shows the above results.

[0051]

[Table 1]

[0052]

According to the present invention, by using a solid product (a) obtained from magnesium metal, an alcohol and a halogen-containing metal compound as a catalyst for polyolefin, a particle size adjusting treatment such as grinding is performed. At least, it is possible to obtain a polymer which exhibits high catalytic activity and high tacticity and has good powder morphology.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a manufacturing method of the present invention.

Claims (6)

(57) [Claims] 1. A solid product used for preparing a solid catalyst component for olefin polymerization, comprising a metal magnesium, an alcohol, and a halogen atom in an amount of 0.0001 gram atom or more per gram atom of the metal magnesium. And a sphericity (S) represented by the following formula (1) is S <1.60, and a particle diameter represented by the following formula (2): A solid product with a distribution index (P) of P <5.0. S = (E1 / E2) ² (1) (where E1 indicates the contour length of the projection of the particle, and E2 indicates the circumference of a circle equal to the projection area of the particle.) P = D90 / D10. (2) (Here, D90 indicates a particle diameter corresponding to a cumulative weight fraction of 90%, and D10 indicates a particle diameter corresponding to a cumulative weight fraction of 10%.) 2. (a) the solid product of claim 1;
(B) A solid catalyst composition obtained using a tetravalent titanium compound. 3. A solid catalyst composition obtained by using (a) the solid product according to claim 1 or 2; (b) a tetravalent tetravalent titanium compound; and (c) an electron donating compound. Stuff. 4. Use of (A) (a) a solid product according to claim 1, (b) a solid catalyst component obtained using a tetravalent titanium compound, and (B) an organometallic compound. A method for producing a polyolefin, comprising: 5. A solid catalyst component obtained by using (A) (a) the solid product according to claim 1, (b) a tetravalent titanium compound, and (c) an electron-donating compound. A method for producing a polyolefin, comprising using (B) an organometallic compound and (C) an electron-donating compound. 6. The obtained polyolefin powder has a sphericity (S) represented by the above formula (1) satisfying S <1.60 and a particle size distribution index (P) represented by the above formula (2). The method for producing a polyolefin according to claim 4, wherein P <5.0.