JPH051114A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain the polymer having high stereoregularity and excellent morphology by preliminarily polymerizing an olefin in the presence of a solid formed product comprising metal Mg with an alcohol, a halogen, etc., and a titanium halide. CONSTITUTION:(A) An olefin is preliminarily polymerized by using a solid catalytic component obtained by reacting a solid formed product, prepared by reacting metal Mg with an alcohol and 0.0001g atom based on 1g atom metal Mg of a halogen or a halogen atom-containing compound, with a titanium halide compound in the presence or absence of an electron donative compound while stirring a stirring blade consisting of a bottom paddle blade part 2 and an upper blade part 3 attached to a stirring shaft 1 set at the center of an agitating tank 10 under a condition wherein the formula H/L>0.5 (L is liquid level; H is height up to the highest part of the upper blade part) is satisfied and the bottom paddle blade part 2 is under the liquid level and then (B) the olefin is polymerized by using a catalyst system blended with an organometallic compound to give the objective polyolefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyolefin by using a specific solid catalyst component for olefin polymerization and preliminarily polymerizing it with a small amount of olefin.

[0002]

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

However, when these magnesium compounds are used as a carrier raw 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, as the particle size adjusting means, only the magnesium compound may be pulverized or may be co-pulverized when the unpulverized magnesium compound is treated with an ester or the like, but in any case, mechanical pulverization, classification, etc. Processing is an essential operation.

When a material which is not subjected to such pulverization treatment is used as a carrier raw material, the polymerization activity of the catalyst is low and the amount of the transition metal (for example, titanium) itself supported is low, so that the productivity per unit catalyst is low. Get lower. Due to this, there arises a problem that the amount of residual chlorine in the polymer increases. In addition, a problem occurs in the shape and particle size distribution of the obtained polymer particles, which causes troubles in the process of producing the polyolefin (for example, clogging of the transfer line due to frequent fine polymer particles). Therefore, it is recognized that the crushing process of magnesium compounds is very important, but this mechanical crushing process sets the conditions for that (wet or dry crushing method, crushing that affects the shape of the crushed product). It took a lot of labor and cost even if one process such as a machine, a crushing strength, a crushing time) was taken.

Further, a method of supporting magnesium on an inorganic oxide such as silica for the purpose of improving the so-called morphology such as the particle size and shape of the produced polymer (Japanese Patent Laid-Open No. 6-58242)
1-291604, 61-291105, 62
-119203, 62-119204)
Alternatively, a method in which a magnesium compound is once dissolved in a solvent such as alcohol and then re-precipitated is used (Japanese Patent Application Laid-Open No. Sho 5).
No. 6-811) is also known, but in these methods, although a crushing step can be omitted, a supporting process, a dissolution process, and a precipitation process are required, which makes the process extremely complicated and the performance of the catalyst. It has the drawback of poor stability. Therefore, there is a demand for a method of controlling the particle size, particle size distribution and morphology of an olefin polymerization catalyst carrier without performing complicated operations such as mechanical pulverization and classification.

By the way, when a highly active catalyst is put into a polymerization vessel as it is and exposed to a high temperature near the polymerization temperature, the activity and the stereoregularity of the obtained polymer become insufficient, or the catalyst adheres to the reactor wall. There's a problem. On the other hand, as a method for solving the above problem, a small amount of α-
So-called prepolymerization in which olefin is polymerized is performed. This prepolymerization is usually carried out in a stirring tank in a slurry state with a diluting solvent. But,
At this time, if an attempt is made to increase the amount of prepolymerization, there is a problem that the capacity of the stirring tank becomes enormous, which is disadvantageous in terms of equipment cost. Moreover, as a method of solving the disadvantage,
A method of increasing the slurry concentration is considered, but under normal stirring conditions, if the concentration becomes high, sufficient stirring will not be performed, and therefore the catalyst performance will deteriorate due to local heat generation, and the activity and stereoregularity of the resulting polymer will be insufficient. Becomes on the other hand,
When the slurry concentration is kept low, long-term prepolymerization is required to obtain a predetermined amount of prepolymerization, which causes a remarkable decrease in activity. Therefore, conventionally, in the production of polyolefin using a solid catalyst component,
A method capable of performing a prepolymerization treatment with a high slurry concentration is desired.

[0007]

In view of the present situation, the present inventors have diligently studied about producing a catalyst carrier raw material having a spherical shape and a controlled particle size and particle size distribution by a one-step reaction. As a result, when the metal magnesium and alcohol were reacted with a specific amount of halogen and / or a halogen-containing compound, the particle size distribution was narrow, and the olefin polymerization was carried out without any particle size adjustment treatment such as pulverization or classification. To obtain a solid product that can be used as a carrier raw material for a catalyst for use in the polymerization, and when an olefin is polymerized using a catalyst component for olefin polymerization using the solid product as a carrier, the amount of supported titanium and the polymerization activity are equal to or higher than those of the conventional case. It was found that a polymer having markedly improved morphology while exhibiting stereoregularity can be obtained. Furthermore, the present inventors can freely control the particle size of the obtained solid product by appropriately selecting the reaction conditions of the metal magnesium, the alcohol, and the halogen-containing compound, and thus control the morphology of the produced polymer. I found that I could do it freely.

Further, the inventors of the present invention have conducted various researches for producing a polymer excellent in morphology, particularly for carrying out a prepolymerization treatment at a high slurry concentration, and as a result, the solid catalyst component (A) was used. When a prepolymerization treatment with the solid catalyst component (A) is carried out in the production of a polyolefin by using a specific stirring blade and stirring conditions, good stirring is performed even at a high slurry concentration, and an efficient prepolymerization treatment is carried out. Found that is possible.

By the way, a solid product obtained by reacting metallic magnesium, an alcohol and a specific amount of halogen and / or a halogen-containing compound according to the present invention is a substance which is completely different from any conventionally known magnesium-based carrier raw material. Is. In fact, it has been conventionally known that a small amount of iodine, ethyl orthoformate, or the like is added when reacting metallic magnesium and alcohol (Japanese Patent Publication No. 46-
7093, U.S. Pat. No. 4,412,132), iodine and the like are merely used as reaction initiators in these reactions, and the amount thereof is very small. In comparison, the amount of halogen used in the present invention is much larger than that used as the reaction initiator, and therefore the solid product according to the present invention is completely different from those shown in these prior arts. I understand. That is, the present invention provides a method for producing a polyolefin by using a novel prepolymerization treatment using a completely new solid catalyst component for olefin polymerization which has not been known so far.

Therefore, the present invention provides (a) magnesium metal, alcohol, and halogen in an amount of 0.0001 gram atom or more per 1 gram atom of the metal magnesium or 0.0 per gram atom of the metal magnesium.
A solid product obtained by reacting a halogen-containing compound containing halogen atoms in an amount of 001 gram atom or more;
(B) In preparing a polyolefin using the solid catalyst component (A) obtained by reacting a titanium halide compound with or without an electron donating compound, a preliminary treatment with the solid catalyst component (A) is carried out. Provided is a method for producing a polyolefin, characterized in that the polymerization treatment is carried out in a stirring tank under the following stirring conditions or conditions. Arranged on a stirring shaft provided at the center of the stirring tank,
An agitating blade composed of a bottom paddle blade located near the bottom of the tank and an upper blade located above the bottom paddle, wherein the liquid level during the reaction is L, and the top of the blade from the bottom of the tank to the upper blade. When the height of the paddle is H, H / L> 0.5, and stirring is performed using a stirring blade such that the uppermost portion of the bottom paddle blade portion is lower than the liquid level surface. The above-mentioned stirring blade is used, and the diameter of the stirring blade is d (m),
When the number of rotations is n (rpm), 4.3 × 10 ³ <n ³ d ²
Stirring is performed under the condition of <4.0 × 10 ⁶ .

The present invention will be described in more detail below. In the present invention, at least (a) a solid product obtained by reacting magnesium metal, an alcohol, halogen and / or a halogen-containing compound, and (b) a solid catalyst component obtained by reacting a titanium halide compound ( A preliminary polymerization treatment is carried out using A).

In this case, the shape of metallic magnesium in the solid product (a) is not particularly limited. Therefore, metallic magnesium of any particle size, eg granular,
Ribbon-shaped or powdered metallic magnesium can be used. The surface state of the metallic magnesium is not particularly limited, but it is preferable that the surface of the metallic magnesium is not coated with magnesium oxide.

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 the water content of the alcohol are not limited, but when an alcohol having a high water content is used, magnesium hydroxide [Mg (OH) ₂ ] is produced on the surface of magnesium metal, so that the water content is 1% or less, particularly 2000 ppm.
It is preferable to use the following alcohols. Furthermore, in order to obtain a solid product (a) having a better morphology, the smaller the water content, the more preferable, and generally 200 ppm or less is desirable.

The type of halogen is not particularly limited, but chlorine, bromine or iodine, especially iodine is preferably used. The kind of the halogen-containing compound is not limited, and any compound containing a halogen atom in its chemical formula can be used. In this case, the type of halogen atom is not particularly limited, but chlorine, bromine or iodine is preferable. Further, among the halogen-containing compounds, halogen-containing metal compounds are particularly preferable. As the halogen-containing compound, specifically, MgCl ₂ , MgI ₂ , M
g (OEt) Cl, Mg (OEt) I, MgBr ₂ , C
ACl ₂ , NaCl, KBr, etc. can be preferably used. Of these, MgCl ₂ and MgI ₂ are particularly preferable. These states, shapes, particle sizes and the like are not particularly limited and may be arbitrary, and for example, they can be used in the form of a solution in an alcohol solvent (for example, ethanol).

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

The amount of halogen used is 1 magnesium metal.
The amount of gram atom is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, and more preferably 0.001 gram atom or more. The halogen-containing compound has a halogen atom in the halogen-containing compound of 0.0001 gram atom or more, preferably 0.0005 gram atom or more, based on 1 gram atom of metallic magnesium.
More preferably, it is used in an amount of 0.001 gram atom or more. If the amount is less than 0.0001 gram atom, there is no great difference from the amount of halogen used as the reaction initiator, and the pulverizing and classifying treatment of the solid product is indispensable to obtain the desired particle size.

Each of the halogen and the halogen-containing compound may be used alone or in combination of two or more. Further, halogen and a halogen-containing compound may be used in combination. When halogen and a halogen-containing compound are used in combination, the total amount of halogen atoms is 0.0001 gram atom or more per 1 gram atom of metallic magnesium.
The amount is preferably 0.0005 gram atom or more, and more preferably 0.001 gram atom or more. The upper limit of the amount of halogen and / or halogen-containing compound used is not particularly limited and may be appropriately selected within a range in which the desired solid product is obtained. Generally, the amount of all halogen atoms is 1 g of magnesium metal. It is preferably less than 0.06 gram atom per atom. In this case, halogen and /
Alternatively, the particle size of the solid product can be freely controlled by appropriately selecting the amount of the halogen-containing compound used.

The reaction itself between the magnesium metal, the alcohol, the halogen and / or the halogen-containing compound can be carried out in the same manner as a known method. For example, metallic magnesium, an alcohol, a halogen and / or a halogen-containing compound are reacted under reflux (about 79 ° C.) until generation of hydrogen gas is no longer recognized (usually about 20 to 30 hours) to produce a solid. It is a way to get things. Specifically, for example, when iodine is used as the halogen, a method in which solid iodine is introduced into metallic magnesium and alcohol, and then heated and refluxed, metallic alcohol is added after the alcohol solution of iodine is dropped into the alcohol and heated. And the like, and a method of dropping an alcohol solution of iodine while heating the magnesium metal or alcohol solution. Both methods are preferably carried out under an inert gas (for example, nitrogen gas or argon gas) atmosphere, optionally using an inert organic solvent (for example, saturated hydrocarbon such as n-hexane).

Regarding the addition of magnesium metal, alcohol, halogen and / or halogen-containing compound, it is not necessary to add the whole amount to the reaction tank from the beginning, and it may be added in a divided manner. A particularly preferable form is a method in which the entire amount of alcohol is charged from the beginning, and metallic magnesium is charged in several times. If you do this,
It is possible to prevent the generation of a large amount of hydrogen gas temporarily, which is highly desirable from the viewpoint of safety. Also, the reaction tank can be downsized. Further, it becomes possible to prevent the entrainment of alcohol, halogen and / or halogen-containing compound caused by the temporary large generation of hydrogen gas. The number of divisions may be determined in consideration of the scale of the reaction tank,
Although not particularly limited, it is usually 5 to 10 in consideration of complexity of operation.
Times are preferred.

It goes without saying that the reaction itself may be either batch type or continuous type. Furthermore, as a modified method, a small amount of metal magnesium is first added to the alcohol that has been entirely added from the beginning, the product produced by the reaction is separated and removed in another tank, and then a small amount of metal magnesium is added again. It is also possible to repeat. When the solid product thus obtained is used for the next synthesis of the 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 can be used in the following steps without pulverization or classification operation for adjusting the particle size distribution.

The solid catalyst component (A) used in the present invention is obtained from at least (a) the above solid product and (b) a titanium halide compound. Examples of the titanium halide compound (b) in the solid catalyst component (A) include, for example, the general formula TiX ¹ n (OR ¹ ) _4-n (wherein, X ¹ is a halogen atom, particularly a chlorine atom, and R ¹
Is a hydrocarbon group having 1 to 10 carbon atoms, in particular 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 0-4
Is an integer. ) And titanium compounds. 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) can be exemplified _2, TiCl ₄ or the like.

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

Aromatic carboxylic acids such as benzoic acid, p
-Oxybenzoic acid; acid anhydrides such as succinic anhydride,
Benzoic anhydride, p-toluic anhydride; C3 to C1
5 ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone; aldehydes having 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, octylaldehyde, benzalded, 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 acid, 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;

Aromatic dicarboxylic acid mono and diesters such as phthalic acid monoesters and diesters are preferred, 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,
The acid portion (acyl group portion) of the acid halide is an aliphatic (including those having a ring such as alicyclic) carbon atoms of about 2 to 20, monobasic, dibasic or tribasic. A monovalent to trivalent acyl acid obtained by removing each hydroxyl group from an acid, or an aromatic (alkali-containing) having about 7 to 20 carbon atoms.
Also includes le-type and aralkyl-type. ) Monovalent to trivalent acyl groups obtained by removing each hydroxyl group from a monobasic, dibasic or tribasic acid of the system are preferred. The halogen atom in the acid halide is preferably a chlorine atom, a bromine atom, etc., and particularly preferably a chlorine atom.

Acid halides that can be preferably used include, for example, acetyl chloride, acetyl bromide, propionyl chloride, butyryl chloride, isobutyryl chloride, 2-methylpropionyl chloride,
Valeryl chloride, isovaleryl chloride, hexanoyl chloride, methylhexanoyl chloride, 2-ethylhexanoyl chloride, octanoyl chloride, decanoyl chloride, undecanoyl chloride, hexadecanoyl chloride, octadecanoyl chloride, benzylcarbonyl Chloride, cyclohexane carbonyl chloride, malonyl dichloride, succinyl dichloride, pentane dioil dichloride, hexane dioil dichloride, cyclohexane dicarbonyl dichloride, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride. , Benzene-1,2,4-
Tricarbonyl trichloride etc. can be mentioned. Among these, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride and the like are preferable, and phthaloyl chloride is particularly preferable. These acid halides may be used alone or in combination of two or more.

Ethers having 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether; acid amides such as acetic acid amide, benzoic acid Acid amide, toluic acid amide; amines such as tributylamine, N, N′-dimethylpiperazine, tribenzylamine, aniline, pyridine,
Pyroline, tetramethylethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolunitrile; Tetramethylurea, nitrobenzene, lithium butyrate;

Organosilicon compounds having a Si--O--C bond, such as trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, phenyltri. Methoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyl Triisopropoxysilane,
Examples thereof include vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, and dimethyltetraethoxydisiloxane. Among these, preferred are esters, ethers, ketones, acid anhydrides and the like.

The solid catalyst component (A) can be prepared by a known method using (a) a solid product, (b) a titanium compound and, if necessary, (c) an electron donating compound. . For example, it is preferable to contact the solid product (a) with the electron-donating compound (c) and then contact with the 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 depending on various circumstances. Usually, 0.01 to 10 moles of the electron-donating compound (c), preferably 0.1 to 1 mole of the solid product (a) in terms of magnesium atom.
05 to 5 moles may be added, and the catalytic 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. Incidentally, an inert hydrocarbon such as pentane, hexane, heptane or octane can be added to this reaction system as a solvent.

The titanium compound (b) is added to the solid product (a) or to the contact product of the solid product (a) and the electron-donating compound (c).
There are no particular restrictions on the conditions for contacting, but usually 1 to 50 mol, preferably 2 to 20 mol of the titanium compound (b) is added to 1 mol of magnesium in the product. The reaction is performed at ˜200 ° C. for 5 minutes to 10 hours, preferably at 30 to 150 ° C. for 30 minutes to 5 hours. The liquid titanium compound (for example, titanium tetrachloride) is used alone for the contact with the titanium compound (b), and the titanium compound other than the above is used for any inert hydrocarbon solvent (for example, hexane,
It can be carried out in a state of being dissolved in heptane, kerosene). In addition, prior to the contact between the solid product (a) and the titanium compound (b), and optionally the electron donating compound (c), for example, a halogenated hydrocarbon, a halogen-containing silicon compound, It is also possible to bring halogen gas, hydrogen chloride, hydrogen iodide, or the like into contact with the solid product (a).
After the reaction, it is preferable to wash the product with an inert hydrocarbon (for example, n-hexane or n-heptane).

In the present invention, as the prepolymerization, the solid catalyst component (A) is previously contacted with a small amount of olefin to form an olefin polymer. The prepolymerization is carried out by bringing the solid catalyst component (A) into contact with an olefin. In this case, the olefin may be introduced immediately after preparation of the solid catalyst component (A), or 0.2 to
It may be introduced after aging for about 3 hours. Furthermore, the solid catalyst component (A) can be supplied by suspending it in an inert solvent or olefin.

There is no limitation on the kind of the olefin used in the prepolymerization, but in general, R ³ --CHCH ₂ (wherein R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group) A), for example, linear monoolefins such as ethylene,
Propylene, butene-1, hexene-1 or octene-
1; branched monoolefins such as 4-methyl-pentene-1; or dienes such as butadiene. Among these, the same olefin as the olefin to be polymerized is particularly preferable. The amount of the prepolymerized product (olefin polymer) is 0.0 per gram of the solid catalyst component (A).
It is preferably from 3 to 1.0 gram, particularly preferably from 0.06 to 0.1 gram. Further, the prepolymerization temperature is preferably 60 ° C or lower, and particularly preferably 10 to 30 ° C.

The prepolymerization is carried out in a stirring tank using a stirring blade satisfying the above conditions. As a result, the prepolymerization treatment with the high-concentration slurry can be performed under good stirring. An example of such a stirring blade is shown in FIG.
Particularly preferable are lattice blades such as Maxblend blades (manufactured by Sumitomo Heavy Industries, Ltd.) shown in FIG. 2 and multistage blades such as full zone blades (manufactured by Shinko Pantech Co., Ltd.) shown in FIG. The stirring blades are arranged on a stirring shaft 1 provided at the center of the stirring tank 10, and are composed of a bottom paddle blade portion 2 located near the tank bottom portion 11 and an upper blade portion located above it. ing. In this case, when the liquid level during the reaction is L and the height from the tank bottom 11 to the uppermost part of the upper blade is H, H / L> 0.
5, and the uppermost part of the bottom paddle blade is lower than the liquid level surface.

The agitating blades may be, for example, the following (1) to (5). (1) The clearance between the bottom paddle blade portion 2 attached to the rotary shaft 1 and the tank bottom portion 11 is preferably as small as possible in order to sufficiently suspend the particles. Further, the bottom paddle blade portion 2 does not have to be one piece, and may be a combination of several pieces such as a turbine blade. Further, the bottom paddle blade portion 2 may be a retreat blade. (2) The upper blade portion 3 is for sufficiently mixing the particles discharged by the bottom paddle blade portion 2, and may be integrated with the bottom paddle blade portion 2 or may be a multi-stage one. Further, the angle may be offset from the bottom paddle blade portion 2, but the one having a lattice shape is preferable. (3) Height H from the bottom 11 of the tank to the top of the upper wing 3
When the ratio of the liquid surface height L to the liquid surface height L is 0.5 or less, a retention part is generated in the upper part, and agglomerates are generated to increase the amount of coarse powder. There is a method of increasing the rotation speed of the stirring blade to avoid the formation of the agglomerates, but the amount of fine powder increases and the particle size distribution expands. Therefore, H / L is particularly preferably 0.7 or more and 1 or less. (4) The ratio between the blade diameter d and the tank diameter D is not particularly limited, but is preferably 0.3 <d / D <0.8, more preferably 0.1.
4 <d / D <0.6. (5) A plurality of baffles 12 along the axial direction may be arranged on the side surface of the wall of the stirring tank 10. In addition, 1 in the figure
3 indicates a jacket.

When the prepolymerization treatment is carried out using the above stirring tank, 4.3 × 10 ³ <n ³ d ² <when the diameter of the stirring blade is d (m) and the number of rotations is n (rpm). It is preferably carried out under the condition of 4.0 × 10 ⁶ . As a result, the stirring process is performed even better. Also, more preferably 9.8 × 1
The condition is 0 ³ <n ³ d ² <3.6 × 10 ⁵ , more preferably 6.5 × 10 ⁴ <n ³ d ² <7.8 × 10 ⁴ . When the value of n ³ d ² is 4.3 × 10 ³ or less, the mixing of the particles in the slurry is reduced, and aggregates may be formed during the reaction. On the other hand, when the particle size is 4.0 × 10 ⁶ or more, the particles are crushed, the fine powder is increased, the particle size distribution is easily expanded, and the particle shape is deteriorated (not spherical).

The polyolefin production method of the present invention uses at least (A) a solid catalyst component and (B) an organometallic compound. Further, as the other component, for example, (C) an electron donating compound can be used if necessary. As the organic metal compound (B), any organic compound containing a metal of Groups 1 to 3 of the periodic table can be preferably used. Examples of the metals of Groups 1 to 3 of the periodic table include lithium, sodium, potassium, zinc, cadmium, aluminum and the like, and aluminum is particularly preferable. Specific examples of the organometallic compound (B) include alkyl lithium such as methyl lithium, ethyl lithium, propyl lithium or butyl lithium; dialkyl zinc such as dimethyl zinc and diethyl zinc.
Examples include dipropyl zinc or dibutyl zinc.

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 Compounds represented by atoms such as chlorine or bromine are widely used. Specifically, trialkyl aluminum compounds such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum or trioctyl aluminum; or dialkyl aluminum monohalide compounds such as diethyl aluminum monochloride and dipropyl aluminum monochloride. Alternatively, dioctylaluminum 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 the preparation of the solid catalyst component (A) can be used. In this case, 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 which can be polymerized by the production method of the present invention is usually represented by the general formula R ³ —CH═CH ₂ (wherein R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group). A), for example, linear monoolefins such as ethylene,
Propylene, butene-1, hexene-1 or octene-
1; branched monoolefins such as 4-methyl-pentene-1; or dienes such as butadiene. The method of the present invention can be effectively used for homopolymerization of these or copolymerization of various olefins.

As the polymerization conditions, the same conditions as in the known method can be used. For example, under a partial pressure of olefin higher than atmospheric pressure, at a temperature of −80 ° C. to + 150 ° C., and optionally an inert hydrocarbon. It can be carried out in the liquid or gas phase in the presence of a diluent. The polyolefin powder thus obtained is close to spherical and has a sharp particle size distribution.

As is apparent from the above description, the method for producing a polyolefin of the present invention is a method for producing a polyolefin using a so-called Ziegler-type catalyst, in which a specific solid product (a) is used as a carrier. It is characterized by using the component (A) after prepolymerization. Therefore, regarding the components other than the solid product (a), that is, the titanium compound (b), the organometallic compound (B) and other desired components (for example, an electron donating compound), the polymerization conditions of the olefin, etc. The conventional technology can be applied as it is. These conventional methods are described, for example, in Japanese Patent Publication No. 46-34098 and Japanese Unexamined Patent Publication No. 52-9807.
6, JP-A-53-2580, JP-A-53-4309.
4, JP-A-61-181807, JP-A-62-12
7305, JP-A-60-63207, JP-A-60-
No. 139706, etc.

[0042]

EXAMPLES Next, the present invention will be specifically shown by Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the following reagents were used in the following Examples and Comparative Examples. Metallic magnesium: Granular (average particle size 350 μm) Ethanol: Wako Pure Chemical Industries, Ltd., reagent special grade Iodine: Wako Pure Chemical Industries, Ltd., reagent special grade Magnesium chloride: Wako Pure Chemical Industries, Ltd., reagent special grade

Example 1 (1) Preparation of solid product (a) A reactor made of SUS equipped with a stirrer (internal volume 80 liters) was sufficiently replaced with nitrogen gas, and 31 kg of ethanol, 0.2 kg of iodine and magnesium metal 2 were added. Injecting 2 kg,
The reaction was carried out under reflux conditions with stirring until no hydrogen was generated from the system to obtain a solid reaction product. By drying the reaction liquid containing the solid reaction product under reduced pressure,
A solid product was obtained.

(2) Preparation of solid catalyst component (A) The same SUS reactor (internal volume 80 liters) equipped with a stirrer as used in (1) was sufficiently replaced with nitrogen gas to obtain the solid product. (A) 4 kg (not crushed) and 20 liters of dehydrated heptane were added, and 0.6 liter of silicon tetrachloride was added under stirring. Further, 0.63 liter of diethyl phthalate was added and the temperature was kept at 60 ° C. Next, add 20 liters of titanium tetrachloride and add 11
After maintaining at 0 ° C for 2 hours, it was washed with heptane at 80 ° C. Then, add 25 liters of titanium tetrachloride and add 11
After maintaining at 0 ° C for 2 hours, the solid catalyst component (A) was obtained by washing with heptane.

(3) A reactor made of SUS equipped with a prepolymerization stirrer (a vertical tank with four baffles and having the contents shown in Table 1) was sufficiently replaced with nitrogen gas, and 40 liters of purified heptane were added. 2.6 ml of triethylaluminum and 2.7 mmol of the solid catalyst component (A) in terms of titanium were added, and at a temperature of 30 ° C.,
Polymerization of propylene was carried out for 3 hours. In this case, propylene was continuously supplied so that the total pressure would be 0.8 Kg / cm ² · G. As the stirring blade, a Maxblend blade as shown in FIG. 1 (having the contents shown in Table 1, manufactured by Sumitomo Heavy Industries, Ltd.) was used, and the stirring rotation speed was 130 rpm.

(4) 400 m of purified heptane was placed in an autoclave made of SUS (internal volume of about 1.0 liter) which was sufficiently replaced with polymerized argon gas.
1, 1 mmol of triethylaluminum, 0.25 mmol of cyclohexylmethyldimethoxysilane and 0.005 mmol of the above solid catalyst composition (A) in terms of titanium.
Was added, 0.5 kg / cm ^{2 of} hydrogen was added, and the total pressure was 8 kg.
Polymerization of propylene was carried out for 2 hours at 70 ° C./cm ² . The above results are shown in Tables 1 and 2. The stereoregularity in Table 2 means the insoluble content after extraction with boiling heptane for 6 hours.

Example 2 (1) Preparation of solid product (a) The procedure of Example 1 (1) was repeated. (2) Preparation of solid catalyst component (A) It carried out like Example 1 (2). (3) The same procedure as in Example 1 (3) was performed except that the pre-polymerization reaction blade was changed to a full zone blade (manufactured by Shinko Pantech Co., Ltd.) as shown in FIG. 2 and the stirring blade rotation speed was changed to 300 rpm. It was (4) Polymerization The same procedure as in Example 1 (4) was carried out. The above results are shown in Table 1.
2 shows.

Example 3 (1) Preparation of solid product (a) The procedure of Example 1 (1) was repeated. (2) Preparation of solid catalyst component (A) It carried out like Example 1 (2). (3) The procedure of Example 1 (3) was repeated, except that the prepolymerized slurry concentration was changed to 450 g / l and the propylene pressure was changed to 3.8 Kg / cm ² · G. (4) Polymerization The same procedure as in Example 1 (4) was carried out. The above results are shown in Table 1.
2 shows.

Example 4 (1) Preparation of solid product (a) The procedure of Example 1 (1) was repeated. (2) Preparation of solid catalyst component (A) It carried out like Example 1 (2). (3) Prepolymerized slurry concentration of 300 g / l, propylene pressure of 3.8
Kg / cm ² · G, the stirring blade rotation speed was 40 rpm, and the temperature was changed to 20 ° C. (4) Polymerization The same procedure as in Example 1 (4) was carried out. The above results are shown in Table 1.
2 shows.

Comparative Example 1 (1) Preparation of Solid Product (a) The procedure of Example 1 (1) was repeated. (2) Preparation of solid catalyst component (A) It carried out like Example 1 (2). (3) The procedure of Example 1 (3) was repeated except that the paddle blade 4 shown in FIG. 3 was used as the prepolymerization reaction blade. (4) Polymerization The same procedure as in Example 1 (4) was carried out. The above results are shown in Table 1.
2 shows.

Comparative Example 2 (1) Preparation of Solid Product (a) The procedure of Example 1 (1) was repeated. (2) Preparation of solid catalyst component (A) It carried out like Example 1 (2). (3) Preliminary Polymerization In Comparative Example 1 (3), the slurry concentration was 300 g / l.
When the prepolymerization was carried out with increasing temperature, a runaway reaction occurred, the temperature rose uncontrollably, and aggregates were generated. 0.
The temperature reached 110 ° C. after 5 hours, so the prepolymerization operation was stopped. (4) Polymerization The same procedure as in Example 1 (4) was carried out. The above results are shown in Table 1.
2 shows, in this example, as a result of polymerization, catalytic activity,
The stereoregularity was remarkably reduced, and the bulk density was also significantly reduced. .

Comparative Example 3 (1) Preparation of Solid Product (a) The procedure of Example 1 (1) was repeated. (2) Preparation of solid catalyst component (A) It carried out like Example 1 (2). (3) The pre-polymerization stirring blade was changed to a Fiddler blade 5 as shown in FIG. 4,
And Example 1 except that the polymerization time was extended to 25 hours.
It carried out like (3). (4) Polymerization The same procedure as in Example 1 (4) was carried out. The above results are shown in Table 1.
In the present example, the amount of prepolymerization is the same as in Example 1.
Although almost the same result as in (3) was obtained, the catalytic activity was remarkably reduced as a result of the polymerization.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

As described above, according to the present invention,
The prepolymerization treatment of the solid catalyst component (A) at a high slurry concentration can be efficiently carried out without causing deterioration in catalyst performance. Therefore, when the present invention is used, the size of the prepolymerization tank can be small, which is advantageous in facility construction. Further, since the reaction rate is increased, it is possible to carry out the prepolymerization treatment at a low pressure for a short time, and as a result, it is possible to achieve cost reduction by reducing variable costs in the prepolymerization.
Further, according to the present invention, by using the solid product (a) obtained from magnesium metal, alcohol, halogen and / or a halogen-containing compound for the catalyst for polyolefin, the particle size adjusting treatment such as pulverization is not performed. In both cases, a polymer exhibiting high catalytic activity and high stereoregularity and having good powder morphology can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic view showing a stirring tank provided with a Maxblend blade.

FIG. 2 is a schematic view showing a stirring tank provided with a full zone blade.

3 (a) is a schematic view showing a stirring tank provided with paddle blades, and FIG. 3 (b) is a plan view of the paddle blades.

FIG. 4 is a schematic view showing a stirring tank provided with a Fiddler blade.

FIG. 5 is a flowchart showing the manufacturing method of the present invention.

[Explanation of symbols] 1 ... stirring shaft 2 ... Bottom paddle wings 3 ... Upper wing 4 ... Paddle wings 5 ... Furdler Tsubasa 10 ... stirring tank

Claims (2)

[Claims] 1. (a) Metal magnesium, alcohol, and 0.000 per 1 gram atom of the metal magnesium.
A solid product obtained by reacting a halogen in an amount of 01 gram atom or more or a halogen-containing compound containing a halogen atom in an amount of 0.0001 gram atom or more with respect to 1 gram atom of the magnesium metal, and (b) halogenating A method for producing a polyolefin using a solid catalyst component (A) obtained by reacting a titanium compound with or without an electron-donating compound, wherein a small amount of the solid catalyst component (A) is used in advance. When carrying out the polymerization treatment with olefins in a stirring tank, the bottom paddle blade section, which is arranged as a stirring blade on the stirring shaft provided in the center of the stirring tank and located near the bottom of the tank, and above it. A stirrer blade composed of an upper blade portion positioned and a liquid level during the reaction is L, and a height from the bottom of the tank to the uppermost portion of the upper blade portion is H, L> 0.5, and the and method for producing a polyolefin top of the bottom paddle blade portion is characterized by using a stirring blade such as lower than the liquid level surface. 2. A condition in which 4.3 × 10 ³ <n ³ d ² <4.0 × 10 ⁶ is satisfied, where d (m) is the diameter of the stirring blade and n (rpm) is the number of revolutions. The method for producing a polyolefin according to claim 1, wherein the stirring is carried out with.