JP2757206B2 - Method for producing polyolefin - Google Patents

Description

The present invention relates to a method for producing a polyolefin. More particularly, the present invention relates to a process for producing a polyolefin, comprising polymerizing at least one olefin at a reaction temperature below the melting point of the polymer in the presence of a novel catalyst system.

[Conventional technology]

It is already known to use a catalyst system comprising a transition metal compound and an organometallic compound for low pressure polymerization of olefins. In recent years, many proposals have been made on the production of solid catalyst components containing magnesium, titanium, and halogen as main components as highly active catalysts. However, many of them require further improvement in activity, polymer powder properties, and the like.

The present inventors have proposed JP-B-52-15110 as a highly active olefin polymerization catalyst. There, a catalyst component (A) obtained by reacting a magnesium metal with an organic compound containing hydroxide or an oxygen-containing organic compound of magnesium, an oxygen-containing organic compound of a transition metal, and an aluminum halide and a catalyst component (B) of an organometallic compound are obtained. An extremely active catalyst system comprising:

However, the polymer particles obtained in the presence of these catalysts have a small average particle size or a wide particle size distribution, and the proportion of fine particles contained in the polymer particles is large, and the powder characteristics are low. It was still insufficient.

That is, when the polyolefin has the above-mentioned particle size distribution, various troubles are caused in processes such as polymerization, separation of particles from a polymer slurry, powder drying, and powder transfer when producing a polyolefin, and sometimes a long term. Or continuous production over a long period of time. In addition, when a polymer is obtained by a multi-stage polymerization method, if the particle size distribution of the polymer particles is wide, the classification of the powder is likely to occur in the additive compounding stage and the transporting stage after drying, and the physical properties are different for each particle size, so the quality is high. There are times when the above adverse effects cannot be ignored.

Furthermore, the present inventors have previously proposed Japanese Patent Application Laid-Open No. 60-262802. There, a catalyst component (A) obtained by reacting a magnesium metal with an organic compound containing hydroxide or an oxygen-containing organic compound of magnesium, an oxygen-containing organic compound of a transition metal, an organoaluminum compound, a silicon compound, and an aluminum halide compound is combined with an organic compound. Although a catalyst system comprising a metal compound as the catalyst component (B) has been used to solve the above problems, it has not yet been sufficiently solved.

[Problems to be solved by the invention]

Accordingly, the present inventors have conducted intensive studies to overcome the various disadvantages of the conventional technology as described above and to find a method for producing a polyolefin having good powder characteristics in a high yield in olefin polymerization. Was.

[Means for solving the problem]

As a result, the present inventors have found that by performing olefin polymerization in the presence of a novel catalyst system, a polyolefin having good powder properties can be obtained in high yield, and the present invention has been completed. Reached.

That is, the present invention provides a method for producing a polyolefin at a reaction temperature lower than the melting point of a polymer in the presence of a catalyst comprising a transition metal compound and an organometallic compound. And at least one member selected from the group consisting of a compound and an oxygen-containing organic compound of magnesium; and (II) a general formula [TiO _a (OR ² ) _b X _c ] _m (wherein R ² is a carbon atom having 1 to 20 carbon atoms) X represents a hydrogen group, and X represents a halogen atom.
a, b and c are a ≧ 0, b> 0, 4> c ≧ 0, and are numbers compatible with the valence of tetravalent titanium, and m is an integer. The homogeneous solution containing an oxygen-containing organic compound of titanium represented by), (III) In the general formula AlR ¹ _l X _3-l (wherein, hydrocarbon radical R ¹ containing 1 to 20 carbon atoms And X represents a halogen atom. L is a number satisfying 0 <l ≦ 2), and (IV) a solid product obtained by reacting the silicon compound with a silicon compound. (V) General formula AlR ⁶ _t X _3-t (wherein, R ⁶ is a hydrocarbon group containing 1 to 20 carbon atoms, X is a halogen atom. T is a number of 1 ≦ t ≦ 3) there.) was treated with an organic aluminum compound represented by, then (VI) formula Ti (OR ⁷⁾ in _u X _4-u (wherein the hydrocarbon radical R ⁷ are of 1 to 20 carbon atoms X represents a halogen atom, and u represents a number satisfying 0 ≦ u <4.) A solid catalyst obtained by reacting a halogen-containing titanium compound represented by the following formula: A method for producing a polyolefin, comprising using a catalyst system comprising a component and at least one trialkylaluminum compound as a component (B).

[Action]

Examples of the reactant used in the present invention as the above-mentioned (I) metal magnesium and an organic hydroxide compound and an oxygen-containing organic compound of magnesium include the following.

First, in the case of using metal magnesium and a hydroxylated organic compound, various shapes can be used as the metal magnesium, that is, any shape such as powder, particles, foil, or ribbon can be used. , Alcohols, organic silanols and phenols are suitable.

Alcohols have from 1 to 18 carbon atoms. Straight or branched chain aliphatic, alicyclic or aromatic alcohols can be used. Examples include methanol, ethanol, n-butanol, n-octanol, n-stearyl alcohol, cyclopentanol, ethylene glycol and the like.

The organic silanol has at least one hydroxyl group, and the organic group is an alkyl group, a cycloalkyl group, or an arylalkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. , An aryl group, or an alkylaryl group. For example, the following example can be given. Trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol and the like.

Further, phenols include phenol, cresol, xylenol, hydroquinone and the like.

In addition, when the solid component described in the present invention is obtained using metallic magnesium, a substance that reacts with metallic magnesium or purifies an additional compound, for example, iodine or chloride for the purpose of accelerating the reaction. It is preferable to add one or more polar substances such as mercury, alkyl halides, organic acid esters and organic acids.

Compounds belonging to the oxygen-containing organic compounds of magnesium include magnesium alkoxides such as methylate, ethylate, isopropylate, decalate, and cyclohexanolate, magnesium alkyl alkoxides such as ethyl ethylate, magnesium hydroalkoxides such as hydroxymethylate, Magnesium phenoxides such as phenate, naphthenate, phenanthrate and cresolate, magnesium carboxylate such as acetate, stearate, benzoate, phenylacetate, adipate, sebacate, phthalate, acrylate and oleate, oxygen-containing organic magnesium compounds and additionally nitrogen , Ie, a magnesium-oxygen-nitrogen-organic group bond in this order. Oxymates, especially butyl oximate, dimethylglyoximate and cyclohexyl oximate, hydroxamic acid salts, hydroxylamine salts, especially N-nitroso-N-phenyl-hydroxylamine derivatives, magnesium chelates, i.e. One magnesium-oxygen-organic group bond in this order;
Furthermore, oxygen-containing organic compounds having at least one ligand bond to form a magnesium-containing heterocycle, such as enolates, especially acetylacetonates, such as phenol derivatives having an electron-donating group ortho or meta to the hydroxy group The resulting complexes, in particular 8-hydroxyquinolinates and magnesium silanolates, ie compounds containing, in this order, a magnesium-oxygen-silicon-hydrocarbon group bond, for example triphenylsilanolate. Of course, this series of oxygen-containing organic compounds also includes the following compounds: That is, compounds containing several different organic groups, such as magnesium methoxyethylate, complex alkoxides of magnesium with other metals and phenoxides, such as
It also includes Mg [Al (OC ₂ H ₅ ) ₄ ] ₂ and Mg ₃ [Al (OC ₂ H ₅ ) ₆ ] ₂ . These oxygen-containing organomagnesium compounds are used alone or as a mixture of two or more. As the oxygen-containing compound of titanium (II), a compound represented by the general formula [TiO _a (OR ² ) _b X _c ] _m is used. However, in the general formula, R ² represents a hydrocarbon group such as a linear or branched alkyl group having 1 to 20, preferably 1 to 10 carbon atoms, a cycloalkyl group, an arylalkyl group, an aryl group, or an alkylaryl group. , X represents a halogen atom. a, b and c are numbers such that a ≧ 0, b> 0, 4> c ≧ 0 and are compatible with the valence of titanium, and m is an integer. In particular, it is desirable to use an oxygen-containing organic compound in which a is 0 ≦ a ≦ 1 and m is 1 ≦ m ≦ 6.

Specific examples include Ti (OC ₂ H ₅ ) ₄ , Ti (OnC ₃ H ₇ ) ₄ ,
i (OiC ₃ H ₇ ) ₄ , Ti (OnC ₄ H ₉ ) ₄ , Ti ₂ O (OiC ₃ H ₇ ) ₆ , Ti (O
C ₂ H ₅ ) ₂ Cl ₂ and Ti (OC ₂ H ₅ ) ₃ Cl. The use of oxygen-containing organic compounds containing several different hydrocarbon groups and the use of oxygen-containing organic compounds that include the scope of the present invention are within the scope of the invention. It is also within the scope of the present invention to use these oxygen-containing compounds of titanium alone or as a mixture of two or more.

As the aluminum halide compound (III), those represented by the general formula AlR ¹ _l X _3-l are used.
However, in the general formula, R ¹ is a hydrocarbon group containing ¹ to 20, preferably 1 to 6 carbon atoms, X represents a halogen atom, and is F, Cl, Br or I. l is 0 <
1 ≦ 2. Preferably, R ¹ is selected from linear or branched alkyl, cycloalkyl, arylalkyl, aryl, alkylaryl groups.

The above aluminum halide compounds can be used alone or as a mixture of two or more.

Specific examples of the aluminum halide compound include, for example, Al (C ₂ H ₅ ) Cl ₂ , Al (C ₂ H ₅ ) ₂ Cl, and Al (iC ₄ H ₉ ) Cl ₂ .

As the silicon compound as the reactant (IV), the following polysiloxanes and silanes are used. As polysiloxane, the general formula (Wherein R ³ and R ⁴ are a hydrocarbon group such as an alkyl group or an aryl group having 1 to 12 carbon atoms, hydrogen, halogen, 1 carbon atom)
12 alkoxy group, aryloxy group, an atom or a residue capable of binding to silicon, such as fatty acid residue, R ³ and
R ⁴ may be the same or different, and n is usually 2 to 10000
A siloxane polymer having a linear, cyclic or three-dimensional structure in which one or more of the repeating units represented by R ³ and R ⁴ except when they are hydrogen or halogen).

Specifically, examples of the linear polysiloxane include hexamethyldisiloxane, octamethyltrisiloxane, dimethylpolysiloxane, diethylpolysiloxane, methylethylpolysiloxane, methylhydropolysiloxane, ethylhydropolysiloxane, and butylhydropolysiloxane. , Hexaphenyldisiloxane, octaphenyltrisiloxane, diphenylpolysiloxane,
Phenylhydropolysiloxane, methylphenylpolysiloxane, methylphenylpolysiloxane, 1,5-dichlorohexamethyltrisiloxane, 1,7-dichlorooctamethyltetrasiloxane, dimethoxypolysiloxane, diethoxypolysiloxane, diphenoxypolysiloxane, etc. can give.

Examples of the cyclic polysiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, Examples include tetraphenyltetramethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, and octaphenylcyclotetrasiloxane.

Examples of the polysiloxane having a three-dimensional structure include those in which the above-mentioned chain or cyclic polysiloxane has a crosslinked structure by heating or the like.

These polysiloxanes are desirably liquid in handling, and have a viscosity at 25 ° C. of 1 to 10,000 centistokes, preferably 1 to 1000 centistokes. However, the grease is not necessarily limited to a liquid, and may be a solid such as generally called silicone grease.

Formula ^{_{H p Si q R 5 r X}} s ( wherein as silanes, R ⁵ is an alkyl group having 1 to 12 carbon atoms, a hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms such as aryl group, aryloxy group , Represents a group capable of bonding to silicon such as a fatty acid residue, each R ⁵ may be different or the same, X represents a different or same halogen, p is 0 or more and less than 4, r and s Is an integer of 0 or more, q is a natural number, and p + r + s = 2q + 2
Or p + r + s = 2q).

Specifically, for example, silahydrocarbons such as trimethylphenylsilane and allyltrimethylsilane, chain and cyclic organic silanes such as hexamethyldisilane and octaphenylcyclotetrasilane, organic silanes such as methylsilane, dimethylsilane and trimethylsilane; Silicon halides such as silicon tetrachloride and silicon bromide, alkyl and aryl halogenosilanes such as dimethyldichlorosilane, diethyldichlorosilane, n-butyltrichlorosilane, diphenyldichlorosilane, triethylfluorosilane and dimethyldibromosilane, and trimethylmethoxysilane And aryl and halogenosilanes such as dimethyldibromosilane, trimethylmethoxysilane,
Haloalkoxy and phenoxysilanes, such as alkoxysilanes such as dimethyldiethoxysilane, tetramethoxysilane, diphenyldiethoxysilane, tetramethyldiethoxysilane, dimethyltetraethoxydisilane, dichlorodiethoxysilane, dichlorodiphenylsilane, and tribromoethoxysilane; Examples include silane compounds containing fatty acid residues such as trimethylacetoxysilane, diethyldiacetoxysilane, and ethyltriacetoxysilane.

The above-mentioned organosilicon compounds may be used alone, or two or more thereof may be used by mixing or reacting.

As the organoaluminum compound (V), a compound represented by the general formula AlR ⁶ _t X _3-t is used. However, in the general formula, R ⁶ contains 1 to 20 carbon atoms, X represents a halogen atom, and is F, Cl, Br or I. t is a number satisfying 1 ≦ t ≦ 3. Preferably, R ⁶ is selected from linear or branched alkyl, cycloalkyl, arylalkyl, aryl, alkylaryl groups.

The organoaluminum compounds can be used alone or as a mixture of two or more. Specific examples of the organoaluminum compound include, for example, trimethylaluminum, triethylaluminum, tri-i-propylaluminum, tri-i-butylaluminum, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum dichloride, i-butylaluminum Dichloride, sesquiethyl aluminum chloride, sesqui-i-butyl aluminum chloride, sesqui-i-propyl aluminum chloride,
Examples include sesqui-n-propylaluminum chloride, diethylaluminum chloride, di-i-propylaluminum chloride, di-n-propylaluminum chloride, diethylaluminum bromide, and diethylaluminum iodide.

Further, as the halogen-containing titanium compound as the reactant of the above (VI), a titanium compound represented by the general formula Ti (OR ⁷ ) _u X _4-u is used. In the general formula, R ⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and u represents a number satisfying 0 ≦ u <4. R ⁷ is preferably selected from linear or branched alkyl groups, cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups.

The above-mentioned titanium halide compounds can be used alone or as a mixture of two or more. Specific examples of the titanium halide include, for example, titanium tetrachloride, ethoxy titanium trichloride, propoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, diethoxy titanium dichloride, and triethoxy titanium chloride.

These reactions are preferably performed in a liquid medium.
Therefore, especially when these reactants are not liquid under the operating conditions, or when the amount of the liquid reactants is insufficient, the reaction can be carried out in the presence of an inert organic solvent. As the inert organic solvent, any of those generally used in the art can be used, and examples thereof include aliphatic, alicyclic, or aromatic hydrocarbons or halogen derivatives thereof, and mixtures thereof, such as isobutane, Hexane,
Heptane, cyclohexane, benzene, toluene, xylene, monochlorobenzene and the like are preferably used.

The reactants (I) (II) (III) (I) used in the present invention
The amounts of V), (V) and (VI) are not particularly limited, but the ratio of magnesium atom (I) to titanium atom (II) is 1: 0.
It is preferable to select the amount to be used so as to be from 01 to 1:20, preferably from 1: 0.1 to 1: 5. It is preferable to select the amount of the reactant such that the ratio of magnesium atoms to aluminum atoms in the aluminum halide compound (III) is in the range of 1: 0.01 to 1: 100, preferably 1: 0.02 to 1:20. . In particular, 1:
Good powder characteristics are shown by selecting the range of 0.05 to 1: 1. It is preferable to select the amount of the reactant such that the ratio of the magnesium atom to the silicon atom in the silicon compound (IV) is in the range of 1: 0.01 to 1:20, preferably 1: 0.1 to 1: 5. Outside of these ranges, the result is that the polymerization activity is low or good powder properties are not desired.

The ratio of magnesium atom (I) to aluminum atom in organoaluminum (V) is 1: 0.02 to 1: 100,
The ratio is preferably 1: 0.1 to 1:10. In this range, the bulk density of the polymer increases, and the effect of improving the powder properties is observed.

The ratio of the magnesium atom to the titanium atom in the titanium compound (VI) is 1: 0.02 to 1: 100, preferably 1: 0.05.
It is preferable to select the amount of the reactant to be used so as to be in the range of 1:50. If the ratio is out of this range, problems such as low polymerization activity and coloring of the product occur.

The reaction conditions for obtaining a homogeneous solution with the reactants (I) and (II) are at a temperature in the range of -50 to 300 ° C, preferably 0 to 200 ° C, for 0.5 to 50 hours, preferably 1 to 6 hours. It is carried out at normal pressure or under pressure in an active gas atmosphere. Further, when reacting the reactant (III) and the reactant (IV), -50 to 200
° C., preferably in the temperature range of −30 to 100 ° C., 0.2 to
It is carried out in an inert gas atmosphere or under pressure for 50 hours, preferably 0.5 to 5 hours. The reactant (III) and the reactant (IV) may be reacted simultaneously, or the reactant (IV) may be reacted after the reactant (III).

The solid component thus obtained is particles that are insoluble in the solvent used as a diluent, and after removing the remaining unreacted substances and by-products by filtration or decantation, washed several times with an inert solvent, Reactant (V) suspended in inert solvent
Then, the solid catalyst component (A) can be obtained by performing a contact reaction with (VI). When reacting the reactant (III) and the reactant (IV), the reaction is carried out at a temperature in the range of -50 to 200 ° C, preferably -30 to 100 ° C for 0.2 to 50 hours, preferably 0.5 to 5 hours. It is performed in an active gas atmosphere or under pressure.
The catalyst component (A) may be used as it is, but it is generally filtered or decanted to remove the remaining unreacted substances and by-products, washed several times with an inert solvent, and then washed with an inert solvent. Use it suspended in a solvent. Further, those isolated after washing and heated under normal pressure or reduced pressure to remove the solvent can also be used.

In the present invention, at least one kind of trialkylaluminum is used as the catalyst component (B). As the alkyl group, a linear or branched C1-C20
Is used. Specifically, examples of the catalyst component (B) include trimethylaluminum, triethylaluminum, tri-i-butylaluminum, tri-n-butylaluminum, and tri-n-decylaluminum. In particular, it is preferable to use a trialkylaluminum having a linear or branched alkyl group having 1 to 10 carbon atoms.

An organic aluminum compound obtained by reacting a trialkyl aluminum having an alkyl group having 1 to 20 carbon atoms with a diolefin having 4 to 20 carbon atoms, for example, a compound such as isoprenyl aluminum can also be used.

The above trialkylaluminum compounds can be used alone or as a mixture of two or more.

In carrying out the present invention, the amount of the catalyst component (A) used is
It is preferably used in an amount corresponding to 0.001 to 2.5 mmol of titanium atoms per solvent or per reactor internal volume, and may be used at a higher concentration depending on the conditions.

The trialkylaluminum compound of the catalyst component (B) is added per solvent or per reactor volume.
It is used at a concentration of 0.02 to 50 mmol, preferably 0.2 to 5 mmol.

The polymerization of the olefin or the olefin with another α-olefin is carried out in a liquid phase or a gas phase. When the polymerization is performed in a liquid phase, it is preferable to use an inert solvent. The inert solvent can be any of those commonly used in the art, but especially alkanes and cycloalkanes having 4 to 20 carbon atoms such as isobutane, pentane, hexane, heptane, cyclohexane and the like. Is appropriate.

As the olefin to be polymerized in the method for producing a polyolefin of the present invention, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-
Α-olefins such as 1-pentene. Further, copolymerization can also be carried out using a mixture of two or more of the above α-olefins. It is necessary to select the amount of the α-olefin in accordance with the density of the target polymer. The density of the polymer according to the present invention can be produced in the range of 0.900 to 0.970 g / cm ³ .

The polymerization operation of the present invention can be carried out not only in the usual one-stage polymerization under one polymerization condition but also in the multi-stage polymerization under a plurality of polymerization conditions.

The polymerization conditions in the present invention are polymerization temperatures below the melting point of the polymer, for example, a polymerization temperature of 20 to 100 ° C., and a polymerization pressure of 2 to 50 kg / cm.
^{This is} performed under the conditions of 2G slurry or vapor phase method. The molecular weight can be adjusted by a known means, that is, a method of allowing an appropriate amount of hydrogen to exist in the reaction system.

〔The invention's effect〕

The effect of the present invention resides, first, in that the powder characteristics of the polymer are remarkable. That is, according to the present invention, it is possible to obtain a polymer having a small content of fine particles and a high average bulk particle diameter having a moderate size. It is also possible to obtain a polymer having an extremely narrow particle size distribution. These things are of great industrial significance. That is, in the polymerization step, the formation of deposits in the polymerization apparatus is prevented,
Separation and filtration of the polymer are facilitated, and scattering of the polymer fine particles out of the system is prevented. In addition, the drying efficiency is improved by improving the fluidity. Further, in the transfer step, there is no occurrence of a bridge or the like in the silo, and the transfer trouble is eliminated. Further, it is possible to provide a polymer having a certain quality.

A second effect of the present invention is that a polymer having an extremely high polymerization activity and not requiring a deashing step for removing a catalyst can be obtained. Because of its high activity, there is no need to color or smell the product, and no polymer is required, which is extremely economical.

A third effect of the present invention is that the molecular weight distribution can be easily controlled by the amount of the reactant used for producing the catalyst. Therefore, polymers having various physical properties can be easily produced by the action of the catalyst itself.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

In Examples and Comparative Examples, HLMI / MI is a ratio between a high-load melt index (HLMI, according to ASTM D-1238 condition F) and a melt index (MI, according to ASTM D-1238 condition E).

The activity indicates the amount of polymer produced (g) per gram of solid catalyst component (A) and the amount of polymer produced (g) per gram of transition metal component in solid catalyst component (A).

The result of classifying the polymer particles by a sieve is plotted on a probability logarithmic paper, and the geometric standard deviation is calculated from an approximated straight line by a known method. Expressed. The average particle size is a value obtained by reading the particle size with respect to the weight integrated value of 50% of the approximate straight line. The fine particle content indicates the ratio of fine particles having a particle size of 105 μ or less in percentage by weight.

Example 1 [Preparation of solid catalyst component (A)] 11 g (0.45 mol) of metallic magnesium powder was placed in a 2 liter autoclave equipped with a stirrer, and 0.55 g of iodine was added thereto.
128.9 g (0.99 mol) of 2-ethylhexanol and 61 g (0.18 mol) of titanium tetrabutoxide were added, and further 450 ml were added.
Then, the mixture was heated to 80 ° C., and stirred for 1 hour under a nitrogen seal while excluding hydrogen gas generated. Continue at 120 ° C
And stirred for 1 hour to obtain a homogeneous solution (Mg-Ti solution) containing magnesium and titanium.

Then, 0.053mol in terms of Mg of the obtained homogeneous solution was 500ml
The mixture was placed in a flask, the temperature was raised to 45 ° C., and 2.5 ml (0.0053 mol) of a 50% hexane solution of i-butylaluminum dichloride and 3.2 g (0.021 mol) of tetramethoxysilane were added. After stirring for an hour, a solid product was obtained. Hexane was added to the product, and the product was washed five times. Thereafter, 40.8 ml (0.11 mol) of a 50% hexane solution of i-butylaluminum dichloride was further added over 2 hours. After adding all, the temperature was raised to 70 ° C., and the mixture was stirred for 1 hour. After washing 5 times with hexane,
5.12 g of titanium tetrachloride diluted in 3.0 ml of dichloroethane was added, and the mixture was stirred at 70 ° C. for 1 hour. Hexane was added to the product, and the product was sufficiently washed until no liberated titanium compound was detected to obtain a solid catalyst component (A).

(Polymerization of ethylene)

The stainless steel electromagnetic stirring type reactor having an inner volume of 2 liters was sufficiently replaced with nitrogen, and 1.2 liters of hexane was charged to adjust the internal temperature to 80 ° C. Thereafter, 0.23 g (1.2 mmol) of triisobutylaluminum and 10 mg of the catalyst component (A) were sequentially added as the catalyst component (B). 1 k of nitrogen in the reactor
After adjusting to g / cm ² G, hydrogen was added at 4 kg / cm ² , and then polymerization was carried out for 1.5 hours while continuously adding ethylene so that the internal pressure of the autoclave became 11.0 kg / cm ² G. After the completion of the polymerization, the system was cooled, unreacted gas was expelled, polyethylene was taken out, separated from the solvent by filtration and dried.

As a result, melt index 1.70g / 10min, HLMI / MI
The activity was 40,000 g / g catalyst and the activity per transition metal component was 667,000 g / g transition metal. The bulk density is 0.43 g / cm ³ , the average particle size is 360μ, σ0.
08, the result of 0.7% fine particle content was obtained.

Example 2 In Example 1, i-butylaluminum dichloride 0.00 was used as the reactant (III) aluminum halide compound.
A solid catalyst component (A) was prepared under the same conditions as in Example 1 except that 53 mol was used, except that the used amount was 0.0027 mol. Using triisobutylaluminum as the obtained solid catalyst component (A) and catalyst component (B), ethylene was polymerized under the same conditions as in Example 1. The results are shown in Table 1.

Examples 3 and 4 In Example 1, i-butylaluminum dichloride was used as a reactant (III) as an aluminum halide compound.
A solid catalyst component (A) was prepared under the same conditions as in Example 1 except that 53 mol was used, except that ethyl aluminum dichloride was used in Example 3 and sesquialuminum chloride was used in Example 4. Using triisobutylaluminum as the obtained solid catalyst component (A) and catalyst component (B), ethylene was polymerized under the same conditions as in Example 1. The results are shown in Table 1.

Examples 5 and 6 In Example 1, 0.11 mol of i-butylaluminum dichloride was used as the reactant (V) organoaluminum compound. In Example 5, diethylaluminum chloride was used. In Example 6, triisobutylaluminum was used. Solid catalyst component (A) under the same conditions as in Example 1.
Was prepared. Using triisobutylaluminum as the obtained solid catalyst component (A) and catalyst component (B), ethylene was polymerized under the same conditions as in Example 1. The results are shown in Table 1.

Examples 7 to 9 Instead of the silicon compound and tetramethoxysilane of the reactant (IV) used in Example 1, methylhydropolysiloxane in Example 7, diphenyldimethoxysilane in Example 8, and Example 9 A solid catalyst component (A) was prepared under the same conditions as in Example 1 except that tetraethoxysilane was used. Ethylene was polymerized under the same conditions as in Example 1 using triisobutylaminium as the obtained solid catalyst component (A) and catalyst component (B). The results are shown in Table 1.

Comparative Example 1 0.053 mol in terms of Mg of the homogeneous solution obtained in Example 1 was placed in a 500 ml flask, heated to 45 ° C., and 2.5 ml of a 50% hexane solution of i-butylaluminum dichloride.
(0.0053 mol), and 3.2 g (0.0
After adding 21 mol), the temperature was raised to 70 ° C., and the mixture was stirred for 1 hour to obtain a solid product. Hexane was added to the product, and the product was washed five times. Thereafter, 40.8 ml of a 50% hexane solution of i-butylaluminum dichloride (0.11 mol
l) was added over 2 hours. After adding all, the temperature was raised to 70 ° C., and the mixture was stirred for 1 hour. Washing operation was sufficiently performed with hexane to obtain a solid component.

Using the obtained solid component and triisobutylaluminum as the catalyst component (B), ethylene was polymerized under the same conditions as in Example 1. The results are shown in Table 1. The content of the fine particles was very large, the bulk density was low, and the powder characteristics were poor.

Comparative Example 2 A solid catalyst component was obtained under the same conditions as in Example 1 except that the tetramethoxysilane used in Example 1 was not used. Obtained solid catalyst component and catalyst component (B)
Example 1 using triisobutylaluminum as
Polymerization of ethylene was carried out under the same conditions as described above. Table 1 shows the results
It was shown to.

Comparative Example 3 0.053 mol in terms of Mg of the homogeneous solution obtained in Example 1 was placed in a 500 ml flask, heated to 45 ° C., and 40.8 ml of a 50% hexane solution of i-butylaluminum dichloride was added.
(0.11 mol) and 3.2 g of tetramethoxysilane (0.021
mol), the temperature was raised to 70 ° C., and the mixture was stirred for 1 hour to obtain a solid product. Add hexane to the product and add 5
Washing was performed twice. Next, 5.12 g of titanium tetrachloride diluted in 3.0 ml of 1,2-dichloroethane was added to the hexane slurry containing the solid product, and the mixture was stirred at 70 ° C. for 1 hour. Hexane was added to the product, and the product was sufficiently washed until no liberated titanium compound was detected to obtain a solid catalyst component. Using the obtained solid catalyst component and triisobutylaluminum as the catalyst component (B), ethylene was polymerized under the same conditions as in Example 1. The results are shown in Table 1. The bulk density was low and the powder characteristics were not good.

Example 10 The solid catalyst component (A) obtained in Example 1 and 0.12 g (0.6 mm) of triisobutylaluminum as the catalyst component (B) were used.
ol), and 0.072 g (0.6 m) of diethylaluminum chloride
mol), the polymerization of ethylene was carried out under the same conditions as in Example 1. The results are shown in Table 1.

Example 11 Using the solid catalyst component (A) obtained in Example 1, ethylene was polymerized by a multistage polymerization method. In other words, the content 5l
Using two stainless steel electromagnetic stirring type reactors,
After 3 l of hexane was charged to one of the reactors and the internal temperature was adjusted to 85 ° C., 1.7 g (8.5 mmol) of triisobutylaluminum and 200 mg of the solid catalyst component (A) were added as the catalyst component (B). After adjusting the internal pressure of the reactor to 1 kg / cm ² G with nitrogen gas, hydrogen 19.0 kg / cm ² was added, followed as the internal pressure of the autoclave becomes 25.0 kg / cm ² G, continuously ethylene was added while 65 minutes Polymerization was performed to produce a low molecular weight polymer.

The other reactor was charged with 3 l of hexane, and 1.7 g (8.5 mmol) of triisobutylaluminum and 100 mg of the solid catalyst component (A) were added. Reactor internal pressure by nitrogen gas
After adjusting the pressure to kg / cm ² G, hydrogen was added at 0.1 kg / cm ² , and then polymerization was carried out for 65 minutes while continuously adding ethylene so that the internal pressure of the autoclave became 4.0 kg / cm ² G. Was manufactured.

Next, each reaction mixture containing these polymers was pressure-fed to a stainless steel electromagnetic stirring type reactor having an internal volume of 10 l through a connection pipe. After replacing the gas phase of this reactor with nitrogen, the internal temperature was set to 80 ° C., the internal pressure was set to 1.0 kg / cm ² G, and the hydrogen was set to 1.2 kg.
/ cm ² , and then polymerization was carried out for 45 minutes while continuously adding ethylene so that the internal pressure of the autoclave became 5.2 kg / cm ² G, and the reaction mixture was filtered and dried. The obtained polymer is 36
00 g. The polymer powder properties include bulk density
0.44 g / cm ³ , average particle size 360μ, σ 0.09, fine particle content 0.9%
Was obtained. Furthermore, as a result of grasping the production amount of each stage based on the ethylene flow rate, the production ratio was 40 wt% for the low molecular weight polymer in the former stage and 40 wt% for the high molecular weight polymer.
% And the latter stage were 20 wt%. The weight average molecular weight of the low molecular weight polymer was 30,000.

When the obtained polymer powder was pelletized with an extruder having a screw diameter of 25 mmφ, the MI of the pellet was 0.049, H
LMI / MI was 210. Screw this pellet 25m in diameter
Evaluation was performed using a mφ inflation film forming machine at a resin temperature of 215 ° C., a blow ratio of 4.0 and a film thickness of 30 μm. As a result, a film could be formed in a state in which bubbles were extremely stable, and a good film without wrinkles, blemishes, bumps, and unevenness was obtained.

[Brief description of the drawings]

FIG. 1 is a catalyst preparation diagram (flow chart) in the present invention.
Is shown.

Claims (1)

(57) [Claims] 1. A method comprising the steps of transition metal compound and organometallic compound
At a reaction temperature below the melting point of the polymer in the presence of a catalyst
In producing olefins, (A) components include (I) metallic magnesium and an organic hydroxide compound,
Selected from the group consisting of oxygen-containing organic compounds of
At least one member, (II) General formula [TiO_a(OR^Two)_bX_c]_m(Where R^TwoIs the carbon number
Represents a hydrocarbon group of 1 to 20, and X represents a halogen atom.
a, b and c are a ≧ 0, b> 0, 4> c ≧ 0 and tetravalent titanium
Is a number compatible with the valence of m, and m is an integer.
You. ) Containing oxygen-containing organic compounds of titanium
(III) General formula AlR¹ _lX 3-l (where R¹Is 1 to 20 carbons
X is a halogen atom.
You. l is a number satisfying 0 <l ≦ 2. Halogen represented by)
Solid product obtained by reacting aluminum halide compound with (IV) silicon compound
(V) General formula AlR⁶ _tX 3-t (where R⁶Is 1 to 20 carbons
A hydrocarbon group containing an atom, X represents a halogen atom. t is
1 ≦ t ≦ 3. Organic aluminum represented by)
Treatment with a compound, and then (VI) the general formula Ti (OR⁷)_uX_4-u(Where R⁷Is 1-20 charcoal
X represents a halogen atom having a hydrogen atom
And u represents a number satisfying 0 ≦ u <4. )
The solid obtained by reacting the halogen-containing titanium compound
And at least one trialkyl alcohol as the component (B).
Uses a catalyst system consisting of a luminium compound
A method for producing a polyolefin.