JP2762499B2 - Process for producing improved stereoregular polyolefin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a stereoregular polyolefin. More specifically, the present invention provides a method for producing a highly stereoregular aggregate having a good particle shape by using a specific catalyst in the polymerization of α-olefins having 3 or more carbon atoms (hereinafter, also includes other α-olefin copolymerization). The present invention relates to a method for producing a compound in a high yield.

[Conventional technology]

Conventionally, olefin polymerization catalysts include α-type titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, purple γ-type titanium trichloride obtained by reducing titanium tetrachloride with aluminum, or ball mill Δ-type titanium trichloride and the like obtained by pulverization with a powder are known. Further, as a method for reforming these catalysts, a method of mixing and pulverizing with various improvers is also known. However, when polymerization is carried out using these catalysts, the polymerization activity is low and the resulting polymer has a large amount of catalyst residues, so that a so-called deashing step is indispensable. In recent years, many proposals have been made on the production of solid catalyst components containing magnesium, titanium, and halogen as main components. However, many of them are required to be further improved in activity, stereoregularity of the polymer, powder characteristics and the like.

The present inventors have already disclosed a method for obtaining a stereoregular polyolefin in a high yield by using a specific fixed catalyst component containing Mg, Ti, and halogen as main components.
14210, JP-A-63-317502, Japanese Patent Application 64-105, Japanese Patent Application 62-32
2861 proposed. In these methods, the reaction product of a homogeneous solution containing Mg, Ti, and an electron-donating compound with an aluminum halide compound is reacted with a titanium halide and an electron-donating compound to obtain activity and stereoregularity of the polymer. Although a catalyst component having excellent particle properties has been obtained, further improvement in catalytic activity has been desired.

[Problems to be solved by the invention]

Thus, the present inventors have overcome the inadequacy of the prior art, and obtain a highly stereoregular polymer having good powder properties in a higher yield in the polymerization of α-olefins having 3 or more carbon atoms. We worked diligently to find a manufacturing method that could not be performed.

[Means for solving the problem]

As a result, in the method disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 63-3007, etc., an oxygen-containing organic compound of silicon and an oxygen-containing organic compound of aluminum are used instead of the oxygen-containing organic compound of titanium. The present invention has been completed by using a solid catalyst component produced using the obtained homogeneous solution, an organometallic compound and an electron-donating compound as a co-catalyst. That is, the present invention, in the presence of a catalyst comprising a transition metal compound and an organometallic compound, when producing a stereoregular polyolefin,
As the component (A), (i) at least one member selected from the group consisting of metal magnesium, a hydroxylated organic compound, and an oxygen-containing organic compound of magnesium; and (ii) a general formula Al (OR ¹ ) _m X _3-m (formula In the formula, R ¹ has 1 to 20 carbon atoms.
M represents a number satisfying 0 <m ≦ 3, and X represents a halogen atom. )) And a homogeneous solution containing (iii) an oxygen-containing organic compound of silicon, and (iv) at least one of the general formulas AlR ² _n X _3-n (wherein R ² Represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents a number satisfying 0 <n ≦ 2.) more solid product (v) an electron-donating compound (vi) general formula _{^{Ti (OR 3) f X 4}} -f ( wherein, R ³ represents a carbon hydrogen group having 1 to 20 carbon atoms, X represents a halogen atom, and f represents a number satisfying 0 ≦ f <4), and a solid catalyst component obtained by reacting a titanium halide compound represented by the following formula: and at least one trialkylaluminum as component (B). Component (C) is an electron-donating compound. In the manufacturing method of stereoregular polyolefins using a catalyst system.

(Operation)

The solid catalyst component used in the present invention comprises (i) a metal magnesium and an organic compound of hydroxide or an oxygen-containing organic compound of magnesium, and (ii) an oxygen of aluminum represented by the general formula Al (OR ¹ ) _m X _3-m. (Iv) an aluminum halide compound represented by the general formula AlR ² _n X _3-n is reacted with a homogeneous solution obtained by reacting an oxygen-containing organic compound such as silicon alkoxide with a silicon-containing alkoxide. The obtained solid product can be obtained by reacting (v) an electron donating compound and (vi) a titanium halide compound represented by the general formula Ti (OR ³ ) _f X _4-f .

In the above (i), when metal magnesium and an organic hydroxide compound are used, the metal magnesium can be in any of various shapes, such as powder, particles, foil, ribbon, and the like. Suitable are alcohols, phenols and organic silanols.

As the alcohols, linear or branched aliphatic alcohols, alicyclic alcohols or aromatic alcohols having 1 to 18 carbon atoms can be used. Examples include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, n-hexanol, 2-
Examples include ethylhexanol, n-octanol, i-octanol, n-stearyl alcohol, cyclopentanol, cyclohexanol, and ethylene glycol. The organic silanol has at least one hydroxyl group, and the organic group has an alkyl group, a cycloalkyl group, an arylalkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. It is selected from an aryl group and an alkylaryl group. For example, the following example can be given. Trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol, and phenols include phenyl, cresol, xylenol, hydroquinone, and the like.

These hydroxylated organic compounds are used alone or as a mixture of two or more.

In addition, when a solid catalyst component of the component (A) described in the present invention is obtained using metal magnesium, a substance which reacts with metal magnesium or forms an addition compound for the purpose of accelerating the reaction. , For example, iodine, chloride 2
It is preferable to add one or more polar substances such as mercury, alkyl halides and organic acids.

Next, compounds belonging to the oxygen-containing organic compounds of magnesium include magnesium alkoxides such as methylate, ethylate, isopropylate, decanolate, methoxyethylate and cyclohexanolate;
Magnesium alkyl alkoxides, such as ethyl ethylate, magnesium hydroalkoxides, such as hydroxymethylate, magnesium phenoxides,
For example, phenates, naphthenates, phenanthrenates and cresolates, magnesium carboxylates such as acetate, stearate, benzoate,
Phenyl acetate, adipate, sebacate, phthalate, acrylates and oleates, oximates such as butyl oximate, dimethylglyoximate and cyclohexyl oximate, hydroxamic acid salts, hydroxylamine salts, such as N-nitroso-N-phenyl-hydroxyamine derivatives And enolates such as acetylacetonate and magnesium silanolate such as triphenylsilanolate. These oxygen-containing organomagnesium compounds are:
Used alone or as a mixture of two or more.

As the oxygen-containing organic compound of aluminum as the reactant (ii), an oxygen-containing compound represented by the general formula Al (OR ¹ ) _m X _3-m is used. However, in the general formula, R ¹ represents a hydrocarbon group such as a linear or branched alkyl group having 1 to 20, preferably 1 to 10 carbon atoms, such as a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group. And m represents a number satisfying 0 <m ≦ 3, and X represents a halogen atom.

Specific examples of the oxygen-containing organic compound copy of aluminum include trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, and tri-i.
-Propoxyaluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-ter
t-butoxyaluminum, tri (2-ethylhexoxy) aluminum, triphenoxyaluminum, tribenzyloxyaluminum, dichloromethoxyaluminum, chlorodimethoxyaluminum, dichloro (2
-Ethylhexoxy) aluminum, chlorodi (2-ethylenehexoxy) aluminum, dichlorophenoxyaluminum, chlorodiphenoxyaluminum and the like. The use of oxygen-containing organic compounds having several different hydrocarbon groups also falls within the scope of the present invention. These aluminum-containing organic compounds of aluminum are used alone or as a mixture of two or more.

Examples of the oxygen-containing organic compound of silicon as the reactant (iii) include tetramethoxysilane, tetraethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, and tetra-i- Pentoxysilane, tetra-n-hexoxysilane, tetraphenoxysilane, tetraski (2-ethylhexoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-methoxyethoxy) silane, methyltrimethoxysilane, ethyltrimethoxysilane, n-butyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, trimethoxysilane, methyltrie Kishishiran, ethyl triethoxysilane, n- propyl triethoxysilane, n- butyl triethoxysilane, phenyl triethoxysilane,
Vinyltriethoxysilane, 3-aminopropyltriethoxysilane, triethoxysilane, ethyltri-i-propoxysilane, vinyltri-i-propoxysilane, i
-Pentyltri-n-butoxysilane, ketyltri-i
-Pentoxysilane, ethyltri-i-pentoxysilane, methyltri-n-hexoxysilane, phenyltri-i-pentoxysilane, n-propyltrimethoxysilane, i-propyltrimethoxysilane, i-butyltrimethoxysilane, dimethyl Dimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, methyldodecyldiethoxysilane, methyloctadecyldiethoxysilane, methylphenyldiethoxysilane, methyl Diethoxysilane, dibenzyldiethoxysilane, diethoxysilane, dimethyldi-n-butoxysilane, dimethyldi-i-pentoxysilane, diethyldi-i-pentoxysilane Di -i- butyl di -i- pent silane, diphenyl -i- pentoxy silanes,
Diphenyldi-n-octoxysilane, diisobutyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethoxysilane, trimethyl-i-propoxysilane, trimethyl-n-propoxysilane, trimethyl-t-butoxysilane, trimethyl-i- Alkoxysilanes such as butoxysilane, trimethyl-n-butoxysilane, rimethyl-n-pentoxysilane, trimethylphenoxysilane or haloalkoxysilanes such as aryloxysilane, dichlorodiethoxysilane, dichlorodiphenoxysilane, tribromoethoxysilane or Haloaryloxysilane and the like.

The above-mentioned oxygen-containing organic compounds of silicon may be used alone, or two or more thereof may be mixed or reacted for use.

As the aluminum halide compound as the reactant (iv), those represented by the general formula AlR ² _n X _3-n are used. In the formula, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents 0 <n ≦
Represents the number 2. R ² is a linear or branched alkyl group,
It is preferably selected from an alkoxy group, a cycloalkyl group, an arylalkyl group, an aryl group and an alkylaryl group.

The aluminum halide compound may be used alone or
It can be used as a mixture of more than one species. Specific examples of the aluminum halide compound include, for example, ethyl aluminum dichloride, n-propyl aluminum dichloride, butyl aluminum dichloride, i-butyl aluminum dichloride, sesquiethyl aluminum chloride, sesquiisobutyl aluminum chloride, sesqui-i-propyl aluminum chloride,
Examples include sex-n-propylaluminum chloride, diethylaluminum chloride, di-i-propylaluminum chloride, di-n-propylaluminum chloride, di-i-butylaluminum chloride, diethylaluminum bromide, and diethylaluminum iodide.

Examples of the electron-donating compound serving as the reactant (v) include ethers, esters, ketones, phenols, amines, amides, imines, nitriles, phosphines, phosphites, stibines, arsines, phosphorylamides, and alcoholates. Of these, esters are preferred, and organic acid esters are most preferred. As organic acid esters, aromatic carboxylic acid mono- or diethyl,
Examples thereof include mono- or diesters of aliphatic carboxylic acids. Specific examples thereof include, for example, butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, malonate Diisobutyl acrylate, diethyl succinate, dibutyl succinate, diisobutyl succinate, glutaric acid, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate, dibutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, monomethyl fumarate, Diethyl fumarate, diisobutyric acid fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, methyl benzoate, ethyl benzoate, methyl p-triylate, p-tertiary
Ethyl tert-butyl benzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, phthalate Examples thereof include di-2-ethylhexyl acid, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, and dibutyl naphthalate. The electron donating compound (v) is used alone or as a mixture of two or more.

As the titanium halide compound as the reactant (vi), a titanium compound represented by the general formula Ti (OR ³ ) _f X _4-f is used. In the formula, R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and f represents 0
≤f <4. R ³ is preferably selected from linear or branched alkyl groups, alkoxy 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 titanium halide compounds include, for example, titanium tetrachloride, ethoxy titanium trichloride, propoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, diethoxy titanium dichloride, and triethoxy titanium chloride. .

The solid catalyst component used in the present invention is obtained by reacting a reactant (iv) with a homogeneous solution obtained by reacting the above reactants (i), (ii) and (iii) to obtain a solid product. And then reacting the reactants (v) and (vi).

These reactions are preferably performed in a liquid medium.
Therefore, especially if these reactants themselves are not liquid under the operating conditions, or if the amount of liquid reactants is insufficient,
It should be performed 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, halogen derivatives thereof, and mixtures thereof. For example, isobutane, hexane , Heptane, cyclohexane, benzene, toluene, xylene, monochlorobenzene, benzyl chloride, methylene dichloride, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-
Examples thereof include dichlorobutane, trichloroethane, tetrachloroethane, tetrachloroethylene, carbon tetrachloride, chloroform and the like. These organic solvents may be used alone or as a mixture. When a halogen derivative or a mixture is used, good results may be obtained in polymerization activity and stereoregularity of the polymer.

The reactants (i), (ii), (ii) used in the present invention
The amounts of i), (iv), (v) and (vi) are not particularly limited, but the molar ratio of magnesium atom (i) to aluminum oxygen-containing organic compound (ii) is 1: 0.01 to 1: 1. : 10, preferably 1: 0.05 to 1: 4, the molar ratio of the magnesium atom (i) to the oxygen-containing organic compound of silicon (iii) is 1: 0.01 to
It is preferable to select the used amount so as to be 1:20, preferably 1: 0.1 to 1: 5. The ratio of magnesium atoms to aluminum atoms in aluminum halide (iv) is 1: 0.
It is preferable to select the amount of the reactant to be used in the range of 1 to 1: 100, preferably 1: 0.1 to 1:20. In particular, 1: 0.4
A range of 1: 1: 5 is preferred. If the ratio of aluminum atoms is out of this range, the catalytic activity is lowered if the ratio is too large, and if the ratio is too small, good powder properties cannot be expected.

It is preferable to select the amount to be used so that the molar ratio of the magnesium atom to the electron donating compound (v) is 1: 0.05 to 1: 2.0, preferably 1: 0.1 to 1: 1.0. Outside of these ranges, problems such as low polymerization activity and low stereoregularity of the polymer arise. Further, it is preferable to select the amount of the reactant to be used so that the molar ratio of the magnesium atom to the titanium halide compound (vi) is in the range of 1: 1 to 1: 100, preferably 1: 3 to 1:50. If the ratio is out of this range, problems such as low polymerization activity and coloring of the product occur.

The reflection conditions for obtaining a homogeneous solution by using the reactants (i), (ii) and (iii) are -50 to 300 ° C, preferably 0 to 200 ° C, for 0.5 to 50 hours, preferably 1 to 50 hours. It is carried out at normal pressure or under pressure in an inert gas atmosphere for 6 hours. Further, in the reaction of the reactants (iv), (v) and (vi), at a temperature in the range of -50 to 200C, preferably -30 to 150C, for 0.2 to 50 hours, preferably 0.5 to 5 hours. The reaction is performed in an inert gas atmosphere at normal pressure or under pressure. Reactant (iv)
Is important and important because it plays a decisive role in the particle shape of the generated particles. In addition, the reaction of the reactant (vi) may be performed in multiple stages. In this case, there are some compounds that result in an increase in polymerization activity. The solid catalyst component (A) thus obtained may be used as it is, but generally, after removing the remaining unreacted products and by-products by an excess or gradient method, the solid catalyst component (A) is washed several times with an inert organic solvent. Used in an inert organic solvent. Isolation after washing and heating under normal pressure or reduced pressure to remove the inert organic solvent can also be used.

The solid catalyst component of the component (A) obtained as described above is used for olefin polymerization by being combined with the organometallic compound of the component (B) and the electron donating compound of the component (C).

As the component B, a trialkylaluminum is used.

The alkyl group has a linear or branched carbon number of 1
Up to 20 alkyl groups are used. Specifically, for example,
Examples 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.

These organometallic compounds are used alone or as a mixture of two or more.

As the electron donating compound of the component (C), an organic acid ester, an oxygen-containing organic compound of silicon, a nitrogen-containing organic compound and the like are preferable.

Examples of the organic acid ester include the same compounds as the reactant (v) used for preparing the solid catalyst component of the component (A). Among them, preferred are aliphatic carboxylic acid esters,
Aromatic carboxylic acid esters can be mentioned. In particular,
Aliphatic carboxylic acid esters include those having 2 to 18 carbon atoms.
And ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, butyl propionate and ethyl butyrate. Examples of the aromatic carboxylate include methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate having 8 to 24 carbon atoms.

The above-mentioned organic acid esters may be used alone, or two or more thereof may be used by mixing or reacting.

Examples of the oxygen-containing organic compound of silicon include the aforementioned (iii)
And the same compounds as the above reactants. The oxygen-containing organic compound of silicon is used alone or as a mixture of two or more kinds, and the same or different compound as the reactant (iii) can be used.

Examples of the nitrogen-containing organic compound include compounds having a nitrogen atom in the molecule and having a function as a Lewis base.

Specifically, acetic acid N, N-dimethylamide, benzoic acid N, N
Amide compounds such as dimethylamide, toluic acid N, N-dimethylamide, 2,2,6,6-tetramethylpiperidine, 2,6-diisopropylpiperidine, 2,6-diisobutylpiperidine, 2,6-diisobutyl- 4-methylpiperidine, 2,2,6-trimethylpiperidine, 2,2,6,6-tetraethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, 2,
2,6,6-tetramethyl-4-piperidyl benzoate,
Piperidine compounds such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate; pyridine compounds such as 2,6-diisopropylpyridine, 2,6-diisobutylpyridine and 2-isopropyl-6-methylpyridine Compound, 2,2,
5,5-tetramethylpyrrolidine, 2,5-diisopropylpyrrolidine, 2,2,5-trimethylpyrrolidine, 1,2,2,5,5-pentamethylpyrrolidine, pyrrolidine-based compounds such as 2,5-diisobutylpyrrolidine, Amine compounds such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, diisopropylethylamine, t-butyldimethylamine, diphenylamine, di-o-tolylamine, N, N-diethylaniline, N, N-diisopropylaniline And the like.

The nitrogen-containing organic compound may be used alone,
Also, two or more kinds can be used by mixing or reacting.

 These electron donating compounds may be used in combination.

The amount of the solid catalyst component (A) used is preferably an amount corresponding to 0.001 to 2.5 mmol (mmol) of titanium atoms per reactor.

The organometallic compound of the component (B) is
It is used at a concentration of 0.02 to 50 mmol, preferably 0.2 to 5 mmol.

The electron-donating compound of the component (C) is used at a concentration of 0.001 to 50 mmol, preferably 0.01 to 5 mmol, per reactor.

The mode of feeding the three components into the polymerization vessel in the present invention is not particularly limited. For example, a method of separately feeding the components (A), (B) and (C) into the polymerization vessel, respectively. Alternatively, a method in which the component (A) and the component (B) are brought into contact and then the component (C) is brought into contact with the component (C) to carry out polymerization, and the component (B) is brought into contact with the component (C) and then brought into contact with the component (A). A polymerization method, a method in which the component (A), the component (B), and the component (C) are brought into contact with each other in advance to perform polymerization, and the like can be employed.

The polymerization of the olefin is performed in a gas phase or a liquid phase at a reaction temperature lower than the melting point of the polymer.

When the polymerization is carried out in the liquid phase, the olefin itself may be used as the reaction medium, but an inert solvent may be used as the reaction medium. 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, cyclohexane and the like. Is appropriate.

The olefin to be polymerized in the method for producing a stereoregular polyolefin of the present invention, the general formula R-CH = CH ₂
Wherein R represents a linear or branched, substituted or unsubstituted alkyl group having 1 to 10, especially 1 to 8, carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 4-methyl-1
-Pentene, 1-octene and the like. They are,
Not only homopolymerization but also random copolymerization and block copolymerization can be performed. At the time of copolymerization, polymerization is carried out using two or more of the above-mentioned α-olefins or α-olefins and dienes such as butadiene and isoprene. In particular, it is preferable to carry out the polymerization using propylene, propylene and ethylene, or the above-mentioned α-olefin other than propylene and propylene, propylene and dienes.

The polymerization reaction conditions are not particularly limited as long as they are carried out at a reaction temperature lower than the melting point of the polymer, but usually the reaction temperature is 20 to 110.
° C, pressure ² ~ 50kg / cm ² · G

The reactor used in the polymerization step can be appropriately used as long as it is commonly used in the art. For example, using a stirred tank reactor, a fluidized bed reactor or a circulation reactor, the polymerization operation can be carried out by any of a continuous system, a semi-batch system and a batch system.
Further, the polymerization can be carried out in two or more stages having different reaction conditions.

〔The invention's effect〕

The first effect of the present invention is that the powder characteristics are excellent, for example, it is possible to obtain polymer particles having a small amount of fine particles and high bulk density having an average particle diameter of an appropriate size. It is effective when applied to a phase polymerization method. It is also possible to obtain polymer particles having a very narrow particle size distribution.
Therefore, in the polymerization step, the formation of deposits in the polymerization apparatus is prevented. Particularly, in the slurry method, the polymer is separated, and in the drying step, the polymer slurry is separated.
This facilitates the dispersion of the fine particles of the polymer out of the system. In addition, the drying efficiency is improved by improving the fluidity. Further, in the transfer step, no fridge or the like is generated 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 residue can be obtained. Due to its high activity, there is no need to worry about coloring, odor, etc. of the product, and it is not necessary to purify the polymer, which is extremely economical.

A third effect of the present invention is that the stereoregularity of the polymer is extremely good. Therefore, it is extremely advantageous for producing a polymer by a gas phase polymerization method without using a reaction medium.

〔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, the melt flow rate (hereinafter abbreviated as MFR) was measured under the condition L of ASTM D-1238. The isotactic index (hereinafter abbreviated as II) indicates the ratio of the insoluble polymer after extraction with n-heptane to the total formed polymer in terms of weight percentage.

The activity indicates the amount of polymer produced (g) per 1 g of the 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. Also,
The average particle diameter is a value obtained by reading the particle diameter corresponding to the weight integrated value of 50% of the above-mentioned approximate straight line. Fine particle content is 105
The ratio of fine particles of μ or less is indicated by weight percentage.

Example 1 (A) Preparation of solid catalyst component (A) 15 g (0.62 mol) of metallic magnesium powder was placed in a 3 flask equipped with a stirrer, and 0.75 g of iodine was added thereto.
401.7 g (3.1 mol) of ethylhexanol and 336.4 g (0.62 mol) of tetrakis (2-ethylhexoxy) silane,
After adding 126.5 g (0.62 mol) of triisopropoxyaluminum and further adding decane 1, the mixture was heated to 90 ° C. and stirred for 1 hour under a nitrogen seal. Subsequently, the temperature was raised to 140 ° C. and the reaction was carried out for 2 hours to obtain a homogeneous solution (Mg—Si—Al solution) containing magnesium, silicon and aluminum.

Mg conversion of Mg-Si-Al solution to a flask with an internal volume of 500 ml 0.0
After 66 mol was added and cooled to 0 ° C., a solution prepared by diluting 20.7 g (0.133 mol) of isobutylaluminum dichloride to 50% with decane was added over 2 hours. After adding the whole amount, 40
When the temperature was raised to ° C., a slurry containing a white solid product was obtained, and then washed with decane. After heating the slurry containing the white solid product thus obtained to 100 ° C,
After adding a total amount of a solution obtained by diluting 125 g (0.66 mol) of titanium tetrachloride in 125 g of chlorobenzene, diisobutyl phthalate was added in an amount of 7.
3 g (0.0264 mol) was added and reacted for 3 hours.

By passing the product, the solid part was collected, again suspended in 125 g of titanium tetrachloride and 125 g of chlorobenzene,
Stirred at 70 ° C. for 1 hour. Hexane was added to the product, and the product was thoroughly washed until no liberated titanium compound was detected. Thus, a slurry of the solid catalyst component (A) suspended in hexane was obtained. Drying under a nitrogen atmosphere from which the supernatant was removed and elemental analysis revealed that Ti was 3.3% by weight.

(Ii) Polymerization of propylene The inside of a stainless steel electromagnetic stirring autoclave having an internal volume of 5 was sufficiently replaced with nitrogen, and 1.4 mmol of triethylaluminum was used as the catalyst component (B), 0.35 mmol of diisobutyldimethoxysilane was used as the catalyst component (C), and sequentially adding the solid catalyst component (a) 10 mg, to adjust the internal pressure of the autoclave to 0.1 kg / cm ² G, hydrogen 0.2 kg / cm ² was added, liquid propylene 2000ml mixture was heated to 70 ° C. after stirring started ,
Polymerized for 90 minutes. After the completion of the polymerization reaction, the stirring was stopped and, at the same time, unreacted propylene in the system was released, and the produced polymer was recovered. As a result, the polymerization product was 611 g and the activity was 6110.
It corresponds to 0 g / g. The properties of the polymer particles were measured. The results were as follows: MFR 3.4 g / 10 min, II 99.4%, bulk density 0.44 g / cm ³ , average particle size 410 μ, σ 0.10, fine particle content 0% by weight. I got

Example 2 When preparing the solid catalyst component (A), the procedure of Example 1 (a) was repeated except that 10.4 g (0.067 mol) of isobutylaluminum chloride was used in (a) of Example 1 as the component (iv). A solid catalyst component was obtained in the same manner as described above.

Using the obtained solid catalyst component, propylene was polymerized under the same conditions as in (b) of Example 1. The result is activity 49
000 g / g. In addition, various properties of the polymer particles were measured to be MFR 2.9 g / 10 min, II 99.5%, and bulk density 0.48 g / cm ³ . The average particle size was 3180 μm, which was extremely large, σ 0.30, and the amount of fine particles was 0% by weight.

Example 3 In preparing solid catalyst component (A), component (iii)
A solid catalyst component (A) was obtained in the same manner as in Example 1 (A) except that diisobutyldimethoxysilane was used instead of the tetrakis (2-ethylhexoxy) silane used in (A) of Example 1. .

Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (b) of Example 1. The result was an activity of 56250 g / g. In addition, when the properties of the polymer particles were measured, MFR 3.7 g / 10 min, II 99.2%, bulk density 0.4
0g / cm ³ , average particle size 342μ, σ0.14, fine particle content 0.2% by weight
Was obtained.

Example 4 When preparing the solid catalyst component (A), the procedure of Example 1 (a) was repeated except that ethyl aluminum dichloride was used as the component (iv) in place of the isobutyl aluminum dichloride used in (a) of Example 1. )) To obtain a solid catalyst component (A).

Using the obtained solid catalyst component (A), propylene was polymerized under the same conditions as in (b) of Example 1. The result was 51200 g / g of activity. The properties of the polymer particles were measured, MFR 3.1 g / 10 min, II 98.7 g, bulk density 0.40 g
/ cm ³ , average particle diameter 400 μ, σ 0.13, fine particle content 0% by weight.

Comparative Example 1 Titanium tetrachloride 62.7 was used as the component (iv) in place of the isobutylaluminum dichloride used in (a) of Example 1.
A solid catalyst component was obtained in the same manner as in Example 1 (a) except that g (0.33 mol) was used.

Using the obtained solid catalyst component, propylene was polymerized under the same conditions as in (b) of Example 1. The result is an activity of 46
It was 100 g / g. The properties of the polymer particles were measured. The results were as follows: MFR 4.4 g / 10 min, II 97.7%, bulk density 0.30 g / cm ³ , average particle size 210 μ, σ 0.36, fine particle content 3.9% by weight. I got

Comparative Example 2 In the preparation of the solid catalyst component (A), the reaction was carried out in the same manner without adding tetrakis (2-ethylhexoxy) silane and triisopropoxyaluminum in Example 1, resulting in an agar-like heterogeneous liquid. . Using this heterogeneous liquid, isobutylaluminum dichloride was added in the same manner as in Example 1 and the temperature was raised, but no solid product was produced.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a preparation diagram (flow chart) of a catalyst used in the present invention.

Claims (1)

(57) [Claims] 1. A process for producing a stereoregular polyolefin in the presence of a catalyst comprising a transition metal compound and an organometallic compound, wherein component (A) comprises (i) metal magnesium, an organic hydroxide compound, or an oxygen-containing organic compound of magnesium. And at least one member selected from the group consisting of (ii) a general formula Al (OR ¹ ) _m X _{3 -m} (wherein R ¹ has 1 to 20 carbon atoms)
M represents a number satisfying 0 <m ≦ 3, and X represents a halogen atom. )) And a homogeneous solution containing (iii) an oxygen-containing organic compound of silicon, and (iv) at least one of the general formulas AlR ² _n X _3-n (wherein R ² Represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents a number satisfying 0 <n ≦ 2.) more solid product (v) an electron-donating compound (vi) general formula _{^{Ti (OR 3) f X 4}} -f ( wherein, R ³ represents a carbon hydrogen group having 1 to 20 carbon atoms, X represents a halogen atom, and f represents a number satisfying 0 ≦ f <4), and at least one trialkylaluminum compound as component (B) obtained by reacting a titanium halide compound represented by the following formula: And an electron donating compound as component (C) Method for producing a stereoregular polyolefin, wherein the use of Ranaru catalyst system.