JPH0813855B2 - Method for producing stereoregular polyolefin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyolefin. More specifically, the present invention relates to α-containing 3 or more carbon atoms.
The present invention relates to a production method capable of obtaining a highly stereoregular polymer having a good particle shape in a high yield in the polymerization of olefins (hereinafter, also including copolymerization with other α-olefins).

[Conventional technology]

Conventionally, as the catalyst component for olefin polymerization, α-type titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, and purple γ obtained by reducing titanium tetrachloride with aluminum
Known are titanium type trichloride, and δ type titanium trichloride obtained by crushing these with a ball mill. Also,
As a method of modifying these catalysts, a method of mixing and pulverizing with various modifiers is also known. However, when the polymerization is carried out using these catalysts, the polymerization activity is low, and the catalyst residue in the obtained polymer is large, so that the so-called deashing step was 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 and powder characteristics.

The present inventors have proposed Japanese Patent Publication No. 52-15110 as a highly active olefin polymerization catalyst. There, a catalyst component (A) obtained by reacting a magnesium metal with an oxygen-containing organic compound such as a hydroxide organic compound or magnesium, an oxygen-containing organic compound of a transition metal, and an aluminum halide and a catalyst component (B) of an organometallic compound. )
A highly active catalyst system consisting of and has been used.

However, the polymer particles obtained in the presence of these catalysts have a small average particle size or a large proportion of fine particles contained in the polymer particles, and are still insufficient in terms of powder characteristics. It was a thing. In addition, α- having 3 or more carbon atoms
When olefin polymerization is carried out, the disadvantage is that the production ratio of the stereoregular polymer is low.

Furthermore, the present inventors have proposed a method for producing an ethylene copolymer of ethylene and an α-olefin having 3 or more carbon atoms in JP-A-59-58005. It is obtained by reacting magnesium metal with an organic hydroxide compound or an oxygen-containing organic compound of magnesium or an organic magnesium compound containing a halogen, an oxygen-containing organic compound of titanium or vanadium, a silicon compound, an aluminum halide compound, or a titanium tetrahalide. An ethylene copolymer is obtained in high yield by a catalyst system consisting of the catalyst component (A) and the organometallic compound catalyst component (B).

However, using this catalyst, α- with 3 or more carbon atoms
When the olefin was polymerized, only a polymer having insufficient powder characteristics and stereoregularity was obtained, and the polymerization activity was also insufficient.

[Problems to be solved by the invention]

Therefore, the present inventors have overcome the disadvantages of the prior art,
In the polymerization of α-olefins, particularly in the polymerization of α-olefins having 3 or more carbon atoms, earnest studies were conducted to find a production method capable of obtaining a highly stereoregular polymer having good powder properties in a high yield. .

[Means for solving problems]

As a result, the inventors of the present invention can obtain a highly stereoregular polymer having excellent powder characteristics in a high yield by using a specific catalyst system in the polymerization of an α-olefin having 3 or more carbon atoms. By discovering this, the present invention has been completed.

That is, the present invention provides: (A) (i) at least one member selected from metallic magnesium, a hydroxylated organic compound, and an oxygen-containing organic compound of magnesium; (ii) at least one tetravalent titanium alkoxide; (iii) An organoaluminum compound (iii-1),
The product obtained by reacting at least one member selected from the group consisting of polysiloxane or silanes (iii-2) and electron donating compound (iii-3), with (iv) at least one organic halogenation One obtained by reacting an aluminum compound, or after reacting the above (i) to (iv), further reacting (v) an electron donating compound with (vi) a tetravalent titanium halide compound. A solid catalyst prepared by contacting and absorbing at least one olefin with a solid composite having a valence divalent titanium content of less than 30% when expressed as a percentage of total titanium. Component (A), (B) at least one catalyst component (B) selected from the group of organometallic compounds of Group Ia, IIa, IIb, IIIb and IVb metals of the periodic table, (C) electron At least one selected from donor compounds In producing a polyolefin, which comprises using a catalyst system consisting of a catalyst component (C).

[Action]

The solid composite used in the production of the solid catalyst component (A) used in the present invention contains Mg, Ti, Al and Cl and has a valence of 2 when expressed as a percentage relative to total titanium.
It is satisfied that the valence of titanium is less than 30%, and the following solid composites can be used.

(I) at least one member selected from metallic magnesium, an organic hydroxide compound and an oxygen-containing organic compound of magnesium, (ii) at least one tetravalent titanium alkoxide, (iii) an organoaluminum compound (iii-1), Polysiloxane or silanes (iii-2), electron donating compounds (iii
-3) A homogeneous solution obtained by reacting at least one member selected from the group consisting of (3) with (iv) at least one organic aluminum halide compound, or (i) to
After the reaction of (iv), a compound obtained by further reacting (v) an electron donating compound with (vi) a tetravalent titanium halide compound can be mentioned.

As the component (i), for example, metallic magnesium and alcohols such as ethanol and n-butanol, or organic silanols can be used, and magnesium oxygen-containing organic compounds such as magnesium alkoxides can also be used.

As the component (ii), 4 such as titanium tetrabutoxide can be used.
Valent titanium alkoxides.

As the component (iii), an organoaluminum compound (iii-1) such as tri-i-butylaluminum, diethylaluminum chloride, polysiloxane such as dimethylpolysiloxane, diphenyldiethoxysilane or silanes (iii-2), benzoin Ethyl acid, ethyl p-anisate,
An electron donating compound (iii-3) such as 2,2,6,6-tetramethylpiperidine may be mentioned.

Examples of the component (iv) include organic aluminum halide compounds such as ethyl aluminum dichloride and i-butyl aluminum chloride. As the component (v), an electron donating compound which is the same as or different from the component (iii-3) can be used, and as the component (vi), a tetravalent titanium halide compound such as titanium tetrachloride can be mentioned.

A preferred example of a production method for providing such a solid composite is
JP-A-56-155205, JP-A-59-58005, JP-A-60-2487
05, JP-A-60-262802, Japanese Patent Application No. 60-275135, Japanese Patent Application Sho
Details are given in No. 61-144893.

It is essential that the solid composite containing Mg, Ti, Al and Cl thus obtained contains less than 30% of divalent titanium with respect to total titanium. If you have a lot of divalent titanium,
The stereoregularity of the polyolefin obtained by polymerization is poor. In order to reduce the valence of divalent titanium to less than 30%, the component (iii-
1) Organoaluminum compound and / or component (i
The reaction step of the organic aluminum halide compound of v) is important. For example, a trialkylaluminum such as triethylaluminum or tri-i-butylaluminum may be used in place of the organic aluminum halide compound of the component (iv) shown in the present invention, or the above-mentioned JP-A-60-24870.
Good results can be obtained by excessively reducing the amount of divalent titanium by using a large amount of the organoaluminum compound of component (iii-1) exceeding the range described in No. 5, etc. I can't.

Examples of α-olefins to be absorbed by contact with the solid composite include α-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, pentene-1, hexene-.
1, octene-1 can be mentioned, and ethylene, propylene and butene-1 are particularly preferable.

The amount of α-olefin absorbed by contact is preferably 10 parts by weight or less, and particularly preferably 0.01 to 10 parts by weight, per 1 part by weight of the solid composite. This contact treatment can be carried out in the gas phase or without solvent or in the presence of an inert organic solvent. When the reaction is carried out in the presence of an inert organic solvent, as the organic solvent, any of those usually used can be used, but aliphatic, alicyclic or aromatic hydrocarbons or halogen derivatives thereof, or a mixture thereof can be used. For example, isobutane, hexane, heptane, cyclohexane, benzene, toluene, xylene, monochlorobenzene and the like are preferably used.

The contact conditions are not particularly limited, but it is necessary to perform the contact in a state where oxygen, moisture, etc. are substantially absent. However, the so-called prepolymerization method in which the α-olefin is brought into contact with the solid composite in the presence of the catalyst component (B) cannot obtain the effective results as in the present invention. Generally, this contact treatment can be carried out at a temperature range of −50 to 150 ° C., preferably 0 to 100 ° C. under normal pressure or under pressure. In the case of treatment in the liquid phase, it is preferable to bring them into sufficient contact with stirring.

The amount of the solid complex used is not particularly limited, but preferably 1 titanium atom per 1 solvent or 1 reaction vessel.
An amount of solid complex corresponding to millimolar to 1 mol is used. It can also be carried out in the presence of hydrogen.

Further, during the contact treatment, the polysiloxane or silane represented by the component (iii-2) or the electron donor represented by the component (iii-3) can be coexistent.

After the contact treatment, washing may be further performed with an inert organic solvent, or washing may be omitted.

It is also possible to use a product which is isolated after washing and heated under normal pressure or reduced pressure to remove the inert organic solvent.

The solid catalyst component of the component (A) obtained as described above is the organometallic compound of the group Ia, IIa, IIb, IIIb, IVb metal of the periodic table of the component (B) and the component (C). Used in olefin polymerization by combining with an electron donating compound.

Examples of the organometallic compound as the component (B) include organometallic compounds composed of a metal such as lithium, magnesium, zinc, tin or aluminum and an organic group.

As the above organic group, an alkyl group can be mentioned as a representative. As this alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms is used. Specifically, for example, n-butyl lithium, diethyl magnesium, diethyl zinc, trimethyl aluminum, triethyl aluminum, tri-i-butyl aluminum, tri-n-butyl aluminum, tri-n-decyl aluminum, tetraethyl tin or tetrabutyl tin, etc. Can be given. Above all, it is preferable to use trialkylaluminum having a linear or branched alkyl group having 1 to 10 carbon atoms. Further, alkyl metal halides having an alkyl group having 1 to 20 carbon atoms, such as ethyl aluminum sesquichloride, diethyl aluminum chloride,
Diisobutyl aluminum chloride or alkyl metal alkoxides such as diethyl aluminum ethoxide can also be used.

These organometallic compounds are used alone or as a mixture of two or more kinds. It is of course possible to use them alone, but when they are used as a mixture of two or more kinds, they may bring about unique effects on the polymerization activity, the stereoregularity of the polymer, the powder properties and the like. As the electron-donating compound as the component (C), organic acid esters, oxygen-containing organic compounds of silicon, nitrogen-containing organic compounds and the like are preferable.

Examples of the organic acid ester include the same compounds as the reaction agents (iii-3) and (V) used for preparing the solid catalyst of the component (A). Of these, aliphatic carboxylic acid esters and aromatic carboxylic acid esters are preferred.
Specifically, examples of the aliphatic carboxylic acid ester include ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, butyl bromionate, and ethyl acetate having 2 to 18 carbon atoms. The aromatic carboxylic acid ester has 8 to 24 carbon atoms,
Methyl benzoate, ethyl benzoate, methyl toluate,
Examples thereof include ethyl toluate, methyl anisate and ethyl anisate.

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

The oxygen-containing organic compound of silicon has 1 to 12 carbon atoms.
And a compound wherein the hydrocarbon group is bonded to silicon by oxygen.

Specifically, for example, trimethylmethoxysilane, trimethylethoxysilane, dimethylethoxysilane, trimethyl-i-propoxysilane, trimethyl-n-propoxysilane, trimethyl-t-butoxysilane, trimethyl-i-butoxysilane, trimethyl-n. -Butoxysilane, trimethyl-n-pentoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane,
Methylphenyldimethoxysilane, diphenyldimethoxysilane, methyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, methyldodecyldiethoxysilane, methyloctadecyldiethoxysilane, methylphenyldiethoxysilane, methyldiethoxy Silane, dibenzyldiethoxysilane, diethoxysilane, dimethyldi-n-
Butoxysilane, dimethyldi-i-pentoxysilane,
Diethyldi-i-pentoxysilane, di-i-butyldi-i-pentoxysilane, diphenyldi-i-pentoxysilane, diphenyldi-n-octoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-
Butyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-
Chlorophenyltrimethoxysilane, trimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane , Triethoxysilane, ethyltri-i-propoxysilane, vinyltri-i-propoxysilane, i-pentyltri-n-butoxysilane, methyltri-i-pentoxysilane, ethyl-i-pentoxysilane, methyltri-n-hexoxysilane, Phenyltri-i-pentoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-i-pentoxy Alkoxysilanes such as amine, tetra-n-hexoxysilane, tetraphenoxysilane, tetramethyldiethoxydisilane, dimethyltetraethoxydisilane or aryloxysilane, dichlorodiethoxysilane, dichlorodiphenoxysilane, tribromoethoxysilane and other haloalkoxy. Examples thereof include silane and haloaryloxysilane.

The above-mentioned oxygen-containing organic compounds of silicon may be used alone, or may be used by mixing or reacting two or more kinds.

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 diethylamide and 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,
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate piperidine compound, 2,6-diisopropylpyridine, 2,6-diisobutylpyridine, 2-isopropyl-
Pyridine compounds such as 6-methylpyridine, 2,2,5,5
-Tetramethylpyrrolidine, 2,5-diisopropylpyrrolidine, 2,2,5-trimethylpyrrolidine, 1,2,2,5,5-pentamethylpyrrolidine, 2,5-diisobutylpyrrolidine pyrrolidine compound, trimethylamine, triethylamine, Tributylamine, tribenzylamine, tetramethylethylenediamine, diisopropylethylamine, t
-Butyldimethylamine, diphenylamine, di-o-
Examples include amine compounds such as tolylamine and aniline compounds such as N, N-diethylaniline and N, N-diisopropylaniline.

The above nitrogen-containing organic compound may be used alone,
Further, two or more kinds may be mixed or reacted and used.

The amount of the solid catalyst component of the component (A) used is preferably an amount corresponding to 0.001 to 2.5 mmol (mmol) of titanium atom per solvent or reactor 1.

The amount of the organometallic compound as the component (B) is 0.02 to 50 mmol, preferably 0.2 to 5 per 1 solvent or 1 reactor.
Used at a concentration of mmol.

The electron-donating compound as the component (C) is 0.001 to 50 mmol, preferably 0.0, per 1 solvent or 1 reactor.
Used at a concentration of 1-5 mmol.

The mode of feeding the three components into the polymerization vessel in the present invention is not particularly limited, and, for example, a method of feeding the components (A), (B) and (C) separately into the polymerization vessel. Alternatively, a method of contacting the component (A) with the component (C) and then contacting with the component (B) for polymerization, or contacting the component (B) with the component (C) and then contacting with the component (A). A method of polymerizing, a method of polymerizing by contacting the component (A), the component (B) and the component (C) in advance, and the like can be adopted.

Olefin polymerization is carried out in the gas phase or liquid phase at a reaction temperature below the melting point of the polymer.

When the polymerization is carried out in the gas phase, any of the commonly used methods such as a fluidized bed system and a stirred tank system may be used.

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. This inert solvent may be any of those commonly used in the art, in particular alkanes having 4 to 20 carbon atoms, cycloalkanes such as isobutane, pentane, hexane, cyclohexane and the like. Is appropriate.

As the olefin to be polymerized in the method for producing a polyolefin of the present invention, an α-olefin of the general formula R-CH = CH ₂ (wherein R is a linear chain having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms or (Representing a branched / substituted alkyl group). Specifically, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1
-Octene and the like. These can perform not only homopolymerization but also random copolymerization and block copolymerization. Upon copolymerization, two or more kinds of the above α-olefins or α-olefins and dienes such as butadiene and isoprene are used for the polymerization. In particular, it is preferable to carry out the polymerization using propylene, propylene and ethylene, propylene and the above-mentioned α-olefins other than propylene, and propylene and dienes.

The polymerization reaction conditions are not particularly limited as long as it is carried out at a reaction temperature below the melting point of the polymer, but the reaction temperature is usually 20 to 110.
Selected at ℃ and pressure of ^{2 to} 50 kg / cm ² · G.

The reactor used in the polymerization step can be appropriately used as long as it is usually used in the technical field. For example, a fluidized bed reactor, a stirred tank reactor or a circulation reactor can be used to carry out the polymerization operation in any of a continuous system, a semi-batch system and a batch system.
Furthermore, it is possible to carry out the polymerization in two or more stages under different reaction conditions.

〔The invention's effect〕

The effect of the present invention is, firstly, that the polymerization activity is further improved as compared with the conventional method in which the solid composite of the present invention is used as it is as the catalyst component (A). Since it is highly active, there is no need to worry about coloring or odor of the product, and there is no need to purify the polymer, which is extremely economical.

The second 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.

The third effect of the present invention is that the powder properties of the polymer are remarkably good. That is, according to the present invention, as compared with the conventional method, the production ratio of fine particles can be extremely reduced, and the particle diameter can be increased to a desired size. These things have industrially great significance. That is, in the polymerization step, the formation of deposits in the polymerization device is prevented, and in the polymer separation and drying steps, the fine particles of the polymer are prevented from scattering outside the system.
In addition, the improved fluidity improves the drying efficiency. Also,
In the transfer process, bridges and the like do not occur in the silo, and transfer problems are eliminated. Further, it becomes possible to supply a polymer having a certain quality.

[Examples] The present invention will be shown below by examples, but the present invention is not limited to these examples. In the examples and comparative examples, the melt flow rate (hereinafter abbreviated as MFR) was measured under ASTM D-1238 condition L. The isotactic index (hereinafter abbreviated as II) shows the ratio of the insoluble polymer after extraction with n-heptane to the total amount of the produced polymer in percentage by weight.

The Ti activity represents the amount of polymer produced (g) per 1 g of the Ti content in the solid catalyst component (A).

The average particle diameter is a value obtained by plotting the results of classification with a sieve on probability logarithmic paper and reading the particle diameter corresponding to a weight cumulative value of 50%. The fine particle content indicates the proportion of fine particles having a particle size of 105 μ or less as a weight percentage.

Titanium with a valence of two valences can be found in the Journal of Polymer Science A-1, September 1971, p. 235 [J. Boor, GASh
ort, J.Polym.Sci., Part A-1.9,235 (1971)],
Distilled water with sufficient nitrogen substitution was added to the solid complex, and the amount of hydrogen generated at this time was quantified. Further, the divalent Ti / total Ti described in the following Examples and Comparative Examples is the ratio (% by weight) of divalent titanium in the solid composite to total titanium.
Indicates.

Example 1 (a) Adjustment of solid catalyst component (A) In a 2 l flask equipped with a stirrer, under nitrogen atmosphere, 4.9 g (0.20 mol) of magnesium metal powder and 27.2 g (0.08 mol) of titanium tetrabutoxide were added, The temperature was raised to 80 ° C, and 31.1 g (0.42
(mol) was added dropwise over 1 hour, and then the temperature was raised to 120 ° C. for reaction. To the reaction product thus obtained, 340 ml of hexane was added at room temperature, and then a solution of tri-i-butylaluminum (0.20 mol) in hexane was added at 45 ° C over 1 hour. After adding everything, it stirred at 60 degreeC for 1 hour. Next, methylhydropolysiloxane (viscosity of about 30
Centistokes) 11.7 ml (0.20 gram atom of silicon) was added, and the mixture was reacted under reflux for 1 hour.

After cooling to 45 ° C., a 50% hexane solution of i-butylaluminum dichloride (1.1 mol) was added over 2 hours.
After adding everything, stirring was carried out at 70 ° C. for 1 hour. Hexane was added to the product and washed 15 times by the gradient method. Thus, a slurry of the solid complex suspended in hexane (containing 40 g of the solid complex) was obtained. A part of it was collected, the supernatant was removed, dried under a nitrogen atmosphere, and subjected to elemental analysis.
Ti is 8.9 wt%, Mg is 11.2 wt%, Al is 3.2 wt%, Si is 0.2 wt%, C
l was 58.2 wt%.

The divalent Ti / total Ti was 5%.

A slurry containing 30 g of the solid complex was placed in a flask having a volume of 1 and equipped with a stirrer, and n-hexane was added until the amount of n-hexane reached 500 ml.

This corresponds to 56 mmol of titanium atom per hexane.

Start stirring, keep the temperature at 30 ℃, and add ethylene gas to 200m.
The mixture was blown at a rate of 1 / min for 2 hours for absorption. This corresponds to absorbing 1 g of ethylene per 1 g of the solid composite.

Thus, the solid catalyst component (A) suspended in n-hexane
I got

When this catalyst component (A) was analyzed, it contained 45 mg of Ti per 1 g of the solid catalyst component (A).

(B) Polymerization of propylene The inside of a stainless steel electromagnetic stirring type autoclave having an internal volume of 2 l was sufficiently replaced with nitrogen, and 0.57 g of triethylaluminum as a catalyst component (B) and 0.24 g of phenyltriethoxysilane as a catalyst component (C) and 5 ml of a slurry containing 30 mg of the solid catalyst component (A) obtained in b) was sequentially added. The internal pressure of the autoclave was adjusted to 0.1 kg / cm ² G, hydrogen was added at 0.2 kg / cm ^2, and then 0.5 kg of liquid propylene was injected under pressure. While stirring was started, the internal temperature of the autoclave was raised to 60 ° C, and propylene was polymerized at the same temperature for 1.5 hours.

After the completion of the polymerization reaction, stirring was stopped and unreacted propylene in the system was released to collect the produced polymer. as a result,
The polymer produced is 170 g and the Ti activity corresponds to 126 Kg / g. Moreover, when the various properties of the polymer particles were measured, MFR1
5g / 10min, II 95.0%, bulk density 0.34g / cm ³ , average particle size 730μ,
Results with a fine particle content of 0.6% were obtained.

Comparative Example 1 In the method of Example 1, the solid composite was used as it was as the solid catalyst component (A) without being brought into contact with ethylene gas. The Ti activity was 93 Kg / g, MFR 15 g / 10 min, II 95.0%, bulk density was 0.34 g / cm ³ , average particle size was 230μ, and fine particle content was 2.6%. Compared with Example 1, the Ti activity, average particle size, and fine particle content were particularly insufficient.

Comparative Example 2 A slurry containing 30 g of the solid composite prepared in the same manner as in Example 1 was placed in a flask having a volume of 1 and equipped with a stirrer.
N-Hexane was added to a concentration corresponding to 56 mmol of titanium atom per hexane.

Stirring was started and the temperature was kept at 30 ° C., then 21.2 g of triethylaluminum was added. Immediately, blowing of ethylene was started, and ethylene was polymerized at a rate of 200 ml / min for 2 hours. As a result, a suspension containing 60 g of the polymer-solid composite mixture was obtained.

The amount of polymerization per 1 g of the solid composite was 1.0 g.

Polymerization of propylene was carried out in the same manner as in Example 1 except that the slurry containing 30 mg of the polymer / solid composite mixture was used instead of the catalyst component (A).

Ti activity is 110Kg / gTi, MFR14g / 10min, II94.0%, bulk density 0.34
The results were g / cm ³ , average particle size 360μ, and fine particle content 1.7%.

Compared to Example 1, the Ti activity was low, the average particle size was small, and the fine particle content was high.

Example 2 A solid catalyst component (A) was obtained in the same manner as in Example 1 except that the amount of ethylene to be contacted with and absorbed by the solid composite was 2 g per 1 g of the solid composite to polymerize propylene. went.

Ti activity 113Kg / g, MFR 14g / 10min, II 94.5%, bulk density 0.33g /
cm ³ , average particle size 800μ, fine particle content 0.5%.

Example 3 In the method of Example 1, propylene gas was used in place of ethylene at a rate of 150 ml / min for 3 hours for catalyst / absorption to obtain a solid catalyst component (A).

This is equivalent to absorbing 1 g of propylene per 1 g of the solid composite. Polymerization of propylene was carried out in the same manner as in Example 1 except that a slurry containing 30 mg of this solid catalyst component (A) was used.

As a result, Ti activity 270Kg / gTi, II 95.0%, bulk density 0.35g / cm
^{3. The} average particle size was 300μ and the fine particle content was 0.8%.

Example 4 (a) Preparation of solid catalyst component (A) Diethoxymagnesium 21.3 g (0.2 mol) was placed in a 1.6 l autoclave equipped with a stirrer, and titanium tetrabutoxide 68 g (0.2 mol) was added thereto. The temperature was raised to 120 ° C. and the reaction was performed for 1 hour. Then, at 120 ° C., 153 g of dimethylpolysiloxane (viscosity of about 50 centistokes at 25 ° C.) (0.2 gram atom of silicon) was pressure-fed by nitrogen and reacted at 120 ° C. for 1 hour. After the reaction, hexane 340ml
Was added and cooled to 45 ° C, and then 186 g (1.2 mol) of i-butylaluminum dichloride diluted to 50 wt% with hexane.
Was added over 3 hours. After adding everything, it stirred at 60 degreeC for 1 hour, and obtained the solid complex. This composite has a Ti content of 12.4 wt%, a Mg content of 6.3 wt%, an Al content of 1.3 wt%, and a Si content of 1.0 wt%.
%, Cl content was 35.6 wt%, and divalent Ti / total Ti was less than 1%.

Using the obtained solid composite, ethylene was absorbed and brought into contact with it in the same manner as in Example 1 to obtain a hexane suspension of the solid catalyst component (A).

(B) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in Example 1 using the above solid catalyst component (A). As a result, MFR21g / 10
Min, II 93.5%, polypropylene having a bulk density of 0.32 g / cm ³ were obtained.

The Ti activity was 73 Kg / g, the average particle size was 730 μm, and the fine particle content was 1.0 wt%.

Example 5 (a) Preparation of solid catalyst component (A) 12 g (0.49 mol) of metallic magnesium powder was placed in a 2 l autoclave equipped with a stirrer, and iodine 0.6 g, 2-
334.3 g (2.6 mol) of ethylhexanol and 168.0 g (0.49 mol) of titanium tetrabutoxide, 14.8 g of ethyl benzoate
After adding (0.099mol) and decane 1, 90 ℃
The temperature was raised to 1, and the mixture was stirred under a nitrogen blanket for 1 hour while removing generated hydrogen gas. Continue heating up to 140 ℃ 1
The reaction was carried out for a time to obtain a uniform solution containing magnesium and titanium (Mg-Ti solution).

0.048 mol of Mg-Ti solution converted to Mg in a flask with an internal volume of 500 ml
Was rapidly cooled to −20 ° C., and then a solution of 14.9 g of i-butylaluminum dichloride diluted to 50% with decane was added over 2 hours. After adding all, the temperature was raised to room temperature to obtain a slurry containing a white solid product. The slurry containing the white solid product thus obtained was heated to 60 ° C., and then 1.8 g (0.012 mol) of ethyl benzoate was added.
Then, after cooling to 45 ° C., a total amount of a solution prepared by diluting 47 ml of titanium tetrachloride with 47 ml of 1,2-dichloroethane was added and reacted for 4 hours, followed by further stirring at 70 ° C. for 1 hour. The solid part was collected by filtering the product and suspended again in 47 ml of titanium tetrachloride and 47 ml of 1,2-dichloroethane,
Stirred at 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 complex suspended in hexane was obtained.

After removing the supernatant liquid and drying in a nitrogen atmosphere, elemental analysis revealed that Ti6.0wt%, Mg17.7wt%, Al1.6wt%, Cl61.5wt%,
Results of less than 1% of divalent Ti / total Ti were obtained.

Using 30 g of this solid composite, propylene gas was brought into contact with and absorbed in the same manner as in Example 3 to obtain a solid catalyst component (A).

(B) Polymerization of propylene The inside of a stainless steel electromagnetic stirring autoclave with an internal volume of 2 l was sufficiently replaced with nitrogen, and 0.14 g of triethylaluminum as the catalyst component (B), 0.05 g of ethyl benzoate as the catalyst component (C) and the above ( An n-hexane slurry containing 5 mg of the solid catalyst component (A) obtained in b) was sequentially added. The internal pressure of the autoclave was adjusted to 0.1 kg / cm ² G, hydrogen was added at 0.2 kg / cm ^2, and then 0.5 kg of liquid propylene was injected under pressure. Start stirring and adjust the internal temperature of the autoclave to 65
The temperature was raised to ℃, and propylene was polymerized at the same temperature for 1.5 hours.

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.
The activity corresponds to 890 Kg / g. In addition, various properties of polymer particles were measured and found to be MFR 5.2 g / 10 min, II 96.5%, bulk density 0.4
The results were 0 g / cm ³ , average particle size 530μ, and fine particle content 0.1% by weight.

Example 6 Polymerization was carried out in the gas phase using the solid catalyst component (A) prepared in Example 1. Made of stainless steel with an internal volume of 2 liters,
Bulk density 0.34 g / cm ³ in an electromagnetic stirring type autoclave, MFR6g /
50 g of polypropylene powder for 10 minutes was charged and deaerated and dried at 70 ° C. for 2 hours. After thoroughly purging the inside of the autoclave with nitrogen, the internal temperature was adjusted to 60 ° C. Then, 0.57 g of triethylaluminum as catalyst component (B), component (C)
As the component, 0.24 g of phenyltriethoxysilane and 30 mg of the component (A) were sequentially added. Reactor internal pressure is 0.1 kg / cm ² G
After adjusting the pressure to 0.3 Kg / cm ² of hydrogen, the total pressure is 10.4 Kg / cm 2.
While continuously adding propylene to ² G, 2
Polymerization was carried out for a time. 22.0 g of polypropylene with an MFR of 5 g / 10 min and a bulk density of 0.35 g / cm ³ was obtained.

[Brief description of drawings]

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

Claims (5)

[Claims] 1. (A) (i) at least one member selected from magnesium metal, an organic compound containing hydroxide, and an oxygen-containing organic compound of magnesium; (ii) at least one tetravalent titanium alkoxide; (iii) organic Aluminum compound (iii-1), polysiloxane or silanes (iii-2), electron donating compound (iii
-3) A homogeneous solution obtained by reacting at least one member selected from the group consisting of (3) with (iv) at least one organic aluminum halide compound, or (i) to
After the reaction of (iv), the compound is further obtained by reacting (v) an electron-donating compound with (vi) a tetravalent titanium halide compound, and expressed as a percentage based on the total titanium. , A solid catalyst component (A) prepared by contacting and absorbing at least one kind of olefin with a solid composite having a valence of divalent titanium of less than 30%, and (B) of the periodic table.
At least one catalyst component (B) selected from the group of organometallic compounds of Group Ia, IIa, IIb, IIIb and IVb metals, and (C) at least one catalyst component selected from an electron donating compound ( in the presence of a catalyst system consisting a C), at least one of the general formula R-CH = CH ₂ (wherein, R represents a linear or substituted or non-substituted branched alkyl having 1 to 10 carbon atoms A group)) is polymerized to produce a stereoregular polyolefin. 2. An electron donating compound (iii-3) and (v)
The method according to claim (1), wherein is an organic acid ester. 3. The method according to claim 1, wherein at least one member selected from the group consisting of ethylene, propylene, and 1-butene is used as the olefin to be contacted with and absorbed by the solid composite. Method. 4. When contacting and absorbing an olefin to a solid composite, it is carried out in the presence of an inert organic solvent, and the solid composite is used in an amount corresponding to 1 mmol to 1 mol of titanium atom per 11 solvents. The method according to item (1), (2) or (3) in the range. 5. The catalyst component (C) is an oxygen-containing organic compound of silicon. Claims (1), (2), (3)
Alternatively, the method described in (4).