JPH01165608A - Improved production of stereoregular polyolefin - Google Patents

Abstract

PURPOSE:To obtain a highly streoregular polyolefin of a good particle shape in high yields, by using a specified catalyst. CONSTITUTION:A homogeneous solution containing metallic magnesium, a hydroxylated organic compound, an electron-donating compound and an oxygen- containing organic compound of titanium is reacted with an aluminum halide compound. The formed solid product is further reacted with an electron-donating compound and a titanium halide compound. A mixed dispersion comprising the obtained solid composite, an organometallic compound of a metal of group Ia, IIa, IIb, IIIb or IVb of the periodic table and an electron-donating compound is allowed to absorb 0.1-100g of an alpha-olefin per g of the solid composite. An olefin is polymerized in the presence of a catalyst system comprising the obtained solid catalyst component, an organo-metallic compound of a metal of Group Ia, IIa, IIb, IIIb or IVb of periodic table to obtain a stereoregular polyolefin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing stereoregular polyolefins. More specifically, the present invention aims to produce highly stereoregular polymers with good particle shape by using a specific catalyst in the polymerization of α-olefins having 3 or more carbon atoms (hereinafter, also includes copolymerization of other α-olefins). The present invention relates to a production method capable of obtaining coalescence in high yield.

[Conventional technology]

Conventionally, catalysts for olefin polymerization 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 milling. δ-type titanium trichloride obtained by pulverization is known. Furthermore, as a method for modifying these catalysts, a method of mixing and pulverizing them together with various modifiers is also known. However, when polymerization is carried out using these catalysts, the polymerization activity is low, and the resulting polymer contains a large amount of catalyst residue, so that a so-called deashing step is indispensable. Furthermore, in recent years, many proposals have been made regarding the production of solid catalyst components containing magnesium, titanium, and halogen as main components. However, many of them require further improvement in terms of activity, stereoregularity of the polymer, powder properties, and the like.

Therefore, the inventors of the present invention have made intensive studies to solve these problems, and as a result, have published Japanese Patent Applications No. 61-144893 and No. 62-151303. Special request 1986
-154556, proposed a method for obtaining stereoregular polyolefins in high yield. However, when the methods of these inventions are applied to various industrial processes, especially gas phase polymerization, the resulting polymer particles may have a poor shape, a wide particle size distribution, or a large number of fine particles contained in the polymer particles. There was a problem that the powder properties were not good because the proportion of powder was high.

[Problem that the invention seeks to solve]

Therefore, the present inventors overcame the drawbacks of the prior art and produced highly stereoregular polymers with good powder properties in high yields even under gas phase conditions in the polymerization of α-olefins having 3 or more carbon atoms. We conducted extensive research to find a manufacturing method that would allow us to obtain this product.

[Means for solving problems]

As a result, the inventors of the present invention have developed Japanese Patent Application No. 61-144893 and Japanese Patent Application No. 6
2-151303. A specific solid composite shown in Japanese Patent Application No. 62-154556, an organometallic compound, a solid catalyst component obtained by absorbing an α-olefin into an electron-donating compound, an organometallic compound as a co-catalyst, and an electron-donating compound. The inventors have discovered that a highly stereoregular polymer having excellent powder properties can be obtained in high yield by using the method, and have completed the present invention. That is, in the present invention, in producing a stereoregular polyolefin in the presence of a catalyst consisting of a transition metal compound and an organometallic compound, (A-1) (vi) metallic magnesium and a hydroxide organic compound, In a homogeneous solution containing at least one member selected from the group consisting of oxygen-containing organic compounds of magnesium, (stone) an electron-donating compound, and (m) an oxygen-containing organic compound of titanium, A solid composite obtained by reacting an aluminum halide compound, and further reacting an electron donating compound and a titanium halide compound (A-2) I[ a, I[b,
5 to a mixed dispersion consisting of at least one organometallic compound of I[b and IV b group metals and (A-3) an electron-donating compound.
0.1 to 1 g of the solid composite at a temperature below 0°C.
A solid catalyst component obtained by absorbing 100 g of an α-olefin having 3 or more carbon atoms, and component (B) of No. Ja of the periodic table.

A method for producing a stereoregular polyolefin using a catalyst system consisting of at least one selected from the group of organometallic compounds of group IIa, Ilb, llIb and IVb metals and an electron-donating compound as component (C). .

[For production]

The solid composite (A-1) used in the present invention is disclosed in Japanese Patent Application No. 61-144893. Patent application 1986-1513
03. As detailed in Japanese Patent Application No. 62-154556, for example, a homogeneous compound obtained by reacting metallic magnesium with an electron-donating compound such as an organic compound hydroxide or an organic ester, and an oxygen-containing organic compound of titanium such as a titanium alkoxide, etc. It can be prepared by reacting a solution with an aluminum halide compound to obtain a solid product, and then reacting an electron donating compound and a titanium halide compound.

Examples of hydroxylated organic compounds include alcohols such as ethanol and 2-ethylhexanol, and organic silanols such as trimethylsilanol and triphenylsilanol. Examples of electron-donating compounds include esters such as ethyl acetate and diisobutyl phthalate.

Examples of titanium oxygen-containing organic compounds include titanium tetraethoxide and titanium-n-butoxide, and examples of aluminum halides include ethylaluminum dichloride and isobutylaluminum dichloride. Examples of the titanium halide include titanium tetrachloride.

The thus obtained solid composite (A-1) may be used as is, but it is generally used after removing residual unreacted substances and by-products by filtration or decanting, and then washing several times with an inert organic solvent. , suspended in an inert organic solvent. It can also be used which is isolated after washing and heated under normal pressure or reduced pressure to remove the inert organic solvent.

The solid composite (A-1) is then composed of an organometallic compound of a metal of group Ia, IIa, IIb, I[[b, IVb of the periodic table] of component (A-2) and an electron donor of component (A-3). By mixing with a chemical compound, a mixed dispersion liquid is obtained. A surfactant can be added to this mixed dispersion.

Finally, a solid catalyst component (A) is obtained by absorbing an α-olefin into this mixed dispersion.

The organic compound of component (A-2) is lithium.

Examples include organometallic compounds consisting of a metal such as magnesium, zinc, tin, or aluminum and an organic group.

As the above organic group, an alkyl group can be exemplified.

This alkyl group is linear or branched and has 1 to 1 carbon atoms.
Twenty alkyl groups are used. Specifically, for example,
n-butyllithium, diethylmagnesium, diethylzinc, trimethylaluminum, triethylaluminum, trimybutylaluminum, tri-n-butylaluminum.

Examples include tri-n-decylaluminum, tetraethyltin, and tetrabutyltin.

Particular preference is given to using trialkylaluminums having a straight S or branched alkyl group having 1 to 10 carbon atoms, and also alkyl metal halides having an alkyl group having 1 to 20 carbon atoms, such as ethylaluminum sesquichloride, diethylaluminum chloride. , diisobutylaluminum chloride or alkyl metal alkoxides such as diethylaluminum ethoxide can also be used.

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

Suitable examples of the electron-donating compound as component (A-3) include organic acid esters, oxygen-containing organic compounds of silicon, and nitrogen-containing organic compounds.

Examples of the m-acid ester include the same compounds as the reactants (i) and N) used in the preparation of the solid composite of component (A-1).

Among them, aliphatic carboxylic acid esters are preferred.

Examples include aromatic carboxylic acid esters. in particular,
The aliphatic carboxylic acid ester has 2 to 1 carbon atoms.
8, ethyl acetate, #acid probyl, butyl acetate,
Examples include ethyl pionate, butyl propionate, and ethyl butyrate. As the aromatic carboxylic acid ester, methyl benzoate has 8 to 24 carbon atoms.

Examples include ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate.

The above-mentioned organic acid esters may be used alone, or two or more types may be mixed or reacted together.

The oxygen-containing organic compound of silicon has 1 to 12 carbon atoms.
Examples include compounds in which the hydrocarbon group is bonded to silicon via oxygen.

Specifically, for example, trimethylmethoxysilane, trimethylethoxysilane, dimethylethoxysilane, and trimethyl-1-propoxysilane.

trimethyl-n-10 boxysilane, trimethyl-1-
Butoxysilane, trimethyl-1-butoxysilane, trimethyl-n-butoxysilane, trimethyl-n-pentoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane,
Diphenyldimethoxysilane, methyldimethoxysilane, dimethyljethoxysilane, diethyljethoxysilane.

Diphenyljethoxysilane, methyldodecyljethoxysilane, methyloctadecyljethoxysilane, methylphenyldiethoxysilane, methyljethoxysilane, dibenzyljethoxysilane, jetoxysilane, dimethyldi-n-butoxysilane, dimethyldi=i- Pentoxysilane.

Diethyl di-1-pentoxysilane, di-mie butyl di-mie pentoxysilane, diphenyl di-mie pentoxysilane, diphenyl di-n-octoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n
-Butyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane.

4-chlorophenyltrimethoxysilane, trimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-probyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane,
Vinyltriethoxysilane, 3-aminopropyl 1-jethoxysilane.

Triethoxysilane, ethyl-treated propoxysilane, and nyltreamed-propoxysilane.

i-pentyltri-n-butoxysilane, methyltrimypentoxysilane, ethyl-1-pentoxysilane, methyltri-n-hexoxysilane, phenyltrimypentoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-i-propoxy Alkoxysilanes or aryls such as silane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-1-pentoxysilane, tetra-n-hexoxysilane, tetraphenoxysilane, tetramethyljethoxydisilane, dimethyltetraethoxydisilane, etc. roxysilane,
Examples include haloalkoxysilanes or haloaryloxysilanes such as dichlorojethoxysilane, dichlorodiphenoxysilane, and tribromoethoxysilane.

The above oxygen-containing organic compounds of silicon may be used alone, or two or more types may be mixed or reacted together.

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

Specifically, acetic acid N, N-dimethylamide, benzoic acid N
, N-diethylamide, toluic acid N.

Amide compounds such as N-dimethylamide, 2°2.6
．． 6-tetramethylbiperidine, 2,6-diitupropylpiperidine, 2,6-dibutylpiperidine, 2,
6-dibutyl-4-methylpiperidine, 2.2.6
-Dolimethylpiveridine, 2,2,6,6-titraethylbiveridine.

1.2,2,6,6-pentamethylpiperidine.

2.2,6.6-tetramethyl-4-piperidylbenzoate, bis<2.2,6.6-tetramethyl-4-piperidyl) sepagate piperidine-based compound, 2.6-
Pyridine compounds such as diisopropylbyridine, 2゜6-dibutylpyridine, 2-isopropyl-6-methylpyridine, 2゜2.5.5-tetramethylpyrrolidine, 2.5-diisopropylpyrrolidine, 2.2 .5-
pyrrolidine compounds such as monotrimethylpyrrolidine, 1,2,2.5.5-pentamethylpyrrolidine, 2.5-diisobutylpyrrolidine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, diisopropylethylamine, t-butyl Examples include amine compounds such as dimethylamine, diphenylamine, and di-0-tolylamine, and aniline compounds such as N,N-diethylaniline and N,N-diisopropylaniline.

The above nitrogen-containing organic compounds may be used alone, or two or more kinds may be mixed or reacted together.

In the present invention, these (A-1), (A-2), (A-
3) In addition to the ingredients, surfactants can be used.

When absorbing the α-olefin, it is preferable to use a surfactant in order to avoid agglomeration due to adhesion of the solid composite particles.

The surfactants used include anionic surfactants,
Mention may be made of cationic surfactants, nonionic surfactants and amphoteric surfactants. Among them, nonionic surfactants are most preferred; examples of the nonionic surfactants include polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene alkyl ethers. Ethylene oleyl ether, polyoxyethylene polyhydric alcohol ether, polyoxyethylene alkylaryl ethers, such as polyoxyethylene octylphenyl ether.

Polyoxyethylene nonylphenyl ether.

C12-C18 fatty acid esters of C-C polyhydric alcohols, such as sorbitan fatty acid esters.

Ethylene glycol fatty acid ester, diethylene glycol fatty acid ester, propylene glycol fatty acid ester, glycerin fatty acid ester.

Examples include polyoxyethylene alkylamine. Particularly preferred is sorbitan fatty acid ester.

Examples of the sorbitan fatty acid ester include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan sesquioleate, and sorbitan distearate.

Furthermore, fluorine-based surfactants can also be used. Examples of the fluorosurfactant include nonionic perfluoroalkylethylene oxide adducts. Surfactants may be used alone or as a mixture of two or more.

Absorption of α-olefin occurs at temperatures below 50°C.
1), (A-2), (8-3) Further, the mixed dispersion of a surfactant is brought into contact with an α-olefin having 3 or more carbon atoms. Although absorption of α-olefins can be carried out in the gas phase, it is preferably carried out in the liquid phase. When absorbing in a liquid phase, the α-olefin itself may be used as a dispersion medium, but an inert solvent may also be used as a dispersion medium.

If an inert solvent is used as the dispersion medium, any inert solvent commonly used in the art can be used, but in particular alkanes, cycloalkanes having 4 to 20 carbon atoms, such as isobutane, pentane. ,
Hexane, cyclohexane, etc. are suitable.

As the α-olefin having 3 or more carbon atoms to be absorbed, those represented by the general formula R-CH=CH2 (wherein, R is 1 to
straight-chain or branched substituted or unsubstituted alkyl groups having 10, in particular 1 to 8 carbon atoms),
Specifically, propylene, 1-butene, 1-pentene,
Examples include 4-methyl-1-pentene and 1-octene.

Regarding the reaction temperature when absorbing α-olefin,
Although there is no particular limitation as long as the α-olefin is absorbed at a temperature of 50°C or lower, the reaction temperature is usually -50°C to 50°C.
Crawls to 0℃. If the temperature is higher than 50°C, the solid composite particles will stick to each other, which is not preferable. The pressure is not limited, but is selected to be 0.1 to 10 kg/-.G.

The amount of α-olefin to be absorbed is 0.1 to 100 g, more preferably 0.1 to 50 g per 1 g of the nuclear solid composite (A-1). If the amount of α-olefin absorbed is less than this range, the effects of the present invention cannot be obtained, and if it is more than this range, the solid composite particles may stick to each other, which is not preferable. The conditions for absorbing other α-olefins are not limited, but the contact time for absorption is usually 0.1 minutes to 5 hours, and when a dispersion medium is used, the amount of dispersion medium is 1 g of solid composite. The amount of organometallic (A-2) used is 0.11 per 'r'i1moβ in the solid composite (A-1).
1 to 200 moβ, the amount of electron donating compound (A-3) used is 0.1 to 1 per mo1 of organometallic compound (8-2)
selected from the range of moβ. When a surfactant is used, the amount used is 50,000 ppm or less, preferably 100 to 10,000 ppm based on the total content.
selected in the range of OOppm.

Any commonly used reactor can be used as appropriate, such as a stirred tank reactor.

Examples include fluidized bed reactors and circulation reactors, and the operation for absorbing α-olefins is a continuous method.

It can be carried out either by a semi-batch method or a batch method.

Before absorbing the α-olefin, the three components mentioned above (
A-1), (A-2), and (A-3) are fed into the reactor, but the manner in which they are fed into the reactor is not particularly limited. For example, component (8- 1), Ingredients (8-
2).

A method in which components (A-3) are each individually introduced into a polymerization vessel, or a method in which components (A-1) and (A-3) are brought into contact with each other and then brought into contact with component (A-2). (A-1)
A method of bringing component (8-2) and component (A-3) into contact with each other can be adopted.

Component (8) obtained as above is filtered or decanted to remove remaining unreacted substances and by-products, washed several times with an inert organic solvent, and then suspended in an inert organic solvent. and use it. It is also possible to use a product which has been isolated after washing and heated under normal pressure or reduced pressure to remove the inert organic solvent.

Component (A) prepared in the above manner is an organometallic compound of metals in Groups 1a, I[a, IIb, I[Ib, and IVb of the periodic table of component (B) and electron donating property of component (C). Combined with compounds and used for polymerization.

As the organometallic compound of component (B), those similar to those of component (8-2) mentioned above can be used, and as the electron-donating compound of component (C), those similar to those of component (A-3) mentioned above can be used. These do not have to be the same as those used in adsorbing the α-olefins, although they can be used.

The amount of the solid catalyst component (A) used is from o,ooi to 2.5 mmol (+nmol) of titanium atoms per 1β of the reactor.
Preference is given to using amounts corresponding to I).

The organometallic compound of component +8) is 0 per 1β of reactor.
．． 02-501n+ol, preferably 0.2-5+uo
Use at a concentration of 1.

The electron donating compound of component (C) is per reactor 11,
0.001-5011 ol, preferably 0.01-51
Use at a concentration of 1 ol.

The mode of feeding the three components into the polymerization vessel in the present invention is not particularly limited, and for example, component (8), component (B
), a method in which each component (C) is separately fed into a polymerization vessel, or a method in which component (8) and component (C) are brought into contact with each other, and then component (
A method of polymerizing by contacting with component (B) and component [C
) may be brought into contact with component (8) and then polymerized, or component (8), component (B), and component (C) may be brought into contact with each other in advance for polymerization.

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

If the polymerization is carried out in the liquid phase, the olefin itself may be used as the reaction medium, but it is also possible to use an inert solvent as the reaction medium. The inert solvent can be any one commonly used in the art, but especially alkanes having 4 to 20 carbon atoms, such as cycloalkanes such as isobutane, pentane, hexane, cyclohexane, etc. is appropriate.

The olefin to be polymerized in the method for producing polyolefins of the present invention is an α-olefin of the general formula R-CH=CH2 (wherein R is a linear or branched chain having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms). Examples include propylene, 1-butene, 1-pentene, 4-methyl-1-
Penten.

Examples include 1-octene. These can be subjected to not only homopolymerization but also random copolymerization and block copolymerization. During copolymerization, two of the above α-olefins
Polymerization is carried out using at least one α-olefin or dienes such as butadiene and isoprene, particularly propylene, propylene and ethylene, propylene and the above α-olefins other than propylene, propylene and dienes. It is preferable.

The polymerization reaction conditions are not particularly limited as long as the reaction temperature is lower than the melting point of the polymer, but usually the reaction temperature is 20 to 110 ℃.
℃, pressure 2-50 kg/ail + G.

The reactor used in the polymerization process may be any one commonly used in the technical field.
For example, the polymerization operation can be carried out in a continuous mode, a semi-batch mode, or a batch mode using a stirred tank reactor, a fluidized bed reactor, or a circulation reactor. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

[Effects of the invention] If the effects of the present invention are used, the conventional method, that is, the patent application filed in 1983
-144893. Patent application 1986-151303, patent application 1986
A polyolefin with excellent powder properties can be produced under gas phase conditions while maintaining the properties of the catalyst in No. 2-154556, such as high activity, high stereoregularity, and copolymerizability.

That is, the first effect of the present invention is that the powder properties are excellent, such as having fewer fine particles and being able to obtain polymer particles with a moderate average particle size and high bulk density. It is particularly effective when applied to gas phase polymerization. It is also possible to obtain polymer particles with an extremely narrow particle size distribution. Therefore, in the polymerization process, the formation of deposits in the polymerization apparatus is prevented, and in the polymer separation and drying process, separation and filtration of the polymer slurry are facilitated.
This prevents fine particles of the polymer from scattering out of the system. In addition, improved fluidity improves drying efficiency. Additionally, during the transfer process, there is no bridging within the silo.
Transportation problems will be resolved. Furthermore, it becomes possible to provide polymers with constant quality.

The second effect of the present invention is that a polymer having extremely high polymerization activity and requiring no deashing step for removing the catalyst can be obtained. 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, making it extremely economical.

The 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 that does not use a reaction medium.

〔Example〕

The present invention will be illustrated below by examples, but the present invention is not limited in any way by these examples.
In Examples and Comparative Examples, the melt flow rate (hereinafter abbreviated as MFR) was measured under ASTM D-1238 conditions.

The isotactic index (hereinafter abbreviated as II) indicates the proportion of the insoluble polymer after extraction with n-hebutane to the total produced polymer in weight percentage.

The Ti activity represents the amount of polymer produced per unit of Ti in the solid catalyst component (A) (9). The geometric standard deviation was determined by a known method from the approximate straight line and expressed as its common logarithm (hereinafter referred to as σ). Moreover, the average particle diameter is a value obtained by reading the particle diameter corresponding to 50% of the weight integrated value of the approximate straight line. The fine particle content indicates the proportion of fine particles having a particle size of 105 μm or less in weight percentage.

Example 1 (a) [Preparation of solid catalyst component (A-1)] 12 g of metallic magnesium powder (0,49101>) was placed in a 21 autoclave equipped with a stirring device, and 0.4 g of iodine was added thereto.
6g, 2-ethylhexanol 334.3g (2,6
1ol) and titanium tetrabutoxide 168.0g
(0,49nol).

Diisobutyl phthalate 27.6g (0,099101
) was added, and then decane 1β was added, the temperature was raised to 90°C, and 1β was added under a nitrogen blanket while eliminating the generated hydrogen gas.
Stir for hours. Subsequently, the temperature was raised to 140°C and reaction was carried out for 1 hour to form a homogeneous solution containing magnesium and titanium (Mg
-Ti solution) was obtained.

Mg-Ti solution M (
] After adding 0.048 iol (equivalent to 0.048 iol) and rapidly cooling to -20°C,
- A solution prepared by diluting 14.9 g of butylaluminum dichloride to 50% with decane was added over 2 hours. After everything was added and warmed to room temperature, a slurry containing a white solid product was obtained. After the slurry containing the thus obtained white solid product was heated to 60° C., 11,000 PP of sorbitan distearate was added. Then 3.3g (0,012mol) of diisobutyl phthalate
After that, the entire amount of a solution prepared by diluting 47 ml of titanium tetrachloride with 47 ml of 1,2-dichloroethane was added, and the mixture was reacted for 4 hours. At this time, no aggregation of the solid product was observed.

The mixture was further stirred at 70°C for 1 hour. The solid part was collected by filtering the product, and titanium tetrachloride 47
cnl and suspended in 47 ml of 1,2-dichloroethane,
The mixture was stirred at 0°C for 1 hour. Hexane was added to the product and the product was thoroughly washed until no titanium compound released was detected.

Thus, a slurry of solid catalyst component (Ad) suspended in hexane was obtained. Top 1112:a was removed and dried in a nitrogen atmosphere, and elemental analysis revealed that Ti was 3.0% by weight.

(b) Preparation of solid catalyst component (A) 52 g of solid composite (A-1) obtained by the method of (a) above by sufficiently purging the inside of a stainless steel electromagnetic stirring autoclave with a content of 15 Il with nitrogen. .

326 nnol of triethylaluminum as the organometallic compound (A-2) and 81.1 gnol of diphenyldimethoxysilane as the electron-donating compound (A-3) were successively added, followed by 3β of hexane. Thereafter, sorbitan distearate was added at a concentration of 1400 ppm based on the total content. Autoclave internal pressure to 0, 1 kg/
After adjusting the internal temperature to 20°C, start stirring,
While maintaining the temperature at 0° C., 250 g of propylene was fed over 20 minutes, and the mixture was stirred for 30 minutes.

The thus obtained solid catalyst component (8) was separated by P and thoroughly washed with hexane to obtain a slurry of the solid catalyst component (A) suspended in hexane. Remove the supernatant and
The yield after drying under nitrogen atmosphere was 302 g.

(c) Vapor phase polymerization of propylene The interior of a stainless steel electromagnetic stirring autoclave with an internal capacity of 51% was sufficiently purged with nitrogen, and 12.51nol of triethylaluminum was used as the catalyst component (B) and 3% of diphenyldimethoxysilane was used as the catalyst component (C). .1311
0+ and solid catalyst component (A) in terms of Ti 0, 123
111 Iol was added sequentially, and 100 g of glass peas (φ1.0 city) were added. Autoclave internal pressure 0.1kg
After adding 0.2 hg/aa of hydrogen and starting stirring (300 rpm), the temperature was raised to 80°C and propylene gas was added to adjust the internal pressure to 28 kg/aaG. Next, propylene gas was continuously supplied to maintain the pressure in the system, and propylene was polymerized at the same temperature for 2 hours.

After the polymerization reaction was completed, stirring was stopped, unreacted propylene in the system was simultaneously discharged, and the produced polymer was recovered.

As a result, the amount of polymer produced was 277 g, and the Ti activity was 2.
This corresponds to 671qr/g. In addition, when the properties of the polymer particles were measured, the MFR was 5.9 g/10 min, II
99.0%, bulk density 0.45g/-1 average particle size 66
0μ, σ 0.10. A result of fine particle content of 0% by weight was obtained.6 Examples 2 to 3 A solid composite obtained by the same method as in Example 1 (A-
Example 2 When preparing solid catalyst component (A) using 1)
In Example 3, a solid catalyst component (A) was prepared in the same manner as in Example 1, except that 50 g of propylene was treated, and in Example 3, 1500 g of propylene was treated.

Polymerization of propylene was carried out under the same conditions as in Example 1 (c) using the obtained solid catalyst component (A), triethylaluminum, and diphenyldimethoxysilane. The results are shown in Table 1.

Comparative Example 1 Polymerization of propylene was carried out under the same conditions as in Example 1 (c) using the solid composite (A-1) obtained in Example 1 (a), triethylaluminum, and diphenyldimethoxysilane. . The results are shown in Table 1.

Example 4 Solid composite obtained by the same method as Example 1 (8-
When preparing the solid catalyst component (A) using 1), Example 1 except that sorbitan distearate was not used.
A solid catalyst component (A) was prepared in the same manner as above.

Polymerization of propylene was carried out under the same conditions as in Example 1 (c) using the obtained solid catalyst component (A), triethylaluminum, and diphenyldimethoxysilane. The result is T
i activity 253 kg/g.

MFR5, 5g/10min, ll96. ．． 3%.

Bulk density: 0.43g/cd, average particle size: 630μ.

σ　0.10. The fine particle content was 0% by weight.

Examples 5-6 Solid composites obtained by the same method as Example 1 (A-
1) to prepare the solid catalyst component (A), except that ethyl benzoate was used in Example 5 and methyl p-toluate was used in Example 6 as the electron donating compound (A-3). A solid catalyst component (A) was prepared in the same manner as in Example 1.

Polymerization of propylene was carried out under the same conditions as in Example 1 (c) using the obtained solid catalyst component (A), triethylaluminum, and diphenyldimethoxysilane. The results are shown in Table 2.

Example 7 When preparing a solid composite, Example 1 (
A solid composite was obtained by the same method as a).

Using the obtained solid composite, a solid catalyst component (8) was prepared in the same manner as in Example 1 (b), and further Example 1
Polymerization of propylene was carried out under the same conditions as in (c). As a result, the Ti activity was 162 kg/g. In addition, when we measured the overhead properties of polymer particles, we found that MFR6.2g/10
min, 1197.0%, bulk density 0.48g/Cl11.
Average particle size 581μ, σ 0.12. fi fine particle content O
Weight % results were obtained.

Examples 8 to 11 When preparing solid composites, i used in Example 1 (a)
-Example 8 in place of butylaluminum dichloride
In Example 9, 50% ethylaluminum dichloride in decane, in Example 9, ethylaluminum sesquichloride in 50% decane, in Run I13'1llO, 50% i-butylaluminum dichloride in 1,2-dichloroethane, and in Example 11, diethylaluminum dichloride in 50% decane. Example 1 except that a 50% 1,2-dichloroethane solution of dichloride was used and the amount used was as shown in Table 3.
A solid composite was prepared by reacting in the same manner as in (a).

Using the obtained solid composite, a solid catalyst component (A) was prepared in the same manner as in Example 1 (b), and further Example 1
Polymerization of propylene was carried out under the same conditions as in (c). The results are shown in Table 3.

[Brief explanation of the drawing]

FIG. 1 shows a preparation diagram (flow chart) of the catalyst used in the present invention.

Claims (1)

[Scope of Claims] (1) In the production of stereoregular polyolefin in the presence of a catalyst consisting of a transition metal compound and an organometallic compound, as (A) component (A-1) (i) metallic magnesium and hydroxide. (iv) at least one member selected from the group consisting of an organic compound, an oxygen-containing organic compound of magnesium, (ii) an electron-donating compound, and (iii) an oxygen-containing organic compound of titanium; (A- 2) A mixed dispersion consisting of at least one organometallic compound of group Ia, IIa, IIb, IIIb and IVb metals of the periodic table and (A-3) an electron-donating compound is heated at 50°C. A solid catalyst component obtained by absorbing 0.1 to 100 g of α-olefin having 3 or more carbon atoms per 1 g of the solid composite at the following temperature; , IIa, IIb,
A method for producing a stereoregular polyolefin, comprising using a catalyst system comprising at least one selected from the group of organometallic compounds of Group IIIb and IVb metals and an electron-donating compound as component (C). (2) The solid catalyst component (A) is obtained by absorbing the α-olefin under liquid phase conditions, and the polyolefin is produced under gas phase conditions.
) Method described in section. (3) Solid catalyst component (A) by absorbing α-olefin
The method according to claim 1 or claim 2, wherein the method is carried out in the presence of a surfactant.