JPS6352645B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an α-olefin polymer, and more particularly, the present invention relates to a method for producing an α-olefin polymer, which is highly crystalline and has an improved powder shape, using a highly active catalyst with improved thermal stability. This invention relates to a method for manufacturing a combination. It is well known that α-olefins are polymerized by a so-called Ziegler-Natsuta catalyst consisting of a transition metal compound of group ~ of the periodic table and an organometallic compound of a metal of group ~. Among them, titanium trichloride is most widely used as a transition metal compound component to obtain highly crystalline polymers such as propylene and butene-1. Titanium trichloride can be divided into the following three types depending on its manufacturing method. Titanium tetrachloride is activated by reducing it with hydrogen and then pulverizing it in a ball mill (referred to as titanium trichloride (HA)). A compound represented by the general formula Ticl ₃ 1/3 AIcl ₃ (so-called titanium trichloride (AA)), which is activated by reducing titanium tetrachloride with metallic aluminum and pulverizing it in a ball mill. Titanium tetrachloride is reduced with an organic aluminum compound and then heat treated. However, none of these titanium trichlorides is fully satisfactory in terms of either catalytic activity or stereoregularity of the resulting polymer. In order to improve these drawbacks, it is necessary to increase the catalytic activity and completely eliminate the formation of amorphous polymers.
With the aim of minimizing, if any,
Various methods have been considered and tried. As one method, titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound,
A method has already been proposed in which the catalytic activity is increased and the formation of amorphous polymer is reduced by treatment with an electron donor and titanium tetrachloride (for example, JP-A-47-34478). However, these methods have the disadvantage that the catalyst lacks thermal stability. for example,
When polymerizing at a relatively high temperature (for example, 70°C or higher), the polymer particles become fine particles and swell due to the solvent used in the polymerization reaction, and if the treated reduced solid catalyst is left at a relatively high temperature for a long time, polymerization may occur. Activity decreases drastically. This is disadvantageous in industrial implementation because it is not possible to carry out the polymerization reaction at a high temperature to increase the productivity of the polymerization equipment, and special care is required to preserve the catalyst. Become. In addition, a solid catalyst component is prepared by mixing and reacting two reaction solutions in which Ticl ₄ and an organoaluminum compound are each mixed in advance with a certain amount of a complexing agent (an electron donor is also a type of complexing agent). A method to do this has also been proposed (e.g., Japanese Patent Laid-Open No. 53-9296).
This method also has the disadvantage of lacking thermal stability of the catalyst, as in JP-A-47-34478. It is also known that Ticl ₄ can be reacted with a mixture of an organoaluminum compound and a complexing agent without being mixed with the complexing agent in advance (Japanese Patent Publication No. 8768/1987). However, when using this method, the reduction reaction is carried out at 20°C to 200°C.
After the reaction was carried out at a high temperature of 150°C to 200°C, the catalyst activity was not sufficient. Furthermore, a method for producing a liquid material containing titanium trichloride by adding a homogeneous liquid material consisting of an organoaluminum compound and ether to Ticl ₄ , or by reversing the order of addition (Japanese Patent Application Laid-open No. 115797/1983) )
and a method of precipitating fine particulate titanium trichloride by heating the liquid material to 150°C or less (Japanese Patent Application Laid-Open No. 1989-1999).
47594, etc.) have also been proposed. These methods also have drawbacks such as insufficient catalytic activity and lack of thermal stability of the catalyst, and in addition, the catalyst production method requires at least three reaction steps, namely, the reaction of the organoaluminum compound and the ether. The production of liquefied titanium trichloride by the reaction of the liquid with Ticl ₄ , and the precipitation of fine-grained titanium trichloride by heating have not been simplified. As a new and simplified method, a method has been proposed in which Ticl ₄ is reacted with a mixture of an organoaluminum compound and a complexing agent to directly form particulate Ticl ₃ (Japanese Unexamined Patent Publication No. 1989-1999). No. 9296).
However, in this case, it is known that brown Ticl ₃ is produced, the polymerization activity is extremely low, and the crystallinity of the obtained propylene polymer is also low (Japanese Patent Application Laid-Open No. 53-9296, Comparative Example E). The present inventors conducted research to obtain a solid product that can directly produce a highly active and highly crystalline polymer without producing liquefied titanium trichloride.
Ticl ₄ is a reaction product obtained by reacting a certain amount of electron donor with an organoaluminum compound without mixing it with a complexing agent in advance.
The combination of the solid product obtained by reacting Ticl ₄ in the presence of an aromatic compound and then adding a certain amount of an electron donor with organoaluminum is very highly active and has a high thermal resistance. It was discovered that this is a catalyst with improved stability, and that an α-olefin polymer with high crystallinity and improved powder shape can be obtained using this catalyst, and the present invention was achieved. An object of the present invention is to provide a method for producing α-olefin polymers with high polymer yield and good shape using a catalyst with high thermal stability and high polymerization activity obtained by a novel preparation method. It is in. The present invention relates to a reaction product (hereinafter referred to as (A) or After reacting the product (sometimes abbreviated as (A)) with titanium tetrachloride in the presence of an aromatic compound, an electron donor (hereinafter sometimes referred to as the second electron donor) 1 A method for producing an α-olefin polymer, which comprises polymerizing α-olefin in the presence of a catalyst obtained by combining a solid product ( ) obtained by reacting ~7 mol with an organoaluminum compound. It is. The reaction of the organoaluminium compound (1 mol) with the first electron donor (1-2 mol) is carried out in a catalyst by -
It is carried out at 20°C to 200°C, preferably -10°C to 100°C, for 30 seconds to 5 hours. An electron donor may be added to the organoaluminum compound, or vice versa.
The amount of solvent used is per mole of organoaluminium.
0.5 to 5 is appropriate. The reaction solution after the completion of the reaction (sometimes referred to as reaction product solution (A)) is usually used as is in the next reaction as reaction product (A), but it can also be used without the catalyst. In the above reaction, if the amount of electron donor used is less than 1 mol, the effect may not be sufficient even if the second electron donor is reacted afterwards, and if the amount of the first electron donor used is less than 2 mol. If the amount is too large, reacting with the second electron donor has the drawback that the thermal stability of the catalyst is rather poor and the polymerization activity is also reduced. The organoaluminum compound used in the above reaction is
General formula _{AlRnR'n '}
represents a halogen such as fluorine, chlorine, bromine, and iodine, and n and n' represent any number of O<n+n'3), and specific examples include trimethylaluminum, triethylaluminum, and triethylaluminum. Tri-aluminum such as n-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum, tri-n-hexyl aluminum, tri-i-hexyl aluminum, tri-2-methylpentyl aluminum, tri-n-octyl aluminum, tri-n-decyl aluminum, etc. Alkylaluminums, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-i-butylaluminum monochloride,
Diethylaluminum monohalides such as diethylaluminium monofluoride, diethylaluminium monobromide, diethylaluminum monoiodide, alkylaluminum hydrides such as diethylaluminum hydride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichloride, i- Alkylaluminum halides such as butylaluminum dichloride are mentioned, and alkoxyalkylaluminiums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can also be used. As an electron donor, organic compounds having an atom of oxygen, nitrogen, sulfur, or phosphorus, such as alcohols, ethers, esters, aldehydes, fatty acids, ketones, nitriles, amines, and isocyanates. , azo compounds, phosphines, phosphites, phosphinites, thioethers, thioalcohols, and the like. Specific examples include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, cresol, xylenol, ethylphenol, naphthol, diethyl ether, di-n-propyl ether, di-n-butyl ether, di-i -alumyl ether, di-n-pentyl ether, di-n-
Ethers such as hexyl ether, di-n-octyl ether, di-i-octyl ether, ethylene glycol monomethyl ether, diphenyl ether, tetrahydrofuran, ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate,
Ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate,
2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenyl acetate, etc. Esters, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid, propylonic acid, butyric acid, oxalic acid, succinic acid, acrylic acid,
Fatty acids such as maleic acid and benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and benzophenone, nitriles such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, pyridine,
Amines such as aniline, isocyanates such as phenyl isocyanate and tolyl isocyanate, azo compounds such as azobenzene, ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, etc. Phosphites such as dimethyl phosphite, di-n-octyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, ethyl diethyl phosphinite, ethyl dibutyl phosphinite, phenyl diphenyl phosphinite Examples include phosphinites such as diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide, propylene sulfide and other thioethers, and thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol. I can do it. Moreover, these electron donors can also be used in combination. Among these, the above-mentioned ethers, that is, ether-containing components, can be preferably used. Solvents include n-pentane, n-hexane, n-
- Aliphatic hydrocarbons such as heptane, n-octane, i-octane, aromatic hydrocarbons such as benzene, toluene, xylene, carbon tetrachloride, chloroform,
Inert solvents such as hydrogen halides such as dichloroethane, trichloroethylene, and tetrachloroethylene are used. When reacting the reaction product (A) with titanium tetrachloride (hereinafter sometimes abbreviated as (B)) in the presence of an aromatic compound, there is no restriction on the order of addition, and (B) is gradually added to (A). (A) may be added to (B), (A) may be gradually added to (B), or (A) and (B) may be mixed all at once. In addition, aromatic compounds are
It only needs to be present during the reaction between titanium tetrachloride and the reaction product (A), and may be mixed with either titanium tetrachloride or the reaction product (A) in advance, or mixed with both separately. It can be used for reaction. The amount of aromatic compounds used is 300% per mole of titanium tetrachloride.
ml to 3000ml is preferred. When carrying out a reaction by adding (B) to (A), if (A) is the same reaction product as the reaction product using an aromatic compound as a solvent, a new aromatic compound is added. There is no need to use family compounds. The ratio of the reaction product (A) and titanium tetrachloride is
The ratio (atomic ratio) of the number of Al atoms in (A) to the number of Ti atoms in titanium tetrachloride (Al/Ti) is 0.1 to 1.0 (A) and (B)
The mixing and reaction of -10℃ to 65℃, preferably 10℃ to
It is preferable to carry out the reaction at a temperature of 65°C, to add and mix within 30 minutes, and then to continue the reaction for 5 minutes to 5 hours. Aromatic compounds used in the above reaction include aromatic hydrocarbons such as benzene and naphthalene, and their derivatives such as toluene, xylene, mesitylene, duurene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, and 1-phenylnaphthalene. Alkyl substituted products of, halides such as monochlorobenzene, orthodichlorobenzene, etc. are shown. These aromatic compounds can be used alone,
Two or more of them may be used in combination, or they may be used in combination with aliphatic hydrocarbons such as n-pentane, n-hexane, i-hexane, n-heptane, n-octane, and n-decane. . When mixing solvents, it is desirable that aromatic compounds be included at 10% (by volume) or more. After the reaction between titanium tetrachloride and reaction product (A) is completed,
Furthermore, 1 to 7 moles of a second electron donor is added (i.e., the molar ratio of the first electron donor to the previously used organoaluminum is 1 to 2, and the molar ratio of the second electron donor is 1 to 1). ~7) react. If the amount of the second electron donor used is less than 1 mol, the effect will not be sufficient, and if it is used in more than 7 mol, the effect will not increase and is not necessary. The second electron donor need not be the same as the first electron donor. The electron donor may be added after being diluted with a solvent. When diluting with a solvent, it is preferable that the amount is 200 ml or less per mole of the second electron donor.The second electron donor and solvent used in the above reaction should be diluted with the first electron donor and organic The explanation is the same as that given for the reaction of aluminum. The conditions for adding the second electron donor are -10℃~
It is preferably carried out within 30 minutes at a temperature of 65 °C, and after the addition of the electron donor is completed, the temperature is 65 °C to 250 °C,
Preferably, the reaction is carried out at 65°C to 200°C for 5 minutes to 5 hours. A solid product () is thus obtained. After the reaction is completed, the liquid part is separated by separation or decantation, and after repeated washing with a solvent such as n-hexane, the solid product () is used in the next polymerization step in a suspended state. It may be dried, or it may be further dried and taken out as a solid for use. The solid product () is then combined with an organoaluminum compound to serve as a catalyst for α-olefin polymerization. The organoaluminum compound used in this case is the same as that described above, but it does not need to be the same substance as that used in the reaction with the electron donor. The quantitative ratio of the organic aluminum compound to 100 g of the solid product is in the range of 50 to 5,000 g. Just by mixing the two in an inert gas, the activity as a polymerization catalyst for α-olefin can be immediately activated. It can be used in the same way as conventional Ziegler and Natsuta type catalysts. The polymerization reaction is n-hexane, n-heptane, n-
In addition to being carried out in a hydrocarbon solvent such as octane, benzene, or toluene, the process can also be carried out without using a solvent in a liquefied α-olefin monomer such as liquefied propylene or liquefied butene-1. The polymerization temperature is room temperature (approximately 20℃) to 200℃, and the polymerization pressure is normal pressure (0
Kg/cm ² G) to 50 Kg/cm ² G and is usually carried out for about 5 minutes to 10 hours. During polymerization, steps such as adding an appropriate amount of hydrogen to control the molecular weight are the same as in conventional polymerization methods. The α-olefins used in the method of the present invention include linear monoolefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, and 1-decene, and 4-methyl-pentene.
These include branched monoolefins such as 1,2-methyl-pentene-1,3-methyl-butene-1, diolefins such as butadiene, isoprene, and chloroprene, and styrene. Not only homopolymerization but also mutually other α
- Copolymerization can also be carried out in combination with olefin, such as propylene and ethylene, butene-1 and ethylene, propylene and butene-1. The first effect of the present invention is that the thermal stability of the catalyst is improved. For example, the solid product () is 30
Even when left at a high temperature of around 70°C for two months, there is relatively little decrease in polymerization activity, and even when α-olefin polymers are produced at relatively high temperatures of 70°C or higher, the obtained polymer does not turn into fine particles or swell in the solvent used in the polymerization reaction, and even if the solid product () and the organoaluminum compound are combined and left for about a week until polymerization starts,
The decrease in polymerization activity is relatively small. The second effect of the present invention is that 1 g of solid product ()
The yield of α-olefin polymer per unit is 7000~
It can reach up to 10,000g (polymer). Therefore, the amount of catalyst used for polymerization can be reduced, and even if the amount of alcohol used to kill the catalyst after producing the α-olefin polymer or to purify the polymer is reduced,
There is no coloring of the polymer, and there are also effects such as no adverse effects such as impairing the physical properties of the polymer or rusting of the mold during molding of the polymer. The third effect of the present invention is that a highly crystalline α-olefin polymer can be obtained. For example, in the production of propylene polymer, isotactic polypropylene as an n-hexane insoluble material is The index is to reach 98.5 to 99.5, so even if the atactic polypropylene is not removed, the physical properties will not be impaired. The fourth effect of the present invention is that the powder shape of the obtained polymer is improved. For example, in the production of propylene polymer, the powder shape is close to spherical, the particle size of the polymer is uniform, and 32 mesh ~
80 to 90% of it falls within 60 meshes, and the bulk specific gravity also shows a high value of 0.4 to 0.50. Example 1 (1) Preparation of catalyst In a reactor purged with nitrogen, 145 ml of n-hexane,
0.076 mol of diethylaluminium monochloride,
0.076 mol of di-n-butyl ether (initial molar ratio of electron donor to organic aluminum (hereinafter referred to as the initial molar ratio) is 1) was mixed at 25°C for 1 minute, and left at the same temperature for 5 minutes to react. Reaction product solution (A)
I got it. A solution consisting of 300 ml of toluene and 0.300 mol of titanium tetrachloride was heated to 35°C to form the reaction product solution (A).
was added for 3 minutes, reacted for 5 minutes, and
0.228 mol of di-n-butyl ether (the molar ratio of the second electron donor to the organoaluminum (hereinafter referred to as the second molar ratio) is 3) was added at 35°C for 1 minute, and then the temperature was raised to 80°C. It was warmed and allowed to react for 30 minutes. After the reaction, cool to room temperature (approximately 20°C), remove the supernatant liquid by decantation, add 300 ml of n-hexane, remove the supernatant liquid, repeat the operation three times, and then remove under reduced pressure. After drying, a reaction product (2) was obtained. (2) Production of propylene polymer Add 100 ml of n-hexane, 7.0 g of diethylaluminum monochloride, and 350 mg of solid product (), leave it under stirring at 28°C for 24 hours, and then add 1 ml of n-hexane to a stainless steel reactor. , put 6.3 ml of the slurry containing the above catalyst (containing 20 mg of solid product ()), add 150 ml of hydrogen, and then reduce the propylene partial pressure to 10
The polymerization reaction was carried out at Kg/cm ² G and a polymerization temperature of 70° C. for 4 hours. After the reaction is complete, add 50 ml of methanol to the reactor to stop the polymerization reaction, pour the contents into a Buchner funnel, rinse with 500 ml of n-hexane three times, and remove the polymer as an insoluble matter in n-hexane (20°C). (isotactic polypropylene) and n-hexane (20°C) soluble polymer (atactic polypropylene), each of which is dried.
192 g of isotactic polypropylene and 1.0 g of atactic polypropylene were obtained. The isotactic polypropylene polymer yield (hereinafter simply referred to as polymer yield) per 1 g of solid product () is
The weight was 9,600 g (polymer), and the isotactic index (percentage of isotactic polymer to the total amount of produced polymer) was 99.5. The bulk specific gravity of isotactic polypropylene is 0.47,
It was close to a spherical shape, with 82.5% falling between 32 meshes and 60 meshes. Example 2 200ml n-heptane, triethylaluminum
0.08 mol, di-n-butyl ether 0.16 mol at 15℃
Mix for 5 minutes at
mol of diisoamyl ether over 5 minutes at 60°C, reacted for 20 minutes, then added 0.12 mol of diisoamyl ether over 5 minutes at 60°C, and raised the temperature to 90°C.
The reaction was allowed to proceed for 15 minutes. After cooling to room temperature, a solid product () was obtained in the same manner as in Example 1, and propylene was polymerized. Example 3 Toluene 210ml, triisobutylaluminum
0.07 mol of di-n-dodecyl ether and 0.105 mol of di-n-dodecyl ether (initial molar ratio 1.5) were added at 30°C for 30 seconds, and the reaction solution was left to react at room temperature for 1 hour.
15 in a solution consisting of 300 ml and 0.20 mol of titanium tetrachloride.
℃ for 1 minute, reacted for 60 minutes, and then added 0.315 mol of di-n-butyl ether and 200 mol of n-heptane.
ml was added over 30 minutes at 15°C, and the temperature was raised to 68°C and reacted for 120 minutes. After cooling to room temperature, a solid product () was obtained in the same manner as in Example 1, and propylene was polymerized. Example 4 100 ml of ethylbenzene, 0.13 mol of tri-n-octylaluminium, and 0.16 mol of di-n-butyl ether were added at 50°C for 1 minute, and left to react for 30 minutes. To the reaction solution, 800 ml of monochlorobenzene, 0.77 mol of titanium tetrachloride, A solution consisting of was added at 50°C for 30 minutes and reacted for 30 minutes, then 0.49 mol of di-n-octyl ether was added at 50°C over 2 minutes, the temperature was raised to 100°C, and reaction was carried out for 10 minutes. After cooling to room temperature, a solid product () was obtained in the same manner as in Example 1, and propylene was polymerized. Example 5 200 ml of n-decane, 0.10 mol of di-n-propylaluminium monochloride, and 0.11 mol of di-n-octyl ether were mixed at 20°C for 3 minutes and reacted at the same temperature for 25 minutes. The reaction solution was mixed with titanium tetrachloride. A solution consisting of 0.83 mol and 600 ml of toluene was mixed at 20°C for 30 minutes, left at the same temperature for 2 hours to react, and then the di-n
-0.54 mol of dodecyl ether was added at 20°C over 5 minutes, the temperature was raised to 75°C, and the mixture was reacted for 20 minutes. After cooling to room temperature, a solid product () was obtained in the same manner as in Example 1, and propylene was polymerized. Example 6 200 ml of n-heptane, 0.12 mol of diethylaluminum monochloride, diisopropyl ether
A reaction solution consisting of 0.12 mol of toluene and 0.04 mol of titanium tetrachloride was mixed at 10°C for 2 minutes and left to react at the same temperature for 30 minutes, and a solution consisting of 200 ml of toluene and 0.25 mol of titanium tetrachloride was mixed at 55°C for 10 minutes. After reacting at the same temperature for 10 minutes, 0.50 mol of di-n-butyl ether was added at 55°C for 30 seconds, the temperature was raised to 85°C, and the mixture was reacted for 25 minutes. After the reaction is complete, remove the supernatant liquid by decantation, add 300 ml of n-hexane, and remove the supernatant liquid three times. Using the solid product () suspended in n-hexane, Polymerization of propylene was carried out in the same manner as in Example 1. Example 7 The solid product () obtained in Example 1 was stored at 30° C. for 2 months, and then propylene was polymerized in the same manner as in Example 1. Example 8 Catalyst components were combined, stirred, left to stand, and propylene treated in the same manner as in Example 1, except that the amount of solid product () used was 18 mg, the amount of diethylaluminium chloride was 370 mg, and the polymerization temperature was 80 ° C. Polymerization was carried out. The bulk specific gravity of the polymer was 0.45, the polymer particles were not made into fine particles, and there was no problem of swelling caused by the solvent used in the polymerization reaction. Example 9 Solid product 16 obtained analogously to Example 2
420mg of diethylaluminum monochloride and 11g of n-hexane were placed in a reactor, 60ml _{of H2} was added, the polymerization temperature was 60℃, and 10g of ethylene was added each time during polymerization.
While supplying a total of 8 times at 30 minute intervals, the partial pressure of propylene was
The polymerization reaction was carried out at 10 Kg/cm ² G for 4 hours. After the reaction,
A propylene-ethylene copolymer was obtained by the same operation as in Example 1. Example 10 A propylene-butene-1 copolymer was obtained in the same manner as in Example 9, except that a total of 20 g (2.5 g per supply x 8 times) of butene-1 was used instead of ethylene. Example 11 25 mg of the solid product of Example 3 () was combined with 480 mg of triisobutylaluminum at a hydrogen partial pressure of 5 Kg/cm ² G and an ethylene partial pressure of 5 Kg/cm ² G at 85°C.
A time polymerization reaction was carried out and an ethylene polymer was obtained by the same operation as in Example 1. Example 12 32 mg of the solid product () of Example 1 and 290 mg of triethylaluminum were combined, 1 part of n-hexane was added to the same polymerization vessel as in Example 1, and butene-
After adding 510 g of 1, a polymerization reaction was carried out at 70°C for 3 hours. After the reaction was completed, the solvent was distilled off and dried to obtain polybutene. Example 13 16 mg of the solid product () obtained in Example 2 and 380 mg of diethylaluminium monocnylide were heated with hydrogen.
It was added together with 90 ml to 500 g of liquefied propylene, and a polymerization reaction was carried out at a polymerization temperature of 70° C. for 3 hours. After the reaction was completed, unreacted propylene was purged to obtain a propylene polymer. Comparative Example 1 In Example 1, only diethylaluminum monochloride was used instead of the reaction solution of di-n-butyl ether and diethylaluminium monochloride, and 0.228 mol of di-n-butyl ether was used as the second electron donor. Polymerization of propylene was carried out in the same manner as in Example 1, except that 0.304 mol (plus the unused initial electron donor) was used to obtain a solid product. It was very low. Comparative Example 2 In Example 1, instead of reaction product liquid (A) (initial molar ratio 1), 0.053 mol of di-n-butyl ether and 0.076 mol of diethylaluminum monochloride were reacted in the same solvent as in Example 1. A solid product was obtained in the same manner as in Example 1, except that 0.251 mol of di-n-butyl ether was used as the second electron donor instead of 0.228 mol. Polymerization was carried out. Comparative Example 3 In Example 1, only 0.076 mol of diethylaluminium monochloride was used instead of the reaction product solution (A), and 0.300 mol of titanium tetrachloride was reacted with 0.304 mol of di-n-butyl ether instead of 0.300 mol of titanium tetrachloride. A solid product was obtained and propylene was polymerized in the same manner as in Example 1 except that a liquid (reacted in 300 ml of toluene at 35°C for 4 minutes) was used. Comparative Example 4 A solid product was obtained and propylene was polymerized in the same manner as in Example 1, except that 300 ml of n-heptane was used instead of 300 ml of toluene. The polymerization activity is extremely low, and aromatic compounds are essential components in the production of solid products (). Comparative Example 5 A solution of 600 ml of hexane and 150 ml of Ticl ₄ was heated to 1°C.
450 ml of hexane and 173 ml of AlEt ₂ cl were added within 4 hours, the temperature was raised to 65° C., and the resulting solid was washed to obtain 285 g of reduced solid. 285 g of reduced solid is suspended in 1720 ml of hexane, 256 ml of diisoamyl ether is added, stirred at 35° C. for 1 hour, separated and washed. The treated solid thus obtained was added to 850 ml of a 40% by volume solution of Ticl ₄ in hexane.
After stirring at 65°C for 2 hours, the product was washed with hexane to obtain a solid product, which was stored and propylene polymerized in the same manner as in Example 7. Comparative Example 6 150 ml of purified heptane, 10 ml of Ticl ₄ , and 52.4 ml of di-n-octyl ether were added to obtain a homogeneous solution of Ticl ₄ and ether in heptane, and 9.9 ml of diethyl aluminum monochloride was added little by little at 25°C to 30°C. This was added dropwise to obtain a brown homogeneous solution of titanium trichloride. at 25℃
After completing the reduction reaction for 30 minutes, the temperature was raised to 50℃,
Stirring was continued for 60 minutes, the temperature was further raised to 90°C, and the solid obtained by stirring for 60 minutes was washed and dried.
Storage and propylene polymerization were carried out in the same manner. Comparative Example 7 In Example 1, the first electron donor (di-n-
Except that the reaction product liquid (A) was obtained by adjusting the molar ratio of (butyl ether) and organoaluminum to 3.
A solid product was obtained in the same manner as in Example 1, and propylene was polymerized. The results of the above Examples and Comparative Examples are summarized in the following table.

[Table] Example 14 Add 7.0 g of diethylaluminum monochloride and 350 mg of the solid product () obtained in Example 1 to 100 ml of n-hexane, set the propylene partial pressure to 1 Kg/cm ² G,
After preactivation by reacting propylene at 25°C for 10 minutes, and after leaving it under stirring at 28°C for 24 hours, Example 1
Polymerization of propylene was carried out in the same manner. Polymer yield per 1 g of solid product () is 9700 g, isotactic index is 99.5, polymer
BD is 0.46, proportion of 32-60 meshes is 83.0%,
MFR was 6.5.

[Brief explanation of drawings]

FIG. 1 is a flowchart of the catalyst according to the production method of the present invention.

Claims (1)

[Claims] 1 A reaction product obtained by reacting 1 to 2 moles of an ether-containing component with 1 mole of an organoaluminum compound is reacted with titanium tetrachloride in the presence of an aromatic hydrocarbon compound, and then 1 to 1 mole of an ether-containing component is added to the reaction product. A method for producing an α-olefin polymer, which comprises polymerizing α-olefin in the presence of a catalyst obtained by combining a solid product () obtained by reacting ~7 mol of α-olefin with an organoaluminum compound.