JPS5835602B2 - Method for producing α-olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing α-olefin polymers, and more particularly, the present invention relates to a method for producing α-olefin polymers, and more particularly, the present invention relates to a method for producing α-olefin polymers, and more particularly, the present invention relates to a method for producing an α-olefin polymer, which has a high polymer yield per catalytic component, and has a high yield of α-olefin. Highly crystalline α-
The present invention relates to a method for producing an olefin polymer.

Hereinafter, in the present invention, the term "α-olefin polymerization or polymer" includes not only homopolymerization of α-olefin, but also copolymerization or copolymerization of two or more types of α-olefins.

It is well known that α-olefins are polymerized by a so-called Ziegler-Natsuta catalyst consisting of a transition metal compound of groups 1 to 2 of the periodic table and a metal or organometallic compound of groups 1 to 2 of the periodic table.

Conventionally, in order to obtain highly crystalline polymers such as α-olefins such as propylene and butene-1, titanium trichloride or titanium trichloride-containing compounds have been variously improved and most widely used as transition metal compound components. has been done.

Methods for producing titanium trichloride include (1) a method of reducing titanium tetrachloride with hydrogen and then pulverizing it in a ball mill to activate it;
2) A method of reducing titanium tetrachloride with metal aluminum and then activating it by ball milling (the resultant is a titanium trichloride composition having a composition of TiCl3.+AlCl3.

In the following, titanium trichloride (AA) or TiCl
3 (sometimes abbreviated as AA)), (3) a method of heat treatment after reduction with organic aluminum, etc.

However, titanium trichloride or titanium trichloride (AA) described in - is not fully satisfactory in terms of catalytic activity and stereoregularity (use of large amounts of alcohol etc. in the deashing process, There are problems such as coloring of the polymer, changes in physical properties, rusting of molds during molding, etc. Also, a large amount of amorphous polymer is generated as a by-product, requiring a process of removal and post-treatment, and furthermore, it has no industrial value. There were disadvantages such as low yield and loss of raw material monomer.

Various methods have been proposed to improve these drawbacks.

These methods are methods for increasing the catalytic activity and eliminating or minimizing the production of amorphous polymers.

For example, a method in which titanium trichloride (AA) is reacted with an electron donor and titanium tetrachloride (for example, Japanese Patent Publication No. 43-100
65, JP-A No. 48-64170, etc.), titanium trichloride (AA) is treated with ether to form a liquid, and a liberating agent is added to this liquid to produce fine-grained solid titanium trichloride. There are methods of precipitation (for example, JP-A-51-16297).

Even in the methods according to these inventions, the catalytic activity and stereoregularity were unsatisfactory, and even higher catalytic activity and stereoregularity were required.

The purpose of the present invention is to achieve a higher polymer yield per catalyst component than the conventional methods as described above, to produce extremely little amorphous polymer, and to produce polymers without removing the amorphous polymer. It is an object of the present invention to provide a method for producing an α-olefin polymer in which the physical properties of the polymer are not impaired.

The present invention produces α-olefins by homopolymerizing or copolymerizing α-olefins using a catalyst obtained by combining a solid product containing a transition metal of Group 1 Va or Group Va of the periodic table with an organoaluminum compound. In the method for producing a polymer, the solid product is a solid product obtained by dissolving a titanium trichloride composition in an electron donor and precipitating it (
I) is reacted with an electron donor and titanium tetrachloride, washed to obtain a solid product (II), and reacted with titanium tetrachloride to obtain a final solid product. This is a method for producing an α-olefin polymer.

The preparation of the final solid product, which is a fraction of the catalyst used in the present invention, is described.

First, the substances used for preparation will be explained.

A titanium trichloride composition is a titanium trichloride composition containing TiCl4, which is the first compound in the periodic table.
It refers to a composite chloride of titanium and a reducing metal obtained by reducing TiCl4 with a reducing metal selected from metals of Group A, Group 1Ia, Group NB, and Group 1TIa.

Examples of reducing metals include potassium, sodium, magnesium, zinc, calicillum, strontium, barium, aluminum, and boron.

Among them, magnesium and aluminum have the best effect, and alloys of two or more reducing metals can also be used.

The preparation of the titanium trichloride composition now proceeds as follows.

0.1 to 11 atoms, preferably 0.2 to 0.5 v atoms of the reducing metal are added to 1 mol of TiCl4 suspended in 0.1 to 30 mol, preferably 2 to 10 mol of diluent,
Reaction temperature: 80-500°C, preferably 100-200°C
After reacting for 15 minutes to 24 hours, preferably 1 to 6 hours, a solid product (titanium trichloride composition) is obtained by e-separation or decantation.

This titanium trichloride composition can also be used after being ground in advance in a ball mill or vibration mill.

The conditions for pulverization are 20°C to 100°C in an inert gas,
As for the grinding time, 1 to 100 hours with a ball mill and 1 to 20 hours with a vibration mill are sufficient.

The electron donor used in the preparation of the catalyst of the present invention is R-0-R
'(R, R' are hydrocarbon groups such as alkyl groups, aryl groups, aralkyl groups, and alkenyl groups having 1 to 20 carbon atoms.

The same applies to the general formula shown below.

It is also possible to use ethers represented by the general formula ( ) and coexist with other electron donors.

Other electron donors that can coexist include alcohol (R
-OH), ester (RCOOR'), aldehyde (R
CHO), fatty acids (RCOOH), ketones (RCOR'
), nitrile (RCN), amine (RnNH3-n
(n=1.2 or 3), plus alcohol amines and cyclic amines), isocyanates (RNC
O), azo compound (R-NN-R'), phosphine (R
nPR'3-n (n=1.2.3)), phosphite (P(OR)3), phosphinite (RP (OR')
2), thioether (RnSR/2-n (n-1,
2)), thioalcohol (R8H), etc.

Here are some specific examples of electron donors.

Examples of the ether include diethyl ether, di-n-7''lopyl ether, diphenyl ether, diphenyl ether, diphenyl ether, diphenyl ether, di-n-hexyl ether, di-hexyl ether, di-n-octyl ether, diphenyl ether, di-n-dodecyl ether, di-n -) ') Decane ether, n-hexyl n-octyl ether, diphenyl ether, phenol, etc. Other electron donors that can be coexisting include methanol, ethanol, propatool, butanol, pentanol, hexanol, Octatur, phenol, cresol, cumyl alcohol, etc. Esters include ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoate. 2-ethylhexyl acid, methyl toluate,
Ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate,
Propyl naphthoate, butyl naphthoate, naphthoic acid 2
-Ethylhexyl, ethyl natate phenylacetate.

Aldehydes include acetaldehyde and benzaldehyde, and fatty acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid,
Examples include benzoic acid.

Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, and benzophenone.

Nitriles include acetonitrile, and amines include methylamine, diethylamine, tributylamine, triethanolamine, pyridine, aniline, dimethylaniline, and the like.

Examples of incyanates include phenyl isocyanate and tolylisocyanate, and examples of azo compounds include azobenzene.

Phosphines include ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, and triphenylphosphine, and phosphites include dimethylphosphine, di-n-octylphosphite, and tri-n-butylphosphine. , triphenylphosphite, etc., and phosphinites include ethyldiethylphosphinite, ethyldibutylphosphinite, phenyldiphenylphosphinite, etc.

Examples of thioethers include diethyl thioether, diphenyl thioether, methylphenyl thioether, ethylene sulfide, and propylene sulfide.
As a thioalcohol, ethylthioalcohol, n-7
``These include lopylthioalcohol and thiophenol.

Next, the method for preparing the final solid product will be described.

To dissolve the titanium trichloride composition in the electron donor, the two are mixed and then heated.

A solvent can also be present during this dissolution.

Usable solvents: aliphatic hydrocarbons such as normal hexane, normal heptane, normal octane, normal nonane, normal decane, isooctane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobenzene, orthodichlorobenzene. halogenated aromatic hydrocarbons, carbon tetrachloride, chloroform, etc.
These include dichloroethane, trichloroethylene, tetrachloroethylene, carbon tetrabromide, and other rogenated hydrocarbons.

(Hereinafter, it may simply be referred to as a solvent.)

The amount ratio used for dissolving the titanium trichloride composition in the electron donor is 0.5 to 10 moles, preferably 1 to 8 moles, of the electron donor per mole of the titanium trichloride composition, and the solvent is O ~5000rfLl.

Although there is no particular restriction on the mixing order of the titanium trichloride composition, electron donor, and solvent, the solvent, electron donor, and titanium trichloride composition are usually added in this order.

The dissolution is carried out by heating at a temperature of 50° to 300°C, and the time is not particularly limited, but it is usually carried out for 30 minutes to 30 hours.

It is speculated that this dissolution is due to complex formation with the electron donor.

Next, a titanium trichloride compound is precipitated from this melt.

Methods for precipitation include (1) cooling the solution, (2) adding a solvent such as n-hexane in (1), or (3) adding titanium tetrachloride, organic (4), (2)
) and (3) are combined.

In the case of (1), it is only necessary to cool it at -10°C to 70°C for 5 minutes to 10 hours.

In the case of (2) or (3), 0 to 5000 ml of solvent and titanium tetrachloride or organoaluminum compound O to 2000f are added to the titanium trichloride composition i ooy after cooling as in (1) or before cooling. and cool for 5 minutes to 10 hours.

The solid thus produced is called solid product (I).

The solid product (I) is then separated from the reaction solution, washed with a solvent such as n-hexane, and then dried to take out the solid product (I) for use in the next reaction, or washed in a solvent. The solution is suspended in water and used for the next reaction.

The solid product (I) is then reacted in suspension with an electron donor and titanium tetrachloride.

To carry out this reaction in suspension, the presence of a solvent is preferred, but it can also be carried out in the absence of a solvent in suspension in the electron donor and titanium tetrachloride.

In this reaction, it is preferable that the electron donor and titanium tetrachloride coexist.As a more specific reaction mode, after mixing the electron donor and titanium tetrachloride in the presence or absence of a solvent, solid A preferred method is to react by adding the product (I) or by mixing the solid product (I), the electron donor, and titanium tetrachloride substantially simultaneously.

In this reaction, the amounts of raw materials used are 10 to 200 P of electron donor,
Titanium tetrachloride 10~100OP, solvent 0~5000rr
The reaction temperature is preferably in the range of 20°C to 1
A temperature of 50° C. and a reaction time of 10 minutes to 10 hours are sufficient.

The solid product thus produced is called solid product (II).

After reaction production, the solid product (n) is obtained by separating the reaction solution and converting it into n-
After repeated washing with a solvent such as hexane to remove trace amounts of the electron donor and titanium tetrachloride, the resulting solid is either dried and taken out, or suspended in a solvent and used for the next reaction.

The solid product (II) thus obtained is then reacted with titanium tetrachloride in the presence or absence of a solvent.

In this reaction, the amount of raw materials used is the solid product (
n) Solvent is O~5000r/L11 for 100S'
The content of titanium tetrachloride is preferably in the range of 10 to 200 M', and a reaction temperature of 20 DEG to 150 DEG C. and a reaction time of 10 minutes to 10 hours are sufficient.

In this way the final solid product is produced.

The final solid product can then be obtained by separating the reaction solution, washing with a solvent such as n-hexane, and drying to obtain the final solid product, or by suspending it in a solvent such as n-hexane. It is used in combination with an organoaluminum compound to obtain a catalyst for α-olefin polymerization.

Examples of organoaluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-hexylaluminum, dialkylaluminum monochloride such as diethylaluminum monochloride, ethylaluminum sesquichloride, monoethylaluminum dichloride, etc. In addition to these, alkoxyalkyl aluminums such as monoethoxy diethyl aluminum and jetoxy monoethyl aluminum can also be used.

It is sufficient that the amount of organoaluminum compound combined with the final solid product is in the range of organoaluminium compounds 5C1 to 3000P for the final solid product 101.

The catalyst obtained as described above is used for producing an α-olefin polymer.

The α-olefins used in the method of the present invention include ethylene, phlopylene, butene-1, hexene-1, octene-1
, decene-1, other straight chain monoolefins, branched chain monoolefins such as 4-methyl-pentene-1, diolefins such as butadiene, styrene, etc., and each of these can be used not only for homopolymerization, but also for homopolymerization. They can also be copolymerized with other α-olefins, such as propylene and ethylene, butene-1 and ethylene, propylene and butene-1, etc.

The polymerization reaction is usually carried out in a hydrocarbon medium such as n-hexane, n-heptane, or n-octane, or in α-olefins such as liquefied propylene or liquefied butene-1 without using a solvent. It is also possible to use α such as ethylene, propylene, butene
-Olefins can also be polymerized in the gas phase.

Moreover, multistage polymerization can also be performed in which the liquefied α-olefin is polymerized and then polymerized in the gas phase.

In the case of polymerization in the gas phase, the polymer powder that is kept in the polymerization vessel at the beginning of the polymerization is a polymer obtained by polymerization in advance using a catalyst used in the gas phase polymerization, or a ready-made polymer.

The polymerization is carried out under conditions of a polymerization temperature of room temperature (about 20'C) to 150C and a polymerization pressure of normal pressure to 50 kg/crtl.

During polymerization, molecular weight can be controlled by adding an appropriate amount of hydrogen to the polymerization system.

The first effect of the present invention is that α-
The yield of olefin polymer is high, reaching 5,000 to 7,000, making it possible to further reduce the amount of catalyst used in polymerization, reducing the amount of alcohol used during killing and purification with alcohol after polymerization. However, there is no coloration of the polymer, and no adverse effects such as impairing the physical properties of the polymer or rusting the mold for molding the polymer are observed.

The second effect of the present invention is that a highly crystalline α-olefin polymer can be obtained, and especially in the polymerization of propylene etc., the formation of amorphous polymers soluble in n-hexane etc. is extremely difficult. It's a small thing.

For this reason, for example, even in polymerization in liquefied propylene, the production rate of amorphous polymer can be suppressed to a level that does not substantially pose a problem, even without removing the amorphous polymer after the polymerization reaction.

For example, in the production of propylene polymer, the isotactic index reaches 99% or more.

In the present invention, isotactic index is n
- It refers to the percentage of the polymer (isotactic polypropylene) as an insoluble material in hexane (20°C) based on the total amount of produced polymer.

Examples are shown below.

Example 1 (1) Preparation of catalyst In a 10100O three-hole flask equipped with a cooling tube and a stirrer,
n-hexyl ether 65f (0.35 mol), commercially available titanium trichloride (AA) (manufactured by Toyo Stoffer Co., Ltd.) 2i (
0.11 mol), heated at 180°C for 1 hour to dissolve, cooled to room temperature (20°C), and dissolved n~hexane 60
After adding 0ml and leaving it to precipitate for 4 hours, the supernatant was removed by decantation, and further n-hexane 600IrLl was added.
After repeating the operation of adding and decanting 5 times, 14 g of the solid product (I) was added with 6 g of n-hexane.
00rnl.

Next, diisoamyl ether 15.5? and 34.59 g of titanium tetrachloride, reacted at 70°C for 90 minutes, cooled to room temperature (20°C), and removed the supernatant by decantation.
600 ml of n-hexane (1 tr): After repeating the addition and decantation operation twice, the obtained solid product (
I[)14.3S' was suspended in 600rrLl of n-hexane, 38P of titanium tetrachloride was added, and the mixture was stirred at 70°C for 9
The final solid product was obtained by reacting for 0 minutes, cooling to room temperature (20°C), removing the supernatant by decantation, adding 7,400 ml of n-hex and decanting twice, and drying. Ta.

(2) After purging a stainless steel reactor with an internal volume of 1.51 for polymerization of propylene with nitrogen gas, 11 n-hexane, 3801n9 of diethylaluminum monochloride (AIEt2C1), and 38cm of the final solid product were added, and the reactor was closed. After adding 150 rrLl of hydrogen, a polymerization reaction was carried out for 4 hours at a propylene partial pressure of 10 kg/crrtG and a polymerization temperature of 70°C.

After the reaction, 50 ml of methanol was added to the reactor to stop the polymerization reaction, and after cooling to room temperature (20°C), the contents were poured into a Puchner-Rotney and rinsed three times with 500 ml of n-hexane to remove the n-hexane insoluble matter. The polymer was separated into a polymer (so-called active polypropylene) and a polymer soluble in n-hexane (so-called active polypropylene), and each was dried to obtain a polymer.

Isotactic polypropylene is 236? , atactic polypropylene is 1.21? Met.

Isotactic polymer yield per liter of final solid product is 62105', isotactic index is 99
．． 5. Atactic index (100 isotactic index) was 0.5.

The bulk density (BD) of isotactic polypropylene is 0
．． 47 is the melt flow rate (abbreviated as MFR, ASTM
D-1385 (L)) was 4.8.

Example 2 155f (1,19 mol) of n-butyl ether and 4of (0,20 mol) of titanium trichloride (AA) were mixed, and 13
After heating at 0°C for 4 hours to dissolve, cool to 20°C,
150 ml of n-hebutane and 3' diethylaluminum chloride? Which solution was added, allowed to stand for 30 minutes, allowed to precipitate, and after removing the supernatant, 300 ml of n-heptane was added and decantation was repeated three times, and 29 g of solid product (I) was dissolved in n-heptane. It was suspended in 300ml.

Next, 8 g of n-butyl ether, 501 g of titanium tetrachloride
was added, reacted at 90°C for 150 minutes, and cooled to 30°C.
~, remove the supernatant by decantation, n-1\butane 3
The operation of adding 0rnl and decantation was repeated 5 times, and 28.5P of the obtained solid product (n) was converted to n-
Suspended in 15Qmz heptane, 1 soy titanium tetrachloride
was added and reacted at 90°C for 180 minutes, then cooled to 30°C, the supernatant liquid was removed by decantation, and n-hebutane 3
The operation of adding 00ml and decantation was repeated 5 times, and the final solid product was obtained by drying.

Polymerization of propylene was carried out in the same manner as in Example 1 using the final solid product.

The results are shown in Table 1. Example 3 150 g (0.62 mol) of di-n-octyl ether and 65 g (0.33 mol) of titanium trichloride (AA) were mixed,
After heating at 150°C for 10 hours to dissolve, cool to 10°C and add 1000ml of n-hexane, 11 titanium tetrachloride, 30'
? Which solution was added, left at 0℃ for 8 hours to precipitate, removed the supernatant liquid, washed door to door with n-hexane in a dry box purged with nitrogen, and dried to form a solid product. (I) 41P was obtained.

Add 30 r of solid product (■), 170 ml of n-hebutane, 5 Z of diisoamyl ether, and 25 P of titanium tetrachloride,
After reacting at 36° C. for 5 hours, the mixture was washed with n-hebutane in a dry box and dried to obtain 28 g of solid product (n).

This solid product (n) 1M' was suspended in titanium tetrachloride 60P and reacted at 40°C for 40 minutes, then separated in a dry box, washed with n pentane, and dried to obtain the final solid product. Obtained.

Using this final solid product, propylene polymerization was carried out in the same manner as in Example 1.

The results are shown in Table 1.

Example 4 n-hexane 5omf diisoamyl ether 72.5
P (0.20 mol), titanium trichloride (AA) 21' (0
, 10 mol) and the boiling temperature of n-hexane (70 mol).
℃) for 20 hours to dissolve titanium tetrachloride at 60℃. was added and stirred at 60°C for 2 hours to precipitate, then separated in a dry box, washed with n-hexane, and dried to give 12L of solid product (I). I got it.

This solid product (I) 11' was suspended in 80 P of titanium tetrachloride, 13 P of diisoamyl ether, and
After reacting for a minute, add 300ml of n-hexane and repeat the decantation operation three times.The obtained solid product (II) 7P was suspended in lOml of n-hexane, and 10g of titanium tetrachloride was added. After reacting at 60° C. for 4 hours, the mixture was separated in a dry box, washed with n-hexane, and dried to obtain a final solid product.

Using this final solid product, propylene polymerization was carried out in the same manner as in Example 1.

The results are shown in Table 1.

Example 5 n-hebutane 150ml, diisoamyl ether 50r
(0.32 mol), n-butanol 52 (0.07 mol), and titanium trichloride (AA) 20 da (0.10 mol) were mixed and heated at 1.00°C for 8 hours to dissolve. A solution of 600ml of n-hebutane and 30P of titanium tetrachloride was added, cooled to 10°C, left to stand for 2 hours to allow precipitation, the supernatant was removed by decantation, and a further 600ml of n-hebutane was added.
After repeating the operation of adding m1 and decantation three times, the produced solid product (I) 131 was suspended in 300 m1 of n-heptane.

Then n-hexyl ether IOP, titanium tetrachloride 1
After repeating the operation of adding 20 ml of n-hebutane, reacting at 80°C for 1 hour, adding 300 ml of n-hebutane and decantation three times, 11P of the obtained solid product (n) was
- Suspended in 7300 ml of hepta, and further titanium tetrachloride 1
After adding 2 oz and reacting at 80° C. for 1 hour, the mixture was kept in a dry box for 1 hour, washed with n-hexane, and dried to obtain a final solid product.

Using this final solid product, propylene polymerization was carried out in the same manner as in Example 1.

Example 6 In 5 GOr of liquefied propylene, 32 kg of the final solid product obtained in Example 3, 26 kg of diethylaluminium monochloride
0 ■, add 150 rIll of hydrogen, and set the polymerization temperature to 70
The polymerization reaction was carried out at a temperature of 30.5 kg/crilG for 3 hours.

After the polymerization reaction was completed, residual propylene was removed to obtain 222 grams of propylene polymer.

1 ton of final solid product? The polymer yield per unit was 6940Z.

Moreover, the isotactic index of this polymer is 9
9.5%, polymer BD is 0.46, MFR is 5
．． It was 0.

Comparative Example 1 In Example 6, instead of using the final solid product obtained in Example 3, the solid product (I) obtained in Example 3 was used,
Polymerization of propylene was carried out in the same manner as in Example 6.

The results are shown in Table 1. Comparative Example 2 In place of the final solid product obtained in Example 3, the solid product (III) of Example 3 was used to polymerize propylene in the same manner as in Example 6.

The results are shown in Table 1.

Example 7 Polymerization of propylene was carried out in the same manner as in Example 6 using the final solid product obtained in Example 4 instead of the final solid product obtained in Example 3.

The results are shown in Table 1.

Comparative Example 3 In place of the final solid product obtained in Example 3, the solid product (I) obtained in Example 4 was used to polymerize propylene in the same manner as in Example 6.

The results are shown in Table 1.

Example 8 Final solid product obtained in Example 1 30■diethylaluminum chloride 320■ and n-to**xane 11
was charged into the same 1.51 polymerization vessel as used in Example 1, H260rrLl was added, and propylene was added at a polymerization temperature of 60°C, while feeding ethylene 1 (L each, 8 times in total at 30 minute intervals). The polymerization reaction was carried out for 4 hours at a partial pressure of 10 kg/c4G.

After the reaction, a propylene ethylene copolymer was obtained by the same operation as in Example 1.

The results are shown in Table 1. Example 9 In place of ethylene in Example 8, butene 1 was used for a total of 2
A propylene-butene-1 copolymer was obtained in the same manner as in Example 8, except that (1 (2.5?×8 times of one supply) was used).

The results are shown in Table 1.

Example 1゜41㎜ of the same final solid product used in Example 3 was combined with 480㎡ of tri-butylaluminum, hydrogen partial pressure 5ky/crrtG, ethylene partial pressure 5kg/ca, G
Then, a polymerization reaction was carried out at 85° C. for 3 hours, and an ethylene polymer was obtained by the same operation as in Example 1.

The results are shown in Table 1. Example 11 Using 39 μ of the final solid product obtained in Example 4 and 290 μ of triethylaluminum, 11 n-hexane was charged into the same polymerization vessel as used in Example 1, and 1520 P of butene was added.
was continuously supplied for 1 hour, and then the polymerization reaction was further carried out for 2 hours.

After the reaction was completed, the solvent was distilled and dried to obtain polybutene.

The results are shown in Table 1. Example 12 Into a stainless steel reactor with a 31 slanted blade stirrer, an 80
5 g of ~120 mesh polypropylene powder, 450 μ of diethylaluminium chloride, and 22 μ of the final solid product obtained in Example 1 were added, and after adding 150 ml of hydrogen, the propylene partial pressure was 26 kg/c77 fG, 70°C.
A gas phase polymerization reaction was carried out for 5 hours.

After the gas phase polymerization reaction was completed, 50rrLl of methanol was introduced into the reactor to stop the polymerization reaction, and then dried to obtain 138i polypropylene.

Polymer yield per z of final solid product is 6272f, isotactic index is 99.6, polymer BD
was 0.47, and MF″R was 4.3.

Example 13 430 ml of diethylaluminium chloride, 28 ml of the final solid product obtained in Example 3, and 150 ml of hydrogen were mixed with 500 ml of liquefied propylene. 27 kg at 65℃
/caG for 2 hours.

After the reaction was completed, post-treatment was carried out in the same manner as in Example 12 to obtain polypropylene 173r.

The polymer yield per 12 final solid products is 6178P,
The isotactic index was 99.8, the BD of the polymer was 0.46, and the MF'R was 4.3.

Example 14 After carrying out a polymerization reaction in liquefied propylene in the same manner as in Example 13, the unreacted liquefied propylene was transferred to another feed tank kept at 62°C, and fed from there to a polymerization vessel. The gas phase polymerization reaction was further carried out at 70° C. for 1 hour under 27 kg/crtt G.

After the reaction was completed, post-treatment was carried out in the same manner as in Example 12 to obtain polypropylene.

Final solid product 1? The polymer yield per unit is 6900P,
The isotactic index was 99.1, the BD of the polymer was 0.47, and the R was 4.2.

Claims (1)

[Claims] 1. As a titanium trichloride composition, TiCl4 is mixed with a reducing metal selected from metals of Group 1a, Group 1[a, Group IIb, and Group 1IIa of the periodic table]. A titanium trichloride composition consisting of a composite chloride of titanium obtained by reducing TiCl4 and a reducing metal is dissolved in an electron donor, and the resulting solid product (I) is precipitated. and a final solid product obtained by reacting titanium tetrachloride and reacting the obtained solid product (n) with titanium tetrachloride;
A method for producing an α-olefin polymer, which comprises polymerizing an α-olefin in the presence of a catalyst obtained in combination with an organoaluminum compound. 2. When dissolving the titanium trichloride composition in the electron donor,
The method for producing an α-olefin polymer according to claim 1, wherein the α-olefin polymer is dissolved in the coexistence of a solvent. 3 Solid product (I) from the solution of titanium trichloride composition
In precipitating, a solvent, titanium tetrachloride,
Alternatively, the method for producing an α-olefin polymer according to claim 1, wherein an organoaluminum compound is added. 4. The production method according to any one of claims 1 to 3, wherein the α-olefin is polymerized in a hydrocarbon solvent in which the α-olefin is dissolved. 5. The production method according to any one of claims 1 to 3, wherein the α-olefin is polymerized in the liquefied α-olefin. 6 Polymerization of α-olefin in gas phase 54'? A manufacturing method according to claims 1 to 3. 7. The production according to claims 1 to 3, in which the α-olefin is polymerized in the liquefied α-olefin, and then the unreacted α-olefin is vaporized in the gas phase. Method.