JPS58450B2 - Method for producing α↓-olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an α-olefin polymer, and more specifically, provides a method for producing a highly crystalline α-olefin polymer with a high polymer yield per catalyst component. It is something to do.

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 I to II of the periodic table and a metal or organometallic compound of Groups I to II of the periodic table.

This transition metal compound is particularly suitable for propylene, butene-
Titanium trichloride is most widely used to obtain highly crystalline polymers of the order of 1.

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 metallic aluminum and then activating it by ball milling (the resultant is a titanium trichloride composition having a composition of TiCl3 + AlCl3, which is usually marked with the symbol AA), (3)
There are methods such as heat treatment after reduction with organic aluminum.

However, the various titanium trichlorides mentioned above are not fully satisfactory in terms of either catalytic activity or stereoregularity, and the use of large amounts of alcohol, etc. in the deashing process, coloring of the polymer, changes in physical properties, etc. There are problems such as rusting of the mold during molding, and a large amount of amorphous polymer is generated as a by-product, which requires removal and post-treatment steps.In addition, the industrial value is low and there is a loss of raw material monomer. Become.

In order to improve these drawbacks, it is known to use polysiloxane or an electron donor in the preparation of Ziegler-Natsuta catalysts, and methods of using such polysiloxanes are as follows.

(1) A method in which polysiloxane is used in a catalyst system consisting of a transition metal compound (eg, titanium tetrachloride, titanium trichloride) and alkyl aluminum.

(2) A method in which a reaction product of polysiloxane and a metal compound of group 3b of the periodic table, such as aluminum trichloride, is used as a component of the catalyst in combination with a transition metal compound, or a transition metal compound and a metal compound of group 3b of the periodic table A method of producing a catalyst by reacting with a polysiloxane and then adding a polysiloxane.

(3) A method of adding polysiloxane to titanium trichloride or a eutectic composition of it and a metal halide (hereinafter collectively referred to as titanium trichloride composition, etc.) and pulverizing it, or Add other compounds at the same time,
How to process the crushing process.

(4) A method in which a titanium trichloride composition or the like is treated with another compound and then treated with polysiloxane.

(5) A method of treating a titanium trichloride composition or the like with a mixture or reactant of another compound and polysiloxane in a solvent.

(6) A method in which a titanium trichloride composition or the like is treated with an electron donor and then treated with a mixture or reactant of polysiloxane and other compounds (JP-A-5O-114394).

(7) Use titanium trichloride composition etc. as an electron donor or electron 4
% and other compounds or a method of grinding with a reaction product or treating in a solvent (Japanese Patent Publication No. 43-10065, No. 43-1)
5620, 49-22315, 50-9751, JP-A-48-21777, 49-83781, 50-
3188).

(8) A method in which a titanium trichloride composition, etc. is pulverized or reacted with an electron donor or a mixture or reactant of an electron donor and another compound, and then washed with a solvent (Japanese Patent Publication No. 49-33597, No. 4
9-48474, JP 48-60182, JP 52-1
10793).

(9) After treating titanium trichloride composition etc. with a complexing agent, T
A method of conducting a reaction with iCl4 and separating the produced solid catalyst component (Japanese Patent Laid-Open No. 48-64170).

Even with these inventions, the catalytic activity and stereoregularity of the polymer were unsatisfactory, and even higher catalytic activity and higher stereoregularity were required.

The present inventors investigated new combinations of polysiloxane, electron donor, and titanium tetrachloride as reactants for titanium trichloride compositions to obtain catalysts with higher catalytic activity and stereoregularity. invention has been achieved.

The present invention involves the homopolymerization or copolymerization of α-olefins using a catalyst obtained by combining a solid product containing a transition metal of Group Va or Group Va of the Periodic Table with an organoaluminum compound. In a method for producing an olefin polymer, polysiloxane, an electron donor, and titanium tetrachloride (hereinafter these three substances may be referred to as reaction raw materials) are added to a titanium trichloride composition in a suspended state as the solid product. This is a method for producing an α-olefin polymer, which is characterized by using a final solid product obtained by reacting a certain type of α-olefin polymer.

A method for preparing the final solid product, which is a component of the catalyst used in the present invention, will be described.

First, the substances used for preparation will be explained.

The titanium trichloride composition refers to TiC1, 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 11a, Group NB, and Group Ha.

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

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

The titanium trichloride composition is prepared as follows.

0.1 to 1 g atoms, preferably 0.2 to 0.5 g atoms of the reducing metal are added to 1 mole of TiCl4 suspended in 0.1 to 30 moles, preferably 2 to 10 moles of diluent,
Reaction temperature: 80-500°C, preferably 100°C-200°C
After a reaction time of 15 minutes to 24 hours, preferably 1 to 6 hours, a solid product (titanium trichloride composition) is obtained by door-to-door or decanting.

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 in an inert gas and a temperature of 20°C to 100°C.
°C and a grinding time of 1 to 100 hours for a ball mill, and 1 to 20 hours for a vibration mill.

The polysiloxane used in the preparation of the catalyst of the present invention has the general formula (-8i(R1, R2)0+.

A chain or cyclic siloxane polymer represented by
R1 and R2 represent the same or different substituents that can be bonded to silicon, and among them, hydrogen, halogen, hydrocarbon residues such as alkyl groups and aryl groups, alkoxy groups, aryloxy groups, fatty acid residues, etc. Those consisting of species and those in which two or more of these species are distributed and bonded within the molecule in various ratios are used.

Polysiloxanes commonly used are those in which R1 and R2 in the above formula are composed of hydrocarbon residues, and specific examples include lower polymerized alkylsiloxanes such as octamethyltrisiloxane and octaethylcyclotetrasiloxane. products, alkylsiloxane polymers such as dimethylpolysiloxane, ethylpolycyclosiloxane, methylethylpolysiloxane, arylsiloxane polymers such as hexaphenylcyclotrisiloxane, diphenylpolysiloxane, diphenyloctamethyltetrasiloxane, methylphenylpolysiloxane, etc. Examples include alkylarylsiloxane polymers.

Other examples include alkyl hydrogen siloxane polymers, haloalkyl siloxanes, and haloaryl siloxane polymers in which R1 is hydrogen or halogen and R2 is a hydrocarbon residue such as an alkyl group or an aryl group.

Further, a polysiloxane in which each of R0 and R2 is an alkoxy or aryloxy group, or a fatty acid residue can be used.

These various polysiloxanes can also be used in combination.

It is desirable that the polysiloxane be in a liquid phase during the reaction.
Although the polysiloxane itself is liquid under the reaction conditions, when reacting in the presence of a solvent or an electron donor, it is desirable to form a homogeneous liquid phase with them.

The viscosity of the polysiloxane is suitably in the range of 10 to 10,000 centistokes at 25°C, preferably in the range of 10 to 2,000 centistokes.

The electron donor used in the preparation of the catalyst of the present invention is an organic compound containing oxygen, nitrogen, sulfur, or phosphorus, such as an alcohol (general formula ROH1 in the text below).
The numbers inside indicate the general formula) Ether (R-0-R'), Ester (RCOOR/), Aldehyde (RCHO), Fatty acid (RCOOH), Ketone (RCOR'), Nitrile (
RCN), amine (RnNH3-n(n-1,2,3
)), phosphine (RnPR'3, ), thioether (R2H), etc.

In the above general formula, R and R' represent a hydrocarbon group such as an alkyl group or an aryl group.

Here are some specific examples of electron donors.

Alcohols include methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, methanol, xylenol,
Ethylphenol, naphthol, etc. Ethers include diethyl ether, diropropyl ether, di-n-butyl ether, di(isoamyl)ether, moro-pentyl ether, moro-hexyl ether, moro-octyl ether, moro-octyl ether, ethylene glycol monomethyl Ether, Cyphenyl ether, Tetrahydrofuran, etc. Esters include ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, ethinope benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, toluic acid. Methyl, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, methyl naphthoate, 2-ethylhexyl naphthoate , ethyl phenylacetate, etc.
Aldehydes include acetaldehyde and benzaldehyde; fatty acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, and benzoic acid; ketones include methyl ethyl ketone, methyl isobutyl ketone, and benzophenone; nitriles include is acetonitrile, amines include methylamine,
Diethylamine, tributylamine, triethanolamine, aniline, etc.; phosphines include triethylphosphine, tri-n-octylphosphine, triphenylphosphine, etc.; thioethers include thiophenol, dimethyl sulfide, diethyl sulfide, etc.

These various electron donors can also be used in combination.

It is preferable that the electron donor is in a liquid phase during the reaction. Under the reaction conditions, the electron donor itself is in a liquid state, or when reacting in the coexistence with a solvent, polysiloxane, titanium tetrachloride, etc., it is homogeneous with the coexisting substances. It is preferable to form a liquid phase.

In preparing a solid product, a solvent can be used for suspension, dissolution, washing, etc. in each step of the reaction.

The solvents used are normal hexane, normal heptane,
Normal octane, normal nonane, normal decane,
Aliphatic hydrocarbons such as isooctane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, halogenated aromatic hydrocarbons such as chlorobenzene, orthodichlorobenzene, and carbon tetrachloride, chloroform, dichloroethyne, trichlorethylene. , tetrachloroethylene, halogenated hydrocarbons such as carbon tetrabromide, etc.

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

A titanium trichloride composition is reacted with polysiloxane (hereinafter sometimes abbreviated as PS), an electron donor (hereinafter sometimes abbreviated as ED), and titanium tetrachloride (hereinafter sometimes abbreviated as T4). In this case, all of these reaction raw materials may be reacted at the same time, each of the reaction raw materials may be reacted one by one in succession, or one of the reaction raw materials or two of various combinations may be reacted in small quantities. Various methods can be used, such as selecting each reaction raw material to participate in the reaction once and reacting in various orders.

Among these, the following reaction method is preferred.

That is, PS is used first in the reaction, T4 is used in the final reaction, and ED is reacted next to PS, reacted in coexistence with T4 or PS, or these reactions are performed together.

It is particularly preferable that T4 is reacted in coexistence with ED.

For example, the following reaction order can be adopted.

(1) First ps, then (T4 and ED).

(ii) First PS, then ED, finally (T4 and ED)
.

(The song starts with PS, then ED, and ends with T4゜.
T4 and ED) means that T4 and ED are reacted in a coexisting state.

On each of the above sides, it is also possible to allow part or all of ED to coexist during the reaction of PS, that is, (PS and ED) can be used instead of 280.

When performing such a reaction on a titanium trichloride composition, if the T4 reaction is performed in the presence of unreacted PS, the effects of the present invention will be reduced.

Therefore, it is particularly desirable to remove unreacted substances and free reaction products after the reaction of Ps or (PS and ED).

In sequentially reacting the reaction raw materials with the titanium trichloride composition, the titanium trichloride composition or the solid product obtained by the preceding reaction is reacted in a suspended state and is not pulverized. .

In each reaction, the titanium trichloride composition can be reacted in a liquid reaction raw material, but a solvent can also be used.

Although it is desirable to remove reactants and free reaction products after each reaction, the final T4 is removed in the presence of unreacted PS.
Since the effect of the present invention is diminished if the reaction is carried out, a removal operation after the reaction of PS or (PS and ED) is particularly desired.

For this purpose, after the reaction is completed, the mixture is separated, or the mixture is further washed with the solvent, or decanted, or a solvent is added and the decantation is repeated.

The obtained solid product after each reaction is dried and collected, or a solvent is added to it and used in a suspended state for the next reaction.

The amount of reaction raw materials used is 1 to 2000 g of polysiloxane, 1 to 2000 g of electron donor in total, and 5 to 1000 g of titanium tetrachloride per 100 g of titanium trichloride composition, and the amount of solvent can be arbitrarily selected. However, it is usually 0 to 5000.
0ml is used.

Reaction conditions vary depending on the reaction raw materials.

The reaction between the titanium trichloride composition and the polysiloxane is carried out at a reaction temperature of -10°C to 500°C, preferably 0 to 200°C, and a reaction time of 10 minutes to 10 hours.

The reaction between the solid product obtained in the preceding reaction and the electron donor is carried out at a reaction temperature of -10°C to 200°C, preferably 0 to 1
00°C and a reaction time of 10 minutes to 10 hours is sufficient.

The reaction between the solid product obtained in the preceding reaction and titanium tetrachloride is carried out at a reaction temperature of -10°C to 200°C, preferably 30°C.
~150°C and a reaction time of 10 minutes to 5 hours are sufficient.

When the electron donor and titanium tetrachloride are reacted together, the solid product obtained in the preceding reaction, the electron donor and titanium tetrachloride, or these and the solvent are heated at -50°C to
The reaction is carried out at 500°C, preferably -50 to 200°C, with mixing.

A reaction time of 10 minutes to 10 hours is sufficient.

In each of the above reactions, various methods can be adopted for adding and mixing the titanium trichloride composition or its solid product, each reaction raw material, and even a solvent.

For example, you can mix all of these at the same time, add and mix one of them in any order, or if there are three or more types of mixture, two of them can be mixed in advance and then mixed with the others. You can also measure how to do it.

As mentioned above, the solid product produced after all the reactions is separated, decanted, and washed with a solvent to remove the reaction solution, unreacted substances dissolved in the reaction solution, free reaction products, etc. Separate and remove.

The final solid product is thus obtained. The final solid product is combined with an organoaluminum compound to form a catalyst for alpha-olefin polymerization.

Examples of organoaluminum compounds include trialkylaluminum such as tolumethylaluminum, 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 ranges from 507 to 3000 g of organoaluminum compound per 100 g of final solid product.

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, propylene, butene-11hexene-1, octene-1
1, decene-1, other linear monoolefins, 4-
These include branched monoolefins such as methyl-pentene-1, diolefins such as butadiene, and styrene, and each of these can be polymerized not only with homopolymerization but also with other α-olefins, such as propylene. Copolymerization of ethylene, butene-1 and ethylene, propylene and butene-1, etc. can also be carried out.

The polymerization reaction is usually carried out in a hydrocarbon solvent such as normal hexane, normal heptane, normal octane, etc., or in α-olefins such as liquefied propylene and liquefied butene-1 without using a solvent. You can also do that.

Polymerization is carried out at a polymerization temperature of room temperature (20°C) to 150°C, normal pressure to
It is carried out under conditions of a polymerization pressure of 50 kg/cm.

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-
High yield of olefin polymer, 3000 to 4500
The amount of catalyst used for polymerization can be further reduced, and even if the amount of alcohol used is reduced during killing and purification with alcohol after polymerization, the coloring of the polymer can be reduced. Furthermore, no adverse effects such as impairing the physical properties of the polymer or causing rust in the mold for molding the polymer were observed.

The second effect of the present invention is that a highly crystalline α-olefin polymer can be obtained. For example, in the production of a propylene polymer, isotactic polypropylene as a n-hexane insoluble material is The index reaches 0.96-0.99.

The third effect of the present invention is that the shape of the polymer has been further improved, and although the bulk specific gravity is 0.36 to 0.42, the shape of the polymer has become closer to a spherical shape.

The fourth effect of the present invention is that the catalyst is easy to prepare, so α-
The objective is to facilitate the industrial production of olefin polymers.

That is, in the process of producing the final solid product, particles of the solid product settle quickly during door-to-door or decanting, which shortens the production time. This has the effect of greatly improving the production of solid products, such as being able to reduce the amount of solvent used.

The above effects can be obtained when the electron donor and titanium tetrachloride are reacted together in the preparation of the final solid product (for example, in the case of (1) and (11) in the above example), and This is particularly true when the final solid product is used for polymerization.

Example 1 (1) Production of final solid product A cooling tube,
Attach the dropping funnel and add 100ml of toluene. 50 g of titanium trichloride (AA) (commercially available under the trade name "5TAUFFERAA", represented by the general formula of TiCl3.+AlCl3, the same in the following examples), methylhydrogen polysiloxane (Toshiba silicone oil TSF-484, 87 (viscosity: 16 centistokes) was added, and the mixture was reacted at 120° C. for 1 hour.

After the reaction was completed, the mixture was washed separately in a dry box purged with nitrogen, washed three times with 50 ml of n-hexane, and then dried to obtain a solid product (1).

100 mg of n-heptane, 30 g of solid product i), 31.0 g of diisoamyl ether, and 30 g of titanium tetrachloride were mixed at 0°C in a 300 mg Trilo flask purged with nitrogen, and the reaction was carried out at 100°C for 1 hour. .

After the reaction was completed, the mixture was washed separately in a dry box purged with nitrogen, washed three times with 5 Q mg of n-hexane, and then dried to obtain a final solid product.

During the production of the final solid product, the time required for settling the particles was 55 seconds, and the settling was fast, and 150 ml of n-hexane was sufficient for washing.

Production of propylene polymer After purging a stainless steel reactor with an internal volume of 1.51 cm with nitrogen gas, 11 n-hexane, 490 rv of diethyl aluminum monochloride (AIEt2C1), and 42 mg of the final solid product were added, and the reactor was closed. After closing and adding 150 ml of hydrogen, a polymerization reaction was carried out for 4 hours at a propylene partial pressure of 1 Okg/cmG and a polymerization temperature of 70°C.

After the reaction was completed, 50 ml of methanol was introduced into the reactor to stop the polymerization reaction, and the contents were poured into a Puchner funnel.
Rinse three times with 500 ml of n-hexane, separate into n-hexane insoluble polymer (so-called isotactic polypropylene) and n-hexane soluble polymer (so-called atactic polypropylene), and dry each. A polymer was obtained.

The amount of isotactic polypropylene was 161 g, and the amount of atactic polypropylene was 3.67 g.

The isotactic polypropylene polymer yield (hereinafter simply referred to as polymer yield) per 17 of the final solid product is 383
3 g, the isotactic index (expressed as ) was 97.8, and the atactic index (100-isotactic index) was 2.2.

The bulk specific gravity (BD) of isotactic polypropylene is 0.39, the shape of the polymer is close to spherical, and the particle size distribution of the polymer is also uniform, with 88% of the total polymer falling between 32 mesh and 150 mesh. Ta.

Comparative Example 1 Using the solid product (1) obtained in Example 1, propylene was polymerized in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 2 Propylene was polymerized in the same manner as in Example 1 using titanium trichloride (AA).

The results are shown in Table 1.

Example 2 Dimethylpolysiloxane (
Toshiba silicone oil TSF-451-1000 viscosity 1
000 centistokes) 20g, titanium trichloride (AA
) and reacted at 174° C. for 10 minutes to obtain a solid product (1) in the same manner as in Example 1.

10 g of solid product (i) were suspended in 200 g of titanium tetrachloride, and 40 g of zyrooctyl ether were suspended in 20 g of titanium tetrachloride.
It was added at 140°C for 30 minutes.

After the reaction was completed, a final solid product was obtained in the same manner as in Example 1, and propylene was polymerized in the same manner as in Example 1.

The results are shown in Table 1. Example 3 Methyl chlorinated phenyl silicone oil (Toshiba silicone oil TSF-440, viscosity 70 centistokes) 12
Add 20g of titanium trichloride (AA) to 0f at 10℃,
After keeping at 10° C. for 5 hours, a solid product (1) was obtained in the same manner as in Example 1.

Suspend 10 g of the solid generator j) in 7300 ml of n-hexane, cool to 0°C, add 37 g of isopropyl alcohol and 20 g of titanium tetrachloride, and raise the temperature to 30°C.
The reaction was carried out for a period of time, and the final solid product was obtained in the same manner as in Example 1 and polymerization of propylene was carried out.

The results are shown in Table 1. Example 4 3Qml of normal heptane, methylphenylpholysiloxane (Toshiba silicone oil TSF-431, viscosity 10)
0 centistokes) 10 (1, titanium trichloride (AA)
After mixing 50 g at 20°C and reacting at 100°C for 30 minutes, decant 3 times of 150 ml each of n-hebutane to make a total volume of 150 ml, and add 2 ml of tri-n-octylphosphine.
g, after adding 150 g of titanium tetrachloride at 20°C, 100
A final solid product was obtained in the same manner as in Example 1, and propylene polymerization was carried out.

The results are shown in Table 1.

Example 5 Titanium trichloride (AA) 100% n-octane 200%
g and 2 g of dimethylpolysiloxane (Toshiba silicone oil TSF-451-100 viscosity 100 centistokes), reacted at 125°C for 2 hours, cooled, and decanted 159 ml of n-octane 5 times to remove the total volume. After reducing the volume to 250ml, add 5g of benzophenone,
After adding 10 g of titanium tetrachloride, the mixture was reacted at 125° C. for 1 hour to obtain a final solid product in the same manner as in Example 1, and propylene was polymerized.

The results are shown in Table 1. Example 6 Using 58 mg of the final solid product obtained in Example 1 and 580 mg of diethylaluminum monochloride, 80 mg of hydrogen was added.
ml, and at a polymerization temperature of 60°C, while feeding 10 g of ethylene 8 times at 30 minute intervals, the propylene partial pressure was increased to 1.
A propylene-ethylene copolymerization reaction was carried out at 0 kg/cmG for 4 hours.

After the reaction was completed, a polymer was obtained in the same manner as in Example 1.

The polymer yield was 3980 g and the isotactic index was 97.0.

Example 7 Propylene-butene-1 copolymerization was carried out in the same manner as in Example 6 except that butene-1 was used instead of ethylene.

The polymer yield was 3920 g and the isotactic index was 97.2.

Example 8 Using 70 mg of the final solid product obtained in Example 2 and 460 mg of triisobutylaluminum, hydrogen partial pressure was 5 kg.
/cmG, an ethylene partial pressure of 5kg/cmG, and an ethylene polymerization reaction at 85° C. for 2 hours.

After the reaction was completed, a polymer was obtained in the same manner as in Example 1.

The polymer yield was 4200 g.

Example 9 The catalyst conditions were the same as in Example 8 except that the final solid product obtained in Example 3 was used, but after continuously feeding 4807 with butene-1 at 70°C for 4 hours, ,
The polymerization reaction was further carried out for 2 hours.

After the reaction is complete, dry up the solvent and remove polybutene 280.
I got g.

The polymer yield was 3550 g.

Example 9 (1) Production of final solid product Using the same equipment as in Example 1, 100 m
1. Methyl hydrogen polysiloxane (same as Example 1)
10g, add 50g of titanium trichloride (AA), and heat to 100°C.
The reaction was carried out for 1 hour.

After the reaction was completed, the reaction was carried out separately in a dry box purged with nitrogen and washed twice with 50 ml each of n-hexane.The obtained solid was suspended in 100 ml of n-hebutane, 52 g of diisoamyl ether was added, and The reaction was allowed to take place at °C for 1 hour.

After the reaction is completed, the process is carried out door to door in a dry box purged with nitrogen.
After washing twice with 50 ml of n-hexane, drying,
A solid product 11) was obtained.

n at 20°C in a 300 ml three-lough flask purged with nitrogen.
-20.4 diisoamyl ether in 100 ml of heptane
After adding 20 g of solid product *t), 34.5 g of titanium tetrachloride was added, the temperature was raised to 100° C., and the reaction was carried out for 1 hour.

After the reaction is completed, separate in a dry box purged with nitrogen,
After washing twice with 50 ml portions of n-hexane, the final solid product was obtained by drying.

During the preparation of the final solid product, the time required for settling the particles was 40 seconds, and the settling was fast, and 100 ml of n-hexane was sufficient for washing.

(2) Production of propylene polymer Propylene polymerization and n-hexane rinsing were carried out in the same manner as in Example 1, except that 560 mg of diethylaluminum monochloride (AIEt2C1) and the final solid product 38~ obtained above were used. 158 g of isotactic polypropylene and 2.57 g of atactic polypropylene were obtained.

The shape of isotactic polypropylene is close to spherical,
The particle size distribution of the polymer is also uniform, ranging from 32 mesh to 15 mesh.
92% of the total polymer was contained between 0 meshes.

Other results are shown in Table 2.

Comparative Example 3 Using the solid product (11) obtained in Example 9, propylene was polymerized in the same manner as in Example 9.

The results are shown in Table 2.

This shows that there is a large difference between the solid product (11) and the final solid product produced by the method of the present invention, both in terms of polymer yield and isotactic index.

Comparative Example 4 Propylene was polymerized in the same manner as in Example 9 using titanium trichloride (AA).

The results are shown in Table 2.

Example 10 Titanium trichloride (AA) 2 in 200 ml n-octane
0 g, dimethylpolysiloxane (Toshiba silicone oil TSF-451-100, viscosity 100 centistokes), 30 g, and diisoamyl ether 21 g, 125
After reacting at °C for 1 hour, the mixture was washed separately in a dry box purged with nitrogen, washed three times with 5ON of n-hexane, and dried to obtain a solid product (11).

After adding 24.5 g of moro-octyl ether and 54 g of titanium tetrachloride to 100 ml of n-hexane at 30°C,
20 g of solid product i+) was added and reacted at 65°C for 3 hours.

After the reaction was completed, the final solid product was obtained in the same manner as in Example 9.

Using this final solid product, propylene polymerization was carried out in the same manner as in Example 9.

The results are shown in Table 2. Comparative Example 5 Using the solid product 11) obtained in Example 10, propylene was polymerized in the same manner as in Example 9.

The results are shown in Table 2.

Example 11 Methylphenylpolysiloxane (
Add 100 ml of Toshiba silicone oil TSF-431 (viscosity 100 centistokes) and add titanium trichloride (AA
), and after reacting at 40° C. for 1 hour, adding 10 g of methyl toluate and reacting at 60° C. for 2 hours, a solid product (11) was obtained in the same manner as in Example 9.

40 g of solid product B) was added to 100 ml of n-pentane, 3 g of isopropyl alcohol was added at 0°C, and 10
After keeping the temperature at 0°C for a minute, 20 g of titanium tetrachloride was added at 0°C, the temperature was raised, and the reaction was carried out at 30°C for 5 hours.
The final solid product was obtained in the same manner.

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

The results are shown in Table 2.

Example 12 Methyl chlorinated phenyl silicone oil (Toshiba silicone oil TSF-440, viscosity 70 centistokes) 60
ml, add 4 g of ethyl acetate, keep at 10°C, add 201ml of titanium trichloride (AA), and incubate for 30 minutes at 10°C.
Example 9
A solid product (11) was obtained in the same manner as above.

10 g of solid product (11) was suspended in 100 ml of toluene, 1 g of ethyl benzoate was added, 100 g of titanium tetrachloride was added, and the mixture was kept at 10°C for 4 hours to react, and then the same procedure as in Example 9 was carried out. The final solid product was obtained.

Using this final solid product, propylene polymerization was carried out in the same manner as in Example 9.

The results are shown in Table 2.

Example 13 In 200 ml of n-decane, 17 methylhydrogen polysiloxane (same as Example 1) and 2 g of benzophenone were added,
Add 100g of titanium trichloride (AA) and heat at 174℃ for 10
The solid product (11
) was obtained.

50 g of the solid product ii) were suspended in 200 ml of titanium tetrachloride and 8 g of n-octyl ether were heated at 30°C.
and reacted at 140°C for 30 minutes.

After the reaction was completed, the final solid product was obtained in the same manner as in Example 9.

Using this final solid product, propylene was polymerized in the same manner as in Example 9. The results are shown in Table 2.

Example 14 Using 55 mg of the final solid product obtained in Example 9 and 620 mg of diethylaluminum monochloride, 80 mg of hydrogen
ml of 101 ethylene at a polymerization temperature of 60°C.
Propylene partial pressure 10 while feeding 8 times at 0 minute intervals.
A propylene-ethylene copolymerization reaction was carried out at kg/cmG for 4 hours.

After the reaction was completed, a polymer was obtained in the same manner as in Example 9.

The polymer yield per 17 final solid products was 4280 g and the isotactic index was 97.9.

Example 15 Propylene-butene-1 copolymerization was carried out in the same manner as in Example 5 except that butene-1 was used instead of ethylene.

The polymer yield per 17 final solid products was 4180 g and the isotactic index was 98.2.

Example 16 Using 60 mg of the final solid product obtained in Example 10 and 450 mg of triisobutylaluminum, hydrogen partial pressure was 5 k.
g/cmG, ethylene partial pressure 5kg/cmG, 2 at 85℃
The ethylene polymerization reaction was carried out for an hour.

After the reaction was completed, a polymer was obtained in the same manner as in Example 9.

Polymer yield was 4800 g. Example 17 The catalyst conditions were the same as in Example 15 except that the final solid product obtained in Example 11 was used, and 420 g of butene-1 was continuously fed at 70° C. for 4 hours. Thereafter, the polymerization reaction was continued for an additional 2 hours.

After the reaction is complete, dry up the solvent and remove polybutene 280.
I got g.

Polymer yield was 3450 g.

Example 18 (1) Production of solid product Titanium trichloride (AA) and methylhydrogen polysiloxane were reacted in the same manner as in Example 1 except that normal octane was used instead of toluene. After the reaction was completed, Separately in a nitrogen-substituted dry box, add 50ml of n-hexane.
After washing 5 times each and drying, a solid product was obtained.

100 ml of n-hexane, 30 g of the above solid product, and 31.0 g of diisoamyl ether were added to a 300 ml three-lough flask purged with nitrogen, and the reaction was carried out at 40'C for 1 hour.

After the reaction was completed, the mixture was washed 5 times with 50 ml of n-hexane in a dry box purged with nitrogen, and then dried to obtain a solid product (it).

100 ml of 1-heptane was placed in a 300-square-meter nitrogen-purged flask. Solid formation vA+ii) 20 g and 20 ml of titanium tetrachloride were added, and the reaction was carried out at 100'C for 1 hour.

After the reaction was completed, it was separated in a dry box purged with nitrogen, washed five times with 50 ml of n-hexane, and dried to obtain a final solid product.

(2) Production of propylene polymer Propylene polymerization and n-hexane rinsing were carried out in the same manner as in Example 1, except that 480 mg of diethylaluminium monochloride (AIEt, CI) and 60 mg of the above-mentioned final solid product were used. 193 g of isotactic polypropylene and 3.7 g of atactic polypropylene were obtained.

The shape of this isotactic polypropylene was good.

Other results are shown in Table 3. Comparative Example 6 A polymerization reaction was carried out under the same conditions as in Example 18 using titanium trichloride (AA).

The results are shown in Table 3.

The polymer yield per final solid product was about one-third that of the present invention, and the amount of atactic polymer was about 4.4 times higher.

Comparative Example 7 In Example 18, a solid product was obtained by reacting titanium trichloride (AA) with diisoamyl ether and titanium tetrachloride without reacting with polysiloxane.

A polymerization reaction was carried out under the same conditions as in Example 18 using this solid product.

The results are shown in Table 3. The amount of atactic polymer was about 2.7 times that of the present invention.

Comparative Example 8 A polymerization reaction was carried out under the same conditions as in Example 18, using the solid product (11*) obtained in Example 18 instead of the final solid product.

The results are shown in Table 3. Comparative Example 9 In Example 18, a polymerization reaction was carried out under the same conditions as in Example 18, using the solid product obtained by reacting titanium trichloride (AA) only with polysiloxane instead of the final solid product. I did it.

The results are shown in Table 3.

Comparative Example 10 40 g of titanium trichloride (AA) was suspended in 240 ml of n-hexane, 40 ml of diisoamyl ether was added, and the mixture was reacted at 40°C for 1 hour.
A solid product was obtained by separating, washing and drying in the same manner as in 8.

Using this solid product, a propylene polymerization reaction was carried out under the same conditions as in Example 18.

The results are shown in Table 3. Comparative Example 11 30 titanium trichloride (AA) in 100 ml of n-hexane
g, add 31.0 g of diisoamyl ether,
After reacting at 0° C. for 1 hour, separation, washing, and drying were performed in the same manner as in Example 18 to obtain a solid product.

20 g of this solid product was suspended in 40 m of normal octane, 3.2 g of methylhydrogen polysiloxane (same as in Example 18) was added, and the reaction was carried out at 120°C for 1 hour. Separately, washed and dried to obtain a solid product.

15 g of this solid product was suspended in 75 ml of n-heptane, 15 ml of titanium tetrachloride was added, and after reaction under the same conditions as in Example 18, a solid product was obtained in the same manner as in Example 18.

Using this solid product, propylene polymerization was carried out in the same manner as in Example 18.

The results are shown in Table 3.

Example 19 20g of titanium trichloride (AA) was mixed with 10% of normal heptane.
After adding 20 g of dimethylpolysiloxane (Silicone Oil TSF-452-100, viscosity 100 centistokes) at 80°C for 4 hours, the mixture was decanted three times in 150 ml portions of n-heptane. After that, the total volume was adjusted to 150 ml, 30 g of ethyl benzoate was added, the reaction was carried out at 20°C for 30 minutes, the mixture was decanted three times with 150 ml of n-hexane, and further 60 ml of titanium tetrachloride was added, and the reaction was carried out at 60°C for 4 hours. I let it happen.

After the reaction was completed, propylene was polymerized in the same manner as in Example 18.

The results are shown in Table 4. Example 20 20 g of titanium trichloride (AA) was suspended in 50 g of methylphenylpolysiloxane (Silicone Oil TSF-431, viscosity 100 centistokes) at 35°C.
After reacting for 20 minutes, add 150ml of normal hexane.
After decanting 5 times, the total volume was reduced to 150ml.
After adding 7 g of benzophenone and reacting at 60°C for 3 hours, the mixture was decanted three times with 150 ml of n-hexane.
Furthermore, 100 ml of titanium tetrachloride was added, and the reaction was carried out at 45°C for 2 hours.

After the reaction was completed, propylene was polymerized under the same conditions as in Example 18.

The results are shown in Table 4.

Example 21 20 g of titanium trichloride (AA) was suspended in 100 ml of xylene, and dimethylpolysiloxane (TSF-
451-1000, viscosity ↓000 centistokes), reacted at 139°C for 10 minutes, decanted 4 times with 150ml of n-hexane, and reduced the total volume to 1
After the volume was made up to 50 ml, 80 ml of moro-butyl ether was added, and the reaction was carried out at 10°C for 6 hours.
Decant each 50ml three times, then add 5ml of titanium tetrachloride.
was added, and the reaction was carried out at 30°C for 30 minutes.

After the reaction was completed, propylene was polymerized in the same manner as in Example 18.

The results are shown in Table 4. Example 22 Using 55 mg of the final solid product obtained in Example 18 and 620 mg of diethylaluminum monochloride, 8
A propylene-ethylene copolymerization reaction was carried out at a polymerization temperature of 60° C. and a propylene partial pressure of 10 kg/cmG for 4 hours while feeding 10 g of ethylene 8 times at 30 minute intervals.

After the reaction was completed, a polymer was obtained in the same manner as in Example 19.

The polymer yield per 17 final solid products was 3400 g and the isotactic index was 0.972.

Example 23 Propylene-butene-1 copolymerization was carried out in the same manner as in Example 22 except that butene-1 was used instead of ethylene.

The polymer yield per 17 final solid products was 3360 g and the isotactic index was 0.980.

Example 24 Using 80 mg of the final solid product obtained in Example 18 and 380 mg of triisobutylaluminum, hydrogen partial pressure was 5 k.
g/cmG, ethylene partial pressure 5kg/cmG, 2 at 85℃
The ethylene polymerization reaction was carried out for an hour.

After the reaction was completed, a polymer was obtained in the same manner as in Example 18.

Polymer yield was 3800. Example 25 420 g of butene-1 was continuously fed under the catalyst conditions of Example 24.
was fed at 70° C. for 4 hours, and then the polymerization reaction was further carried out for 2 hours.

After the reaction was completed, 252 g of polybutene was obtained by drying up the solvent.

Claims (1)

[Claims] 1. Homopolymerization or copolymerization of 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 and an organoaluminum compound. In the method for producing an α-olefin polymer, the solid product is titanium tetrachloride, which is a reducing material selected from metals of Groups Ia, 11a, NB and 11a of the Periodic Table. A titanium trichloride composition, which is a composite chloride of titanium obtained by reducing titanium tetrachloride with a metal of 1. A method for producing an α-olefin polymer, characterized in that the final solid product obtained is used. 2. As the final solid product, in the reaction with the titanium trichloride composition, polysiloxane is used in the first reaction, and titanium tetrachloride is used as the solid product obtained in the final reaction. The manufacturing method according to item 1. 3. The manufacturing method according to claim 2, in which titanium tetrachloride and an electron donor are used in coexistence in the final reaction. 4. The manufacturing method according to claim 3, wherein the polysiloxane is first reacted with the titanium trichloride composition, and then the titanium tetrachloride and the electron donor are reacted in coexistence. 5. According to claim 3, in the reaction with the titanium trichloride composition, first the polysiloxane, then the electron donor, and finally the titanium tetrachloride and the electron donor are reacted in coexistence. manufacturing method. 6. According to claim 3, in the reaction with the titanium trichloride composition, first the polysiloxane and the electron donor are reacted in a coexisting state, and then the titanium tetrachloride and the electron donor are reacted in a coexisting state. Manufacturing method described. 7. A patent in which, when reacting with a titanium trichloride composition, first the polysiloxane and the electron donor are reacted in a coexisting state, the secondary electron donor is reacted, and finally the titanium tetrachloride and the electron donor are reacted in a coexisting state. The manufacturing method according to claim 3. 8. The manufacturing method according to claim 2, wherein in the reaction with the titanium trichloride composition, the polysiloxane is first reacted, then the electron donor is reacted, and finally the titanium tetrachloride is reacted.