JPS598363B2 - Method for producing α-olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing highly crystalline α-olefin polymers using a highly active catalyst.

Various inventions have been proposed in which an electron donor is used as a component of a catalyst for α-olefin polymerization. For example, the carrier may be MgCl2 (anhydrous), a solid having an Mg-Cl bond, magnesium carbonate, or an oxide or hydroxide of an element in group ■ or ■ of the periodic table, and the electron donor may be one. There are some that use ingredients. On the other hand, the present inventors used various methods to support a transition metal compound on the solid product (I) obtained by the reaction of a trivalent metal halide and a divalent metal compound as a catalyst for ethylene or α-olefin polymerization. We have developed catalysts for use in

For example, 1. A method using a solid product obtained by reacting the solid product (I) with polysiloxane or an electron donor and then reacting it with a transition metal compound (Japanese Patent Publication No. 52-13
No. 827 (Japanese Patent Application No. 50994, 1973), Patent Application No. 52-
No. 127750) 2 Add polysiloxane or an electron donor and a transition metal compound to the solid product (I) at the same time, or add a previously prepared complex of polysiloxane and a transition metal compound or an electron donor and a transition metal compound. Method of adding and reacting a complex of metal compounds (Patent application No. 53-2124)
No. 6, No. 53-21247, No. 53-32031, etc.) 3 After reacting the above solid product (I) with a transition metal compound, once reacting with a trivalent metal alcoholade, reacting with a transition metal compound again. Method (Japanese Unexamined Patent Publication No. 52-19790
(Japanese Patent Application No. 50-96427)) etc. have already been filed. As a result of various studies on improving the inventions of these earlier applications, the present inventors have studied various methods for reacting an electron donor and an electron acceptor with the solid product (I),
We have discovered a method that exhibits even more excellent effects, and have arrived at the present invention.

That is, the present invention provides trivalent metal halides, divalent metal hydroxides, oxides, carbonates, double salts containing these, or divalent metal halides.
A solid product (1) obtained by reacting a hydrate of a valent metal compound with one or more electron donors selected from esters, non-aromatic ethers, fatty acids, and ketones. Either one or both of the above electron acceptors are reacted in multiple steps, and at least one of the electron acceptors is titanium tetrachloride, and the solid product () obtained in this way and the organic This is a method for producing an α-olefin polymer, which comprises polymerizing α-olefin in the presence of a catalyst combined with an aluminum compound.

The method for preparing the catalyst used in the polymerization method of the present invention will be explained in detail below.

First, a solid product (1) is obtained by reacting a trivalent metal halide and a divalent metal compound. As the trivalent metal halide, aluminum trichloride (anhydrous), aluminum tribromide (anhydrous), iron trichloride (anhydrous), etc. are used.

Examples of divalent metal compounds include Mg(0H)2, Ca(0H)2, Zn(0H)2, M
hydroxides such as n(0H)2, MgO. CaO, Zn
O,. Oxides like MnO, MgAl2O4, MgS
Complex oxides containing divalent metals such as iO4, Mg6MnO8, MgCO3, MncO3, MgcO3・CacO3
Carbonates such as SnCl2.2H20, MgCl2
・NH2O (n-1~6), NiCl2・6H20
、． Halide hydrates such as MnC12.4H201KMgC13.6H20, MgCl2.NMg (0H
)2.MH2O (n=1-3, m=1-6) hydrates containing halides and hydroxides, 3Mg0.2S
Hydrate of double salt of oxide such as i02.2H20, 3M
Hydrates of carbonate and hydroxide double salts such as gC03.Mg(0H)2.3H20, and Mg6Al2(0H)
Examples include hydrates of hydroxide carbonates containing divalent metals such as 16C03 and 4H20.

Solid product (1) is produced as follows. Trivalent metal halide and divalent metal compound are mixed in a ball mill for 5 to 5 minutes.
It is preferable to grind for 0 hours, or for 1 to 10 hours in a vibrating mill, to obtain a well-mixed state.

The mixing ratio of the divalent metal compound to 1 mole of the trivalent metal halide is usually 0.1 to 20 moles, and preferably 1 to 10 moles. The reaction temperature is usually room temperature (20°C) to 500°C, preferably 500°C.
~300°C. The reaction temperature is suitable for 30 minutes to 50 hours, and if the reaction temperature is low, the reaction is allowed to take place for a long time, and the unreacted 3
Allow the reaction to proceed sufficiently so that no valence metal remains. The solid product thus obtained is referred to as solid product (1). The solid product (1) is then reacted with an electron donor (hereinafter sometimes abbreviated as ED) and an electron acceptor (hereinafter sometimes abbreviated as EA). ED used in this reaction
means organic compounds containing any of the atoms of oxygen, nitrogen, sulfur, and phosphorus, i.e., alcohols, non-aromatic ethers, esters, aldehydes, fatty acids, ketones, nitriles, amines, isocyanates, These include azo compounds, phosphines, phosphites, bosphinates, thioethers, thioalcohols, and polysiloxanes.

Specific examples include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, cresol, xylenol, ethylphenol, naphthol, and cumyl alcohol, diethyl ether, di-n-propyl ether,
Di-n-butyl ether, di-amyl ether, di-n-
Non-aromatic ethers such as pentyl ether, di-n-hexyl ether, di-n-octyl ether, di-i-octyl ether, ethylene glycol monomethyl ether, tetrahydrofuran, ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate , esters such as propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, and ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, Fatty acids such as acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone, benzophenone, nitriles such as acetonitrile, methylamine, diethylamine, Amines such as butylamine, triethanolamine, pyridine, aniline, isocyanates such as phenyl isocyanate and tolyl isocyanate, azo compounds such as azobenzene, ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octyl Phosphines such as phosphine and triphenylphosphine, phosphites such as dimethylphosphite, di-n-octylphosphite, tri-n-butylphosphite, triphenylphosphite, ethyldiethylbosphinate, ethyldibutylbosphinate , bosphinates such as phenyldiphenylbosphinate, thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide, propylene sulfide, thioalcohols such as ethylthioalcohol, n-propylalcohol, thiophenol, etc. I can give you. As the polysiloxane, linear or cyclic siloxane polymers represented by the general formula (R1 and R2 are the same or different substituents, n is an integer) are used, and among them, Rl. R2 is hydrogen, a hydrocarbon residue such as an alkyl group or an aryl group,
Generally used are those consisting of one type of alkoxy group, aryloxy group, fatty acid residue, etc., or those in which two or more types are distributed and bonded within the molecule in various ratios. Specific examples of those usually preferably used include lower polymers such as octamethyltrisiloxane and octaethylcyclotetrasiloxane, alkylsiloxane polymers such as dimethylpolysiloxane, ethylpolycyclosiloxane, and methylethylpolysiloxane, and hexaphenyl Examples include arylsiloxane polymers such as cyclotrisiloxane and diphenylpolysiloxane, and alkylarylsiloxane polymers such as diphenyloctamethyltetrasiloxane and methylphenylpolysiloxane.

These various polysiloxanes can also be used in combination. Furthermore, these polysiloxanes need to be in a liquid phase during the reaction, and the polysiloxane itself needs to be in a liquid state under the reaction conditions or dissolved in a solvent. The viscosity of such polysiloxane is 10 to 1 at 25°C.
0000 centistokes, more preferably 10-200
It is in the range of 0 centistokes. The various EDs mentioned above can be used not only alone but also in combination. Next, the EA used in the present invention is based on the periodic table ~V
It is represented by the halides of group elements. Specific examples include AlCl3 (anhydrous), SiCl4. SnCl2, SnC
l4. TiClIZrcl4, PCl3, PCl,,V
Cl4, SbCl5, SCl2, MnCl2, FeCl
2, NiCl2, etc. These may also be used in combination. However, TiCl4 must be used only once. There are various methods for reacting the solid product (1) with ED and EA as described below, but any reaction step may be carried out in a suspended state in the presence or absence of a solvent. Alternatively, the reaction may be carried out while being pulverized using a pulverizer such as a vibration mill or a ball mill. When reacting solid product (1) with ED and EA, one or both of them is reacted in multiple batches, and the E
D and EA may each be of multiple types, but it is an important feature of the present invention that at least one of EA is titanium tetrachloride, but the specific and representative order of the reaction is Examples of such methods include the following.

1 After reacting ED and EA with solid product (1), EA2 (
Method 2: After reacting solid product (1) with EAL, ED and EA2 (TiCl4) are reacted once or twice.
4) Method 3 After reacting solid product (1) with EDl and EA1, this time ED2 and EA2 (TiCl4
Method 4 of reacting solid product (1) with EDl and E
Method 5: After reacting ED2 with A (TiCl4), after reacting ED1 with solid product (1), ED2 and EA(Ti
Method 6 of reacting solid product (1) with EDl
After reacting, react with ED2 and further add 1 EA (TiCl4).
Method 7 of reacting once or twice EDl to the solid product (1)
After reacting, ED2 is reacted and further ED3 and EA (TiCl
Method 8: React solid product (1) with ED, then react with EA (TiCl4) twice. Method 9: React solid product (1) with ED, then react with EAL, and then react with EA2 (TiCl4). How to do it.

As mentioned above, dividing one or both of ED and EA multiple times usually means dividing each of them into about 2 to 3 times, and even if you divide them into smaller parts, the operation will be complicated and it will not be very effective. It doesn't get bigger. In addition, in the above reaction mode, for example, reacting solid product (1) with ED and EA means reacting the solid product (1) with ED and EA in the coexistence, or reacting the solid product (1) with ED and EA. and the reaction of ED and EA with a complex compound. Further, a solvent may be added as necessary at any time of these reactions, and the solvents used are n-pentane, n-hexane, n-heptane, n-octane, i-octane, n-nonane, n- -Aliphatic hydrocarbons such as decane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, carbon tetrachloride, chloroform, dichloroethane, trichlorethylene, tetrachlorethylene, carbon tetrabromide, chlorobenzene, orthodichlor These are so-called inert solvents such as halogenated hydrocarbons such as benzene. ED. EA, the amount of solvent used is E per 100 f of solid product (1) in each reaction step.
Dl~5000r1 EA1~5000y1 Solvent 0~50
A range of 00m1 is desirable.

The reaction conditions were a reaction temperature of 0 to 500°C at each reaction stage;
The temperature is preferably 20 to 200°C, and the appropriate range of reaction time varies depending on the reaction method, and the reaction time in a suspended state is 1 minute to 1 minute.
0 hours, for reactions using a crusher, 5 to 5 hours using a ball mill.
200 hours, or about 10 minutes to 50 hours using a vibration mill.

After the reaction is complete, the reaction solution containing unreacted ED or EA is removed by distillation under reduced pressure or normal pressure, or the liquid portion is separated by separation or decantation, and if necessary, washed and dried to obtain a solid product ( ).

In this case, it may be used in the next reaction as a suspension without separating it as a solid, with the addition of a solvent.

Moreover, it is most desirable to remove unreacted substances and the like at each reaction stage.

The solid product thus obtained () is then combined with an organoaluminum compound and serves as a catalyst for alpha-olefin polymerization.

The organoaluminum compound used in this reaction has the general formula AlRnR'n'X3-(n+n') (where R, R
' represents a hydrocarbon group such as an alkyl group, an aryl group, an alkaryl group, a cycloalkyl group, or an alkoxy group;
represents the halogens of fluorine, chlorine, bromine and iodine,
Also N,. n' represents any number of 3 where o<n+n')
Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i
- Trialkylaluminums such as butylaluminum, tri-n-hexylaluminum, tri-i-hexylaluminum, tri-2-methylbentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminum monochloride, di-n- Propyl aluminum monochloride, di-butyl aluminum monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, diethylaluminum monohalides such as diethylaluminium monoiodide, alkyl aluminum hydrides such as diethyl aluminum hydride, methyl aluminum sesquid chloride, ethylaluminum sesquichloride, ethylaluminum dichloride,
Examples include alkyl aluminum halides such as i-butylaluminum dichloride, and alkoxyalkylaluminiums such as monoethoxy diethyl aluminum and diethoxy monoethyl aluminum can also be used.

The quantitative ratio of these organoaluminum compounds to the solid product () is in the range of 50 to 50,007% of the organoaluminum compound per 100V of the solid product (), in an inert gas,
By simply mixing the two, it immediately becomes active as an α-olefin polymerization catalyst, and can be used in the same manner as conventional Ziegler- and Natsuta-type catalysts.

The polymerization reaction is carried out in a hydrocarbon solvent such as n-hexane, n-heptane, n-octane, benzene, toluene, etc., or in liquefied propylene, liquefied butene, etc. without using a solvent.
It can also be carried out in a liquefied α-olefin monomer such as 1.

The polymerization temperature is room temperature (200) to 200°C, the polymerization pressure is normal pressure (0 kg/CdG) to 50 kg/CdG, and usually 5 minutes to 1
It will be carried out for about 0 hours. During polymerization, adding an appropriate amount of hydrogen to control the molecular weight is the same as in conventional polymerization methods. The α-olefins used in the process of the present invention are ethylene, propylene, butene-1, hexene-1,
Linear monoolefins such as octene-1 and decene-1, branched chain monoolefins such as 4-methyl-pentene-1, 2-methyl-pentene-1, and 3-methyl-butene-1, and diolefins such as putadiene, isoprene, and chloroprene. and styrene, etc., and the method of the present invention not only polymerizes each of these individually, but also mutually combines them with other α-olefins, such as propylene and ethylene, butene-1 and ethylene, propylene and butene-1, etc. Copolymerization can also be carried out in combination.

The first effect obtained by the polymerization method of the present invention is α-
Very highly crystalline α in the production of olefin polymers
- An olefin polymer can be obtained.

For example, in the production of a propylene polymer, the content of crystalline isotactic polypropylene as n-heptane insoluble matter was 75 to 96% in the method according to the invention of the present inventors, but in the present invention, the content was 75 to 96%. This improves from 92% to about 97%. The second effect of the present invention is that the shape of the polymer, especially propylene, is improved.

In the method according to the invention of the present inventors, the shape of the ethylene polymer particles was good and the bulk specific gravity (BD) reached up to 0.45, but the shape of the propylene polymer particles was poor and the BD (' The particle size was only 0.08 to 0.18, and the particles were also irregular.In the present invention, the BD reached 0.35, and the particle shape was improved to almost spherical. The effect is that the yield of α-olefin polymer per solid product is sufficiently high, especially in the polymerization of propylene.
Under normal polymerization conditions, a solid product () of 5 x 103 to 2 x 1047 (polymer)/7 (solid product) is reached, and even if the removal of the residual catalyst in the polymer, that is, the deashing step, is omitted, the color of the polymer does not change. Furthermore, there are no adverse effects such as impairing the physical properties of the polymer or rusting the mold when molding the polymer.The fourth effect of the present invention is that transition metals can be used extremely effectively. In normal propylene polymerization, the ratio is 1 x 104 to 5 x 1067 (polymer)/y (transition metal atoms).

Hereinafter, the present invention will be explained in more detail by showing examples.

Example 1 (1) Production of solid products (1) and () When aluminum trichloride (anhydrous) 807 and magnesium hydroxide 58y were reacted in a vibrating mill at 180°C while being pulverized for 10 hours, hydrogen chloride gas was produced. The reaction occurred with the occurrence of

After the heating was completed, the mixture was cooled in a nitrogen stream to obtain a solid product (1). In a vibratory mill, solid product (1) 100y, EA
After adding titanium tetrachloride 207, which was reacted at 120° C. for 5 hours while being pulverized, unreacted titanium tetrachloride was removed under reduced pressure, and the mixture was cooled.

Furthermore, 12.07 of a complex of titanium tetrachloride and ED, ethyl benzoate (1:1 (molar ratio, same hereinafter)) was added,
The reaction was carried out in a vibrating mill while being pulverized at 40° C. for 120 hours to obtain a solid product ().

The content of titanium atoms in the solid product ()1y is 19.5
It was η.

(2) Production volume of propylene polymer 1.51? After replacing the stainless steel reactor with nitrogen gas, 11 n-hexane, 480 η of triisobutylaluminum, and 12 of the solid product obtained in (1) above were added.
Hydrogen 75m2, propylene partial pressure 12kg/C
Propylene polymerization reaction was carried out at 60° C. for 5 hours using dG.

After the polymerization reaction was completed, the solvent was removed by evaporation to obtain a polymer. Using 50 ml of n-heptane, the obtained polymer 5y was heated to the boiling point of n-heptane (9
Extraction was performed at 8° C.), and the n-heptane soluble portion was used as atactic polypropylene, and the remainder was used as isotactic polypropylene. The isotactic index was determined as follows. Isotactic index - amount of isotactic polymer x 100 In addition, the BD of the obtained total polymer was 0.35, and the shape was significantly improved.

The results are summarized in Table 1 together with the results of other Examples. Example 2 Ball mill (SU
80 stainless steel balls with a diameter of 10 mm were placed in a container (made of S3O4), and the solid product (1) 207 obtained in Example 1, EA,
as silicon tetrachloride 3f, . 4.0 r of ethyl cinnamate was added as ED, and the mixture was reacted while being pulverized at 40°C for 75 hours.

After the reaction was completed, unreacted materials were removed under reduced pressure, and then 80y of titanium tetrachloride was added as EA2, and the reaction was further carried out while being pulverized at 80° C. for 40 hours. After the reaction was completed, in a dry box purged with nitrogen, ▲ was separated and 150 m
After washing three times with 1 and drying, the solid product (
) was obtained. Polymerization of propylene was carried out in the same manner as in Example 1 using the solid product (2).

The results are shown in Table 1. Example 3 A complex obtained by mixing and reacting 3V of aluminum trichloride as EAL and 1.77% of dimethylpolysiloxane as EDl was placed in a ball mill, and 20f of the same solid product (1) as in Example 1 was added. After a pulverization reaction at 30°C for 48 hours, 87 g of a complex (1:2) of titanium tetrachloride as EA2 and tetrahydrofuran as ED2 was added, and further 50 g.
A solid product () was obtained by a pulverization reaction at ℃ for 60 hours.

Using this solid product (), in the same manner as in Example 1,
Propylene polymerization was carried out. The results are shown in Table 1. Example 4 80y of aluminum trichloride (anhydrous) and 307% of magnesium oxide were reacted in a ball mill while being ground at 120°C for 48 hours to obtain a solid product (1).

Solid product (1) 201 and EA titanium tetrachloride and E
5f of the complex (1:1) of D with ethyl phenyl acetate
were reacted while being pulverized in a vibration mill at room temperature (20°C) for 30 minutes, and then suspended in a mixed solution of 50ml of n-heptane and 180y of titanium tetrachloride and reacted at 100°C for 4 hours. Ta.

After the reaction was completed, the mixture was separated in a dry box, washed three times with 150 ml of n-hexane, and dried to obtain a solid product (). Polymerization of propylene was carried out in the same manner as in Example 1 using the solid product (2).

The results are shown in Table 1. Example 5 Aluminum trichloride (anhydrous) 60y and hydrotalcite (Mg6Al2(0H)16C03・4H20) 207
A solid product (1) was obtained by heating 40f at 100°C for 2 hours and pulverizing and reacting at 250°C for 1 hour using a vibration mill.

In 200 ml of n-hexane, 20 m' of methylhydrogen polysiloxane as EDl, 507 ml of the above solid product (1)
After reacting at 40° C. for 1 hour, the mixture was separated, washed with n-hexane, and dried.

To this dry solid 20y, methyl toluate 3f as ED2, . 6f of titanium tetrachloride as EA was placed in a ball mill, and after a pulverization reaction at 80°C for 20 hours, the mixture was kept under reduced pressure at 80°C for 2 hours to remove unreacted materials to obtain a solid product ().
Polymerization of propylene was carried out in the same manner as in Example 1 using the solid product (2).

The results are shown in Table 1. Example 6 Iron trichloride (anhydrous) 607 and magnesium aluminum oxide (MgAl2O4) 701 were reacted at 320° C. for 5 hours in a vibration mill to obtain a solid product (1).

20y of solid product (1) was suspended in 180ml of toluene, 107ml of ethanol was added as EDl, and 3
After reacting for 1 hour at 0°C, add 150 ml of toluene and decant twice to make a total volume of 180 m', then add benzophenone 87 as ED2 and add 60 ml of toluene.
After reacting at ℃ for 30 minutes, it was decanted, 150 me of toluene was added and decanted to bring the total volume to 60 m', and then E
A is titanium tetrachloride 100m', ED3 is di-n-
After adding 20 m2 of butyl ether and reacting at 130°C for 1 hour, the mixture was separated, washed with n-hexane, and dried to obtain a solid product (2).

Polymerization of propylene was carried out in the same manner as in Example 1 using the solid product (2).

The results are shown in Table 1. Example 7 80 y of aluminum trichloride (anhydrous) and 65 y of magnesium chloride (hexahydrate) (MgCl2.6H20) were reacted in a vibration mill while being ground at 80'C for 20 hours to produce a solid product (1). I got it.

Solid product (1) 20y was added with n-butyl ether (EDl).
) 37 was added and reacted in a vibration mill at 40°C for 30 minutes, then benzoic acid (ED2) 27 was added and further reacted at 60°C for 30 minutes.
The reaction was carried out in a vibrating mill for 1 minute. This is titanium tetrachloride 12
07, suspended in a mixture of 30 ml of n-hexane, 7
The reaction was carried out at 5°C for 3 hours. After the reaction was completed, unreacted substances were distilled off under reduced pressure to obtain a solid product (). Polymerization of propylene was carried out in the same manner as in Example 1 using the solid product (2).

The results are shown in Table 1. Comparative Example 1 An experiment similar to Example 1 was carried out except that the solid product (1) and titanium tetrachloride reacted in two portions in Example 1 were simultaneously reacted.

That is, 1007 of the solid product (1) obtained in Example 1, 20 f of titanium tetrachloride, and 127 of the complex of titanium tetrachloride and ethyl benzoate (1:1) were mixed together and mixed in a vibrating mill at 120 g.
After pulverizing reaction at 40° C. for 5 hours, the reaction was further carried out while pulverizing at 40° C. for 120 hours, and unreacted titanium tetrachloride was removed under reduced pressure to obtain a solid raw product ().

Using this solid product (2), propylene was polymerized in exactly the same manner as in Example 1. The results are shown in Table 1, including polymer yield, isotactic index, and B.
In all D, it is far inferior to Example 1. Comparative Example 2 An experiment similar to Example 6 was carried out except that the solid product (1) was reacted with three types of ED in three separate batches, but the three types of ED were added and reacted simultaneously.

That is, 200 y of the same solid product (1) obtained in Example 6
Suspended in 180ml of toluene and 1ml of ethanol
07, benzophenone 87, titanium tetrachloride 100m2,
20ml of di-n-butyl ether was added at the same time and reacted at 30°C for 1 hour, 60°C for 30 minutes, and 130°C for 1 hour, separated, washed with n-hexane, and dried to obtain a solid product ( ) was obtained.

Polymerization of propylene was carried out in the same manner as in Example 6 except that this solid product (2) was used.

The results are shown in Table 1, and as is clear from the table, it is clear that this case is also far inferior to Example 6 in all respects. Example 8 Using the solid product () obtained in Example 1, propylene-ethylene copolymerization was carried out.

The same solid product obtained in Example 1 () 1 in the polymerization vessel
Using 420 mg of triethylaluminum, 80 me of hydrogen was added, and a polymerization reaction was carried out at a polymerization temperature of 60°C for 4 hours at a propylene partial pressure of 10 kg/CF7fG while feeding 10 y of ethylene 8 times at 30 minute intervals.
After the reaction, a propylene-ethylene copolymer was obtained through the same operation as in Example 1. The polymer yield per 17 of the solid product was 208,007 (polymer)'(', and the isotach index was 92.0. Example 9 Propylene-butene- 1 was copolymerized.

Instead of using ethylene in Example 8, butene-
Propylene-butene-1 copolymerization was carried out in the same manner as in Example 8 except that 1207 was used.

The polymer yield per 17 of the solid product () is 203,007 (
polymer), and the isotactic index is 91
．． It was 0.

Example 10 The solid product obtained in Example 2 () was used to polymerize ethylene.

Using the solid product () 8η obtained in Example 2 and triisobutylaluminum 480W9, hydrogen partial pressure was 5 kg/C.
The polymerization reaction was carried out at 85° C. for 5 hours using dG and ethylene partial pressure of 5 kg/CriiG.

After the reaction was completed, a polymer was obtained in the same manner as in Example 1.
The polymer yield was 18800 f(polymer)/t(solid product). BD is 0.40 and MI is 6.5. In addition, this polymer was dissolved in trichlorobenzene at a concentration of 0.1 to 0.5% at 140°C and at a flow rate of 1 m1/MJ.
As a result of measuring the molecular weight distribution by passing it through GPC2OO type (manufactured by Waters) under conditions of n, Mw/Mn was 6.8. Example 11 Using the solid product () obtained in Example 3, butene-
Polymerization of 1 was carried out.

Using 20y of the solid product () obtained in Example 3 and 380 ~ triethylaluminum, a polymerization reaction was carried out for an additional 2 hours after continuously feeding 4807 g of butene-1 over 4 hours at 70°C. .

After the reaction is completed, dry up the solvent and add polybutene 2.7
Got 3y. Polymer yield is 136507 (polymer)/f
(Solid product ()). Example 12 After pulverizing aluminum trichloride (anhydrous) 133f and magnesium oxide 407 in a ball mill for 24 hours, the mixture was heated to 120°C.
After heating for 2 hours, the mixture was cooled and ground for another 10 hours to obtain a solid product (1).

Ethyl benzoate (ED) 127 and silicon tetrachloride (EAL
) 4.5y in advance at room temperature (20°C) and the solid product (1) 40y were mixed in a ball mill at 35°C.
The resulting powder 207 was suspended in 180 t of titanium tetrachloride (EA2), and after reacting for 2 hours at 80°C, the supernatant was removed by decant, and 180 t of titanium tetrachloride was added. After reacting at 80° C. for 1 hour, the supernatant was removed by decantation. After repeating the operation of adding 150 ml of n-hexane and removing by decanting twice, the mixture was filtered and dried in a dry box to obtain a solid product (2). Using this solid product (2), propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1. Example 13 Solid product (1) 20y obtained by the same operation as Example 12 was subjected to a pulverization reaction with 2y of cumyl alcohol (ED,) and 57 of ethyl benzoate (ED2) in a ball mill at 40°C for 48 hours. After that, silicon tetrachloride (EAL) 97 was added,
Powder 2 obtained by further pulverizing reaction in a ball mill for 24 hours
0y is suspended in 240y of titanium tetrachloride (EA2), and after reaction at 100°C for 2 hours, the supernatant liquid is removed by decantation.

After repeating the operation of adding 150 ml of n-hexane and removing the supernatant liquid twice, the mixture was filtered in a dry box and dried to obtain a solid product (2). Polymerization of propylene was carried out in the same manner as in Example 1 using the solid product (2).
The results are shown in Table 1. Example 14 To the solid product (1) 407 obtained in the same manner as in Example 12, methyl benzoate (ED,) 127 was added in a ball mill at 30°C.
After 24 hours of pulverization reaction, silicon tetrachloride (EAL)
Powder 207 obtained by adding 15y and reacting for further 48 hours
was suspended in 350y of titanium tetrachloride (EA2),
React at 80'C for 2 hours, remove the supernatant by decant,
Add 200 ml of tetrachlorethylene and decant.

Furthermore, after repeating the operation of adding 200 ml of n-hexane and decanting twice, the n-hexane was distilled off under reduced pressure to obtain a solid product (). Polymerization of propylene was carried out in the same manner as in Example 1 using the solid product (2).

The results are shown in Table 1. Example 15 Powder 20y obtained by pulverizing solid product (1) 407 obtained in the same manner as in Example 12 with 1-propyl benzoate (EDl) 167 in a ball mill at 45°C for 48 hours was converted into tetrachloride. Suspended in titanium (EA) 1907 and heated to 70°C.
After reacting for 4 hours at
After reacting for 1 hour at 0'C, the reaction solution was removed by decant.

After repeating the operation of adding 250 ml of n-hexane and decanting twice, the n-hexane was distilled off under reduced pressure to obtain a solid product (). Polymerization of propylene was carried out in the same manner as in Example 1 using the solid product (2).

The results are shown in Table 1. Example 16 12η of the solid product obtained in Example 12 and 480 g of triisobutylaluminum were suspended in 500 y of liquefied propylene without a solvent, 90 ml of hydrogen was added, and the polymerization temperature was 65° C. and the pressure was 26. The polymerization reaction was carried out at 5 kg/CdG for 3 hours.

Claims (1)

[Claims] 1 Trivalent metal halides and divalent metal hydroxides,
Solid products obtained by reacting oxides, carbonates, double salts containing these, or hydrates of divalent metal compounds (
I) include esters, non-aromatic ethers, fatty acids,
In obtaining the solid product (II) by reacting one or more electron donors selected from ketones with one or more electron acceptors, at least the electron donor or the electron acceptor is One or both of them are reacted in multiple steps, and at least one of the electron acceptors is titanium tetrachloride, and the solid product (II) thus obtained is combined with an organoaluminum compound. 1. A method for producing an α-olefin polymer, which comprises polymerizing an α-olefin in the presence of α-olefin.