JPS591404B2 - Method for polymerizing ethylene or α-olefins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the polymerization of ethylene or alpha-olefins which yields polymers with improved particle size distribution and high stereoregularity.

The most common Ziegler type catalyst used for the polymerization of ethylene or α-olefins consists of a catalyst component containing a titanium compound and an organoaluminum compound.

By crushing titanium trichloride or Ξ titanium chloride composition (Japanese Patent Publication No. 35-14125, Japanese Patent Publication No. 39-2427)
1 etc.), or by adding various compounds to these titanium compounds and co-pulverizing them (Japanese Patent Publication No. 39-24270,
39-24272, 43-10065, 43-1
5620, 49-22315, JP-A-48-6849
7, 48-29694, 48-38295, 49
-53196, etc.) By further modifying these pulverized products with an organic solvent or a compound of this and a modifier (
Special public service No. 49-1947, No. 49-48638 No. 50-1
7319, 49-48637, JP-A-48-6417
0, etc.), it is well known that catalyst performance is improved. However, when such pulverization and reforming treatments are carried out, the particle size distribution of the resulting titanium catalyst component generally becomes significantly wider, with fine particles of 5 mt or less accounting for 10% by weight or more.

In the polymerization or copolymerization of ethylene or α-olefins using a polymerization catalyst consisting of a titanium catalyst component and an organoaluminum compound, the particle size of the resulting polymer or copolymer is strongly influenced by the particle size of the titanium catalyst component used. box office.

That is, the polymer or copolymer obtained by using a titanium catalyst component containing a large amount of fine particles and having a wide particle size distribution similarly has a wide particle size distribution.
Contains 0% by weight. When the particle size distribution of the produced polymer is wide, especially when the amount of fine powder increases, it becomes difficult to separate the produced polymer from the solvent by filtration, centrifugation, etc., and losses due to dissipation increase in the drying process and pelletizing process.

Therefore, in order to prevent these problems, it is necessary to provide extra equipment and perform complicated manufacturing operations, and therefore, improvements are desired. As mentioned above, many methods have been proposed to improve the performance of catalysts.

Among these methods, methods of modifying titanium trichloride raw materials with various modifiers are described, for example, in Japanese Patent Publications No. 49-1947 and No. 49-49.
-48638, JP-A-48-64170, etc. As shown in the comparative examples below, these methods are effective to some extent in terms of improving activity, but the titanium trichloride component becomes finer during the modification process, resulting in the disadvantageous results described above. This is a major drawback for industrial use. The object of the present invention is to produce polymers with extremely low fines content and narrow particle size distribution.
An object of the present invention is to provide a method for polymerizing olefins.

Another object of the present invention is to obtain polymers of engineered tylenes or α-olefins having high stereoregularity.

For the above purpose, titanium trichloride or a titanium trichloride composition with the general formula A/RnlX3-m (
where R is an alkyl group or aryl group, X is hydrogen or halogen, and m is 1 to 3), and then co-pulverized with an inert organic solvent or the organic solvent 1) an oxygen-containing, sulfur-phosphorus, nitrogen or silicon organic compound; 2) a combination of the organic compound of 1) above and aluminum halide; 3) an organoaluminum compound; and 4) a mixture with a modifier selected from the group consisting of Lewis acids. Using a Ziegler type polymerization catalyst consisting of a modified titanium catalyst component and an organoaluminum compound obtained by contacting and separating the co-pulverized product from the organic solvent,
This is achieved by polymerizing ethylene or α-olefins.

The starting materials for the modified titanium catalyst component used in the present invention are titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, and combinations of titanium trichloride and metal chloride obtained by reducing titanium tetrachloride with metal. All titanium trichloride compositions containing titanium trichloride or titanium trichloride as a main component, such as eutectics, titanium trichloride compositions obtained by reducing titanium tetrachloride with a compound having an S1-H bond or an organoaluminum compound. It is. These starting titanium components may be used in finely divided form. These also include a pulverized product obtained by co-pulverizing titanium trichloride or a titanium trichloride composition with the addition of a substance selected from the group of modifiers described above as an additive.
The amount of additive added here is 0.5 to 100 mol based on titanium trichloride or titanium trichloride composition. , preferably in the range of 2 to 70 mol%. The addition is usually carried out before the grinding operation, but it may also be added during the grinding process or in several batches. General formula A used in co-milling with the starting titanium component in the presence of ethylene or α-olefin
The organic aluminum compound of Hx3-m is, for example, triethylaluminum, triisobutylaluminum,
Examples include diethylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminium monobromide, and ethylaluminum sesquitalolide.

Is the amount of ethylene or α-olefin added during co-grinding approximately 10% by weight based on the starting titanium component? The lower limit is usually about 0.01% by weight. As the α-olefin, lower α-olefins such as propylene and butene-1 are used. These need not be of the same type as the monomers used in the catalytic polymerization. The grinding operation is carried out using conventional grinders that grind powder, such as ball mills, vibrating mills,
The process is carried out using a column mill, a dinit mill, etc. in the absence of oxygen, moisture, etc.

The grinding may also be carried out in the presence of a small amount of hydrogen. The grinding temperature is generally in the range of -30°C to 150°C, and the appropriate grinding time is about 1 to 100 hours. The co-pulverized product thus obtained is subjected to a modification treatment comprising contacting it with an inert organic solvent or a mixture of the organic solvent and a modifier, and then separating it from the organic solvent.

In this text, the term "washing treatment" with an organic solvent is used to mean a modification operation by contact with an organic solvent. In this modification treatment, the co-pulverized material is washed with an organic solvent and separated, the co-pulverized material is washed with an organic solvent and then brought into contact with a mixture of an organic solvent and a modifier, and separated. Various embodiments can be taken depending on the starting materials and purpose, such as a method of contacting and separating a mixture, or a method of repeatedly contacting and separating with different types of organic solvents or mixtures of organic solvents and modifiers. Preferred examples of the inert organic solvent used in this modification treatment include hexane, heptane, cyclohexane, benzene, toluene, xylene, and monochlorobenzene.

The organic solvent is used in an amount of 1 to 500 parts by weight based on the co-pulverized material, and O
Process at ~200°C. After the treatment, the solvent and the co-pulverized product are separated by decantation or F-filtration. Further, depending on the case, it may be further heated under normal pressure or reduced pressure to remove the solvent and dry. Further, these washing and separation operations may be repeated several times. The modifier used in the modification treatment is selected from the following groups (1) to (4).

In addition to the starting titanium component, the additives to be co-milled are also selected from the group of additives as well as the modifier. For details of the modifier, please refer to the patent application entitled "Method for producing polymerization catalyst component" filed simultaneously on June 10, 1970 (Japanese Patent Application No. 51-67).
No. 092). (1) Organic oxygen-containing, sulfur, phosphorus, nitrogen or silicon compounds: Examples of organic oxygen-containing compounds include diethyl ether, diphenyl ether,
Preferred are ditolyl ether, 2-chlorophenyl ether, diethyl ketone, diphenyl ketone, ethyl acetate, ethyl benzoate, and the like.

Examples of the organic sulfur-containing compound include diethylthioether, di-n-propylthioether, dibenzylthioether, diphenylthioether, n-dodecylthioalcohol, and thiophenol. Preferred examples of the organic phosphorus-containing compound include triphenylphosphine, triphenylphosphine, triphenylphosphine oxide, triphenylphosphate, and the like. As organic nitrogen-containing compounds, triethylamine, triphenylamine,
Examples include phenyl isocyanate, azobenzene, and acetonitrile. Also, as an organosilicon compound,
Tetrahydrocarbon silanes, halogen derivatives thereof, linear or cyclic organopolysilanes, siloxane polymers, etc. are used. (2) Combination of the compound of (1) above and aluminum halide: As the aluminum halide, aluminum trichloride, aluminum tribromide, etc. are preferable.

These two components may be added separately, may be used in the form of a mixture of both, or may be used in the form of a reaction product or a complex of both. Reaction products or complexes include diphenyl ether/aluminum trichloride complex, diethyl ether/aluminum trichloride complex, thiophenol/
Examples include aluminum trichloride reaction products and diethylthioether/aluminum trichloride reaction products. (3) Organoaluminum compounds: Examples include diethylaluminum monochloride, diisopropylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride.

(4) Lewis acid: titanium tetrachloride, boron fluoride, boron chloride, silicon tetrachloride, etc. are exemplified.

The modification treatment of the co-pulverized titanium component with a mixture of an organic solvent and a modifier and the contact conditions are detailed in the above-mentioned co-filed Japanese Patent Application No. 51-67092.

The organoaluminum compound which is another catalyst component used in the method of the present invention has the same general formula AlRmX3-m (where R, X, and m are the same as above) as used in the preparation of the titanium catalyst component. ) is used, and the same compounds as above are exemplified.

Although the ratio of the titanium catalyst component to the organoaluminum compound component used in the method of the present invention can be varied over a wide range, it is generally preferred that the molar ratio of the organoaluminum compound component to the titanium catalyst component is about 1 to 500.

The method of the present invention involves not only homopolymerization of ethylene and α-olefins, but also copolymerization of these monomers, such as ethylene and propylene-butene-1, benzene-1, hexene-1, 4-methylbenzene-1, propylene It also includes copolymerization of butene-1, hexene-1, etc.

- For the polymerization reaction according to the method of the present invention, conventional methods and conditions commonly used in the art can be employed. The polymerization temperature at that time is 20 to 300
°C, preferably in the range of 50 to 200 °C, and the polymerization pressure is in the range of normal pressure to 200 atm, preferably in the range of normal pressure to 150 atm.

In the polymerization reaction, aliphatic, alicyclic, aromatic hydrocarbons or mixtures thereof can generally be used as a solvent, such as propane, butane, Z-pentane, hexane, heptane, cyclohexane, benzene, toluene, etc. and mixtures thereof are preferably used.

It is also possible to perform bulk polymerization using the liquid monomer itself as a solvent. Furthermore, it can also be carried out under conditions substantially free of solvent, that is, by a so-called gas phase polymerization method in which a gaseous monomer and a catalyst are brought into contact. The molecular weight of the polymer produced in the method of the present invention depends on the reaction mode,
It varies depending on the catalyst system and polymerization conditions, but if necessary,
For example, it can be controlled by adding hydrogen, alkyl halides, dialkylzinc, etc.

According to the present invention, by (co)polymerizing olefins using a polymerization catalyst consisting of a modified titanium catalyst component and an organoaluminum compound, the fine powder content is extremely low.
A (co)polymer with a narrow particle size distribution can be obtained.

Furthermore, surprisingly, in the polymerization of the present invention, the polymerization rate is significantly faster than when using a conventional modified titanium catalyst component, and the stereoregularity of the resulting polymer is extremely high. It turned out to be effective.

Next, the present invention will be explained with reference to examples.

Example 1) Production example of titanium catalyst component: Diameter 12m7! Internal volume approximately 60cm containing approximately 80 L steel balls
Prepare a vibrating mill equipped with a 0m1 grinding pot.

In the pot, a titanium trichloride/aluminum chloride eutectic (hereinafter abbreviated as A-type titanium trichloride) obtained by reducing titanium tetrachloride with metal aluminum in a nitrogen atmosphere.
Add composition tenon TiCl3, XAlCl3) 309,
Milled for 0 hours. (This pulverized product is abbreviated as AA type titanium trichloride in the following examples.) Next, 1.0111 diethyl aluminum monochloride was added and pulverized for 15 minutes, and then 200 ml of propylene gas was charged and pulverized for 3 hours. .

The pulverized contents were separated from the steel balls under a nitrogen atmosphere, 150 ml of n-heptane was added to the titanium component 309 obtained, and after stirring at the boiling point of heptane for 20 minutes, the n-heptane was removed by decantation. Ta. After performing this operation five times, 150 ml of heptane was added at the sixth time and used as an activated titanium component suspension. 2) Polymerization example: In a SUS-32 autoclave with an internal capacity of 210, 11 n-heptane and 0.4 of the above activated titanium component were added under a nitrogen atmosphere.
59 and diethylaluminum monochloride 1.0ml
was loaded.

After evacuating the autoclave with nitrogen and a vacuum pump,
Hydrogen was charged at a partial pressure of 1.0k9/CTil in the gas phase, and then propylene was charged to make the pressure in the gas phase 2kg/C7l gauge.

The contents of the autoclave were heated, and after 5 minutes, the internal temperature was raised to 70°C, and the polymerization was continued at 70°C. During polymerization, propylene was continuously pressurized and the internal pressure was maintained at 5k9/d gauge. After 3.5 hours, the amount of polymerized propylene was approximately 5.
009, the introduction of propylene was stopped, unreacted gas was discharged, 300 ml of methanol was added, and the mixture was stirred for 30 minutes to decompose the catalyst.

After cooling the autoclave, remove the contents and add 200ml of water.
After washing 3 times at 60℃ with
White polypropylene 4989 was obtained by drying under reduced pressure at 0°C.

The intrinsic viscosity of the obtained polypropylene (measured at 135°C with tetralin, hereinafter the same) was 1.63, and the bulk specific gravity was 0.4.
29/ml, and the boiling n-heptane extraction residue (hereinafter abbreviated as Powder 11) was 96.0%.

On the other hand, 229 amorphous polypropylene was obtained by evaporation of the bottom liquid.

The polymerization activity of the catalyst in this polymerization reaction is 3309/9・Hr (
The polypropylene production rate per g of activated titanium per hour (the same applies hereinafter) and the ratio of boiling n-heptane extraction residual polymer to the total polymer (hereinafter abbreviated as total 11)
Is it 91.9? It was hot.

Furthermore, in the dry powder, fine particles with a particle size smaller than 200 mesh (hereinafter abbreviated as fine particles) accounted for 8.3 wt% of the total, and particles finer than 20 mesh and coarser than 100 mesh accounted for 71.0 wt% of the total.

Comparative Examples 1 to 3 AA type titanium trichloride (
Comparative Example 1), a catalyst component in which propylene gas was not charged during pulverization by the method of Example 1 (1) (Comparative Example 2),
The results of polymerization conducted in the same manner as in Example 1 (2) using the catalyst component (Comparative Example 3) in which the heptane washing operation was not performed in the method of Example 1 are compared with Example 1. It is shown in Table 1.

Example 2 A mixture of 309 ml of A-type titanium trichloride and 6.99 ml of aluminum chloride diphenyl ether complex was ground for 40 hours in the same manner as in Example 1 (1), and then 3300 ml of propylene and 10 ml of diethylaluminium monochloride were added.
Time grinding continued.

The pulverized contents were washed with heptane in the same manner as in Example 1 (1) to obtain an activated titanium component, which was used for polymerization in the same manner as in Example 1 (2).

Polypropylene powder 505 with polymerization time 2.10hr
9. Amorphous polypropylene 159 was obtained.

The polymerization activity was 5509/9·Hr, and the resulting polypropylene powder had an intrinsic viscosity of 1.67 and a bulk specific gravity of 0.4.
39/Mll powder was 1197.0%, and total 11 was 94.3%.

The fine particles of the dry powder accounted for 7.3% of the total.

Comparative Example 4 In Example 2, the second stage of pulverization in the coexistence of propylene and diethylaluminum monochloride was omitted, and the catalyst preparation and polymerization were otherwise carried out in the same manner as in Example 2.

Polypropylene 4849 and amorphous polypropylene 169 having an ultimate particle size of 1.58, a powder of 1196.3%, and a bulk specific gravity of 0.409/ml were obtained in a polymerization time of 2.32 hours.

Polymerization activity in this polymerization experiment was 4789/9hr, total 119
It was 3.2%. Also, the fine particles of dry powder are 28.7
It was wt%.

Comparing these results with Example 2, it is clear that the method of the present invention significantly reduces the number of fine particles and improves the polymerization activity and total 11.

Examples 3 to 74 In the method of Example 2, various components were added in place of diphenyl ether/aluminum chloride complex, which was an additive in the first grinding step, to adjust the catalyst, and the results were polymerized. It is shown in Table 2.

Further, in the method of Example 2, experiments were also conducted in which various α-olefins were used in place of propylene in the second step of pulverization, and in which various organic solvents were used in place of n-heptane in the washing step. Note that the cleaning temperature is determined when the solvent is n-hexane and n-hexane.
- When heptane, cyclohexane, benzene, and toluene were used, the test was carried out at the boiling point, and in the case of monochlorobenzene and xylene, the test was carried out at 100°C (the same applies to the following examples).

As a control, Table 2 shows the fine particle content of the resulting polymer when polymerization was carried out using a titanium component obtained by omitting the second pulverization step.

Example 75 (1) Production example of titanium component: In the production example of titanium component in Example 1 (1), AA type Ti
A pulverized product obtained by pulverizing Cl3 in the coexistence of diethylaluminum monochloride and propylene was subjected to a modification treatment using dibutylniter as a modifier.

That is, 259 ml of the pulverized product, 150 ml of n-heptane, 109 ml of di-n-butyl ether were added, and after stirring at the boiling point of heptane for 20 minutes, the supernatant liquid was removed by decantation. Next, add 150ml of n-heptane and
Washing was carried out by stirring for a minute and separating the n-heptane by decantation. After performing this washing treatment five times, 150 ml of n-heptane was added at the sixth time to obtain an activated titanium component suspension. (2) Polymerization example: Example (2) using this activated titanium component of 0.359
Polymerization of propylene was carried out in the same manner.

Polypropylene powder 480 with polymerization time 2.33hr
9. Amorphous polypropylene 259 was obtained. Polypropylene powder intrinsic viscosity number 1.65 bulk specific gravity 0.43
9/Mll powder was 1196.0% and fine particles 9.3%.

Polymerization activity in this polymerization reaction is 619f! /g・Hr, total 11
It was 91.2%. Comparative Example 5 In the production of the titanium component of Example 75, pulverization in the coexistence of diethylaluminum monochloride and propylene was omitted, and AA type Ti
Modification with di-n-butyl ether was carried out using Cl3 as a raw material.

Activity in polymerization reaction 4609/9hr1 total 1190.0%
The fine particles are 45.0%, and the bulk specific gravity of the powder is 0.30.
It was 9/ml.

The polypropylene powder produced in this experiment has an extremely increased number of fine particles and a low bulk specific gravity, so the polymer concentration is approximately 350.
When the polymerization rate approached g/l-heptane, the polymerization rate decreased significantly, demonstrating the effectiveness of the method of the present invention.

Examples 76 to 99 In place of the propylene and diethylaluminum monochloride used in the pulverization step in the production of the titanium component in Example 75, various olefins and organoaluminum compounds as shown in Table 3 were used, and as a modifier in the modification treatment. Table 3 shows the results of an experiment conducted in the same manner as in Example 75 using various modifiers in place of di-n-butyl ether.

Example 100 50 ml of titanium tetrachloride was added to the activated titanium suspension obtained in Example 75 (1) and heated at 70°C for 2 hours.
After stirring for 0 minutes, the supernatant was removed by decantation, and then washed 5 times with 150 ml of n-heptane to obtain a new activated titanium suspension, which (activated titanium component) (used as 0.359) was used in one polymerization experiment in the same manner as in Example 1 (2).

Polypropylene powder 508 with polymerization time of 1.98 hr.
9. Amorphous polypropylene 129 was obtained. Polypropylene powder has an intrinsic viscosity of 1.60 and a bulk specific gravity of 0.4.
39/ml, powder 1198.0%, fine particles 9.8%.

The total polymerization activity in this polymerization reaction was 7559/9-Cathrl, 1195.8%.

Comparative Example 6 The titanium catalyst component obtained in Comparative Example 5 was treated with titanium tetrachloride in the same manner as in Example 100, and compared with Example 100.

Polypropylene powder 408 with polymerization time of 2.33 hours
9. Amorphous polypropylene 171 was obtained.

The polypropylene powder had an intrinsic viscosity of 1.60, a bulk specific gravity of 0.309/Mll fine particles of 50.8%, and a polymerization activity in the main polymerization reaction of 5219/9·Hr, a total of 193.0%.

Comparing this result with the result of Example 100, it is found that when the pulverization step in the coexistence of the organoaluminum compound and olefin in the preparation of the catalyst component of the present invention is omitted, the number of fine particles of the produced polymer increases greatly, and the bulk specific gravity also decreases. It is clear that it has major drawbacks as a polymerization catalyst.

Examples 101 to 107 The catalyst components prepared in Examples 76, 82, 83, 86, 92, 95, and 97 were further treated with titanium tetrachloride in the same manner as in Example 100 to obtain an activated titanium suspension.

Table 4 shows the results of polymerization of 0.359% of this activated titanium component in the same manner as in Example 1. For comparison, the amount of fine particles and the value of bulk specific gravity of polypropylene powder polymerized using a catalyst component in which pulverization in the coexistence of diethylaluminium monochloride and propylene was omitted are also shown. Example 108. (1) Production example of titanium component: AA type titanium trichloride 409, n-heptane 150ml11
10ml of di-n-butyl ether at the boiling point of heptane
After stirring for 0 minutes, n-
Heptane was excluded.

After adding 150 ml of n-heptane and repeating the same washing process of stirring and decantation 5 times, the temperature was increased to 50°C.
, and was dried by heating for 20 minutes under a reduced pressure of 5 ml of Hg.
The obtained dried product 309 was put into a vibration mill and Example 1 (1
) in the same manner as diethylaluminum monochloride 1
．． Grind for 15 minutes with 0ml, then add 200ml of ethylene.
ml was added and pulverized for 3 hours.

The pulverized product was added with 150 ml of n-heptane and 20 ml of di-n-butyl ether, stirred for 20 minutes at the boiling point of n-heptane, the clear soil was removed, and the washing treatment with 150 ml of n-heptane was repeated three times. Next, 150 n-heptane
After adding 50 ml of m11 titanium tetrachloride and stirring at 70° C. for 20 minutes, the washing treatment with n-heptane was repeated three times, and 150 ml of n-heptane was added to obtain an activated titanium component suspension. (2) Polymerization example: Example 1 (1) using the above activated titanium component 0.259
) Polypropylene powder 5139 and amorphous polypropylene 59 were obtained in a polymerization time of 2.0 hr.

The intrinsic viscosity of the obtained polypropylene powder was 1.58.
, bulk specific gravity 0.43f/M4 powder 1198.0%,
The fine particles were 8.9%.

Activity in main polymerization reaction 10369/9・Hrl total 1197
．． It was 0%.

Comparative Example 7 Among the methods of Example 108 (1), the pulverization treatment in the coexistence of an organoaluminum compound and ethylene was omitted, and the
-Butyl ether treatment was performed twice and titanium tetrachloride treatment was performed, and polymerization was carried out in the same manner as in Example 108 (2).

Polymerization time 2.

Polypropylene 3579 and amorphous polypropylene 109 were obtained in 5 hours.

The intrinsic viscosity of the polypropylene powder is 1.55, the bulk specific gravity is 0.29, the powder is 1197.0%, the fine particles are 52.3%, the polymerization activity is 5879/9・Hr, and the total is 1194.4%.
It was hot.

A high-performance catalyst cannot be obtained by simply repeating the reforming process in this manner.

Comparative Example 8 The catalyst components were prepared and polymerized in the same manner as in Example 108 (1) except that the catalyst was ground without adding diethylaluminum monochloride and ethylene.

Polypropylene powder 4079 with polymerization time of 2.5 hours
, amorphous polypropylene 109 was obtained.

The polypropylene powder had an intrinsic viscosity of 1.61, a bulk specific gravity of 0.301, 1197.3% powder, 48.7% fine particles, and a total polymerization activity of 6679/9·Hr 1195.0%.

Comparing this with Example 108, in the comparative example, there are many fine particles of the produced polymer, the bulk specific gravity is low, and the activity and total 11 are also low, indicating that the special crushing operation of the titanium catalyst component used in the present invention is effective. I understand.

Example 109 (1) Production example of titanium component AA type titanium trichloride 409, diphenyl ether 3.7
9. Place 3.29 g of aluminum chloride in a vibrating mill pot, grind for 40 hours, wash with n-heptane in the same manner as in Example 2, then add 150 ml of n-heptane, 20 ml of diisoamyl ether, and stir at 70°C for 20 minutes. After washing 3 times with 150ml of n-heptane, 50℃
, and dried under reduced pressure at 1 mmHq.

Dry product 309, diethylaluminium monochloride 1
．． After adding 0ml of propylene and grinding for 15 minutes, add 30ml of propylene.
0ml was charged over 1 hour while being pulverized, and pulverization was continued for 2 hours.

150ml of n-heptane was added to the resulting pulverized product 25θ.
Add diisoamyl ether 2077L1 and heat at 70°C.
After stirring for 0 minutes, the supernatant was removed by decantation, and then washed three times with 150 ml of n-heptane at the boiling point of n-heptane.

Next, 150 ml of n-heptane and 50 ml of titanium tetrachloride were added and stirred at 70°C for 20 minutes, followed by washing with n-heptane five times at the boiling point of n-heptane to obtain an activated titanium component suspension. (2) Polymerization example: Example 1 (2) using 0.20 g of the obtained activated titanium
Polymerization was carried out in the same manner as in ).

Polypropylene powder 5239 with polymerization time of 2.0 hr.
, amorphous polypropylene 49 was obtained. The obtained polypropylene powder has an intrinsic viscosity of 1.57 and a powder of 1.
198.1%, bulk specific gravity 0.439/Mls fine particles 7.3
It was %.

Polymerization activity in main polymerization reaction 13209/9・Hr total 119
It was 7.4%. Comparative Example 9 The catalyst component was prepared and polymerized in the same manner as in Example 109, except that the second pulverization in the catalyst component production step of Example 109 (1) was performed without adding diethylaluminum monochloride and propylene. Summer.

Polypropylene powder 3589 with polymerization time of 2.3 hours
, 7 g of amorphous polypropylene was obtained, the intrinsic viscosity of the polypropylene powder was 1.57, and the bulk specific gravity was 0.309/
The Mll powder was 1197.3% and the fine particles 48.7%.

Polymerization activity in main polymerization reaction 7939/9・Hrl total 119
It was 5.4%.

Examples 110-116 Examples 2, 7, 73, 83, 100, 108 and 109
Bulk polymerization of propylene was carried out using the catalyst component synthesized in the following method.

That is, a predetermined amount of activated titanium component suspended in 30 ml of heptane and 0.8 ml of diethylaluminium monochloride were charged into a SUS-32 autoclave having an internal volume of 61 (7) under a nitrogen atmosphere. After the nitrogen in the autoclave was evacuated using a vacuum pump, hydrogen and 2.5 kg of 2N11 propylene were charged into the autoclave.

The contents of the autoclave were heated, and after 15 minutes, the internal temperature was raised to 60°C, and polymerization was carried out at 60°C. After 5 hours, the autoclave was cooled, the contents were taken out and dried under reduced pressure at 60°C to obtain polypropylene.

The experimental results are shown in Table 5.

For comparison, Table 4 also shows the fine particles and bulk specific gravity of polypropylene powder obtained by polymerization using a catalyst component prepared without coexistence of an organoaluminum compound and olefin during catalyst component crushing.

Titanium tetrachloride 200mM. Pour 100 ml of n-hexane into a No. 11 round bottom flask equipped with a stirrer, cool to 0°C, and add 220 ml of diethylaluminum monochloride.
A solution of 200 ml of n-hexane was added dropwise over 2 hours, stirred at room temperature for 3 hours, the supernatant liquid was removed by decantation, washed three times with 300 ml of n-hexane at room temperature, and then dried under reduced pressure at 50 °C and 1 mmHg. did. The titanium trichloride composition 309 thus obtained by the reduction reaction was charged into a vibrating mill pot and pulverized for 20 hours, then 1.0 ml of triethylaluminum was added and pulverized for 15 minutes, and further 200 ml of ethylene was added and pulverized for 3 hours. continued. Obtained pulverized product 259, n-hexane 150m
11 Add 20ml of di-1S0-butyl ether and
After stirring for a minute, the supernatant liquid was removed by decantation and washed five times with 150 ml of n-hexane at a temperature of the boiling point of n-hexane to obtain an activated titanium component suspension. Polymerization of ethylene was carried out. (2)
Polymerization Example: Into an autoclave having an internal volume of 21 ml, 111 ml of heptane, 0.109 ml of the above activated titanium, and 0.5 ml of diethylaluminum monochloride were charged under a nitrogen atmosphere.

After exhausting the nitrogen in the autoclave with a vacuum pump,
Hydrogen was charged at a partial pressure of 2.0 k9/d, and then ethylene was charged to make the pressure in the gas phase 4 kg/DG. After 20 minutes of heating the contents of the autoclave, the internal temperature reaches 90°C.
Polymerization continued as follows.

During polymerization, ethylene is continuously pressurized to maintain an internal pressure of 9.5k.
9/Cf! I kept it at 1G. After 2.5 hours of polymerization, stop introducing ethylene, release unreacted gas, and add 300 m of methanol.
1 was added and stirred for 30 minutes to decompose the catalyst.

The contents of the autoclave were taken out, washed three times by adding 200 ml of water, and then dried under reduced pressure at 60° C. to obtain white polyethylene powder 5209.

The resulting polyethylene had an intrinsic viscosity of 2.23 and a bulk specific gravity of 0.
．． 439/ml, fine particles 5.3%, and the activity in the main polymerization was 20809/9·Hr.

Example 118 Using the catalyst prepared in Example 109 (1), a mixture of ethylene and propylene containing 1 m01% of ethylene was blown in instead of propylene, and a mixture of ethylene and propylene was produced in the same manner as in Example 109 (2). Polymerization was carried out.

The bulk specific gravity of the obtained polypropylene powder is 0.42
The amount of fine particles was 6.0%, indicating that the present invention is also effective in copolymerization reactions.

Claims (1)

[Claims] 1. In the polymerization of ethylene or α-olefins, titanium trichloride or a titanium trichloride composition is added with a small amount of ethylene or α-olefin of about 10% by weight or less to the general formula AlR_mX_3_-_m (here R
is an alkyl group or an aryl group, X is hydrogen or halogen, and m is 1 to 3), and then co-pulverized with an inert organic solvent or the inert organic solvent and 1) oxygen-containing , sulfur, phosphorus, nitrogen or silicon organic compounds, 2) a combination of the organic compound of 1) above and aluminum halide, 3) an organoaluminum compound, and 4) a mixture with a modifier selected from the group consisting of Lewis acids. A method for polymerizing ethylene or α-olefins, characterized by using a Ziegler type polymerization catalyst consisting of a modified titanium catalyst component obtained by a catalytic reforming treatment and an organoaluminum compound. 2 The titanium trichloride or titanium trichloride composition is 1)
Oxygen-containing, sulfur, phosphorus, nitrogen or silicon organic compounds, 2)
The claim 1 is a pulverized product obtained by adding an additive selected from the group consisting of 1) a combination of the organic compound and aluminum halide, 3) an organoaluminum compound, and 4) a Lewis acid. The method for polymerizing ethylene or α-olefins according to item 1. 3. The above-mentioned modified titanium component is subjected to the above-mentioned modification treatment before the above-mentioned co-pulverization step, and the titanium component after co-pulverization is further subjected to the above-mentioned modification treatment. A method for polymerizing ethylene or α-olefins according to claim 1, which is obtained by: