JPH0340043B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a high-performance catalyst component that exhibits high activity when subjected to the polymerization of olefins and is capable of obtaining a stereoregular polymer in high yield. Specifically, the present invention relates to a method for producing a catalyst component for polymerizing olefins, which comprises bringing fatty acid magnesium into contact with a titanium halide.

Conventionally, solid titanium halides have been well known and widely used as catalyst components for the polymerization of olefins. Because of the low polymerization activity (per unit polymerization activity), a so-called deashing step to remove catalyst residues was unavoidable. This deashing process uses a large amount of alcohol or chelating agent, so recovery or regeneration equipment is essential, and resources and
There are many energy and other related problems, and it is an important problem that those skilled in the art would like to solve as soon as possible. In order to eliminate this complicated deashing process, many studies have been made and proposals have been made to increase the polymerization activity per titanium in the catalyst component, especially in the catalyst component.

In particular, a recent trend is to support transition metal compounds such as titanium halides, which are active ingredients, on carrier materials such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity per titanium in the catalyst component can be dramatically increased. I've seen many suggestions for increasing it.

However, when magnesium chloride is used as a carrier material, it is common to use an electron-donating substance such as an aromatic carboxylic acid ester when bringing titanium tetrahalide into contact with the carrier material. If contact was attempted in the absence of a chemical substance, only a small amount of titanium was supported, leaving an unresolved problem that sufficient activity could not be obtained when subjected to the polymerization of olefins. was.

In order to compensate for these drawbacks, attempts have been made to use substances other than magnesium chloride that can effectively act as carrier materials. However, the methods proposed so far can not only increase the polymerization activity per catalyst component but also fully satisfy the requirements in the technical field of maintaining a high yield of stereoregular polymers. has not been proposed.

As an example, in JP-A-49-120980, a catalyst component is obtained by reacting magnesium acetate with an aluminum compound, and then contacting the reaction product with titanium tetrahalide in a liquid phase. Although a method for polymerizing olefins has been disclosed, it is not applicable to propylene polymerization, which requires a high yield of stereoregular polymers, as in the present invention. This fact is also demonstrated in the comparative examples described below.

The present inventors have arrived at the present invention as a result of intensive research to solve the problems remaining in the prior art, and hereby propose the present invention.

That is, the present invention is characterized by the polymerization of olefins by bringing (a) fatty acid magnesium into contact with (b) a titanium halide represented by the general formula TiX ₄ (wherein X is a halogen element). The purpose of this invention is to achieve the desired purpose in the absence of electron-donating substances conventionally used in the art.

The fatty acid magnesium used in the present invention includes magnesium palmitate, magnesium stearate, magnesium behenate, magnesium acrylate, magnesium adipate,
Magnesium acetylene dicarboxylate, Magnesium acetoacetate, Magnesium azelaate, Magnesium citrate, Magnesium glyoxylate, Magnesium glutarate, Magnesium crotonate, Magnesium succinate, Magnesium isovalerate, Magnesium isobutyrate, Magnesium octoate, Magnesium valerate, Magnesium decanoate, magnesium nonanoate, magnesium docosenoate, magnesium undecenoate, magnesium elaidate, magnesium linolenate,
Magnesium hexanoate, Magnesium heptanoate, Magnesium myristate, Magnesium laurate, Magnesium butyrate, Magnesium oxalate, Magnesium tartrate, Magnesium suberate, Magnesium sebacate, Magnesium sorbate, Magnesium tetrolate, Magnesium hydroacrylate, Pimelic acid magnesium,
Examples include magnesium pyruvate, magnesium fumarate, magnesium propionate, magnesium maleate, magnesium malonaldehyde, and magnesium malonate, among which saturated fatty acid magnesium is preferred.

Note that it is preferable to use the fatty acid magnesium in a form with as much moisture removed as possible.

The general formula TiX ₄ used in the present invention (in the formula
is a halogen element. Examples of the titanium halide represented by ) include TiCl ₄ , TiBr ₄ , TiI ₄ and the like, with TiCl ₄ being preferred.

In the present invention, the effects of the present invention can be further enhanced by further washing with an organic solvent such as n ^- heptane after contacting fatty acid magnesium and titanium halide.

The ratio of each component used in the present invention is arbitrary as long as it does not adversely affect the properties of the catalyst component produced, and is not particularly limited, but usually the titanium halide is 0.01 mol or more per 1 mol of magnesium fatty acid. It is preferably used in an amount of 1 mol or more.

The contact between fatty acid magnesium and titanium halide in the present invention is usually carried out at a temperature ranging from room temperature to the boiling point of the titanium halide used, preferably in the range of 40 to 100°C. The contact time is arbitrary as long as the fatty acid magnesium and the titanium halide can sufficiently react, but the contact time is usually in the range of 10 minutes to 100 hours.

It is also possible to wash the slurry composition obtained after the treatment using an organic solvent such as n-heptane.

These series of operations in the present invention are preferably carried out in the absence of oxygen, moisture, and the like.

The catalyst component produced as described above is combined with an organoaluminum compound to form a catalyst for polymerizing olefins. The organoaluminum compound used is used in a molar ratio of 1 to 1000, preferably 1 to 300, per mole of titanium atoms in the catalyst component.
Further, it is not prohibited to add and use a third component such as an electron-donating substance during the polymerization.

Polymerization can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in either gas or liquid state. The polymerization temperature is 200°C or less, preferably 100°C or less, and the polymerization pressure is 100Kg/cm ² ·G or less, preferably 50Kg/cm ² ·G or less.

Olefins homopolymerized or copolymerized using the catalyst component produced by the method of the present invention include ethylene, propylene, 1-butene, 4-methyl-
1 pentene etc.

The present invention will be specifically explained below using Examples and Comparative Examples.

Example 1 [Preparation of catalyst component] Commercially available magnesium stearate was vacuum-calcined at 110°C for 7 hours in a round bottom flask with a capacity of 200 ml, which was sufficiently purged with nitrogen gas and equipped with a stirrer.
10 g and 50 ml of TiCl ₄ were charged, and a stirring contact reaction was carried out at 65° C. for 2 hours. After the reaction was completed, the mixture was cooled to 45°C, left to stand, and the supernatant liquid was removed by decantation. Next, washing with 100 ml of n-heptane was repeated, and when chlorine was no longer detected in the washing solution, the washing was completed and the catalyst component was used.
At this time, the solid and liquid in the catalyst component was separated and the titanium content in the solid was measured and found to be 2.97% by weight.

[Polymerization] Add 500 ml of n-heptane to an autoclave with a stirring device and a capacity of 1.5 that was completely purged with nitrogen gas.
108.8 mg of triethylaluminum and ethyl P-toluate were charged while maintaining a nitrogen gas atmosphere.
52.3mg, then the catalyst component as a titanium atom
0.92 mg was charged. Thereafter, the temperature was raised to 60°C, and polymerization was carried out for 2 hours while maintaining a pressure of 4 kg/cm ² ·G while introducing propylene gas.

As a result, 3050 g of polymer was obtained per 1 g of catalyst component. Boil the solid part of this
- When extracted with heptane for 6 hours, the proportion of extraction residue was 91.0% by weight.

Example 2 [Preparation of catalyst component] Example 1 except that 10 g of commercially available magnesium octoate calcined in vacuum at 70°C for 7 hours was used.
The experiment was conducted in the same manner. Note that the titanium content in the solid content at this time was 3.25% by weight.

[Polymerization] An experiment was carried out in the same manner as in Example 1, except that 108.8 mg of triethylaluminum, 44.9 mg of ethyl P-toluate, and 0.92 mg of the above catalyst component as a titanium atom were used.

As a result, 2810 g of polymer was obtained per 1 g of catalyst component. Boil the solid part of this n-
When extracted with heptane for 6 hours, the proportion of extraction residue was 91.2% by weight.

Example 3 [Preparation of catalyst components] An experiment was conducted in the same manner as in Example 1.

[Polymerization] Add 500 ml of n-heptane to an autoclave with a stirring device and an internal volume of 1.0 that was completely purged with nitrogen gas.
While maintaining a nitrogen gas atmosphere, 250 mg of triethylaluminum and 0.63 mg of the catalyst component as titanium atoms were charged. Then the hydrogen gas is heated to an internal pressure of
The mixture was charged to a pressure of 3.5 kg/cm ² ·G, and ethylene gas was further introduced to conduct polymerization at 85° C. for 4 hours while maintaining a pressure of 7.0 kg/cm ² ·G.

As a result, 5770 g of polymer was obtained per 1 g of catalyst component. Note that the FR of the resulting polymer determined from formula (1) was 14.0.

FR=MI at 10Kg load/MI at 2Kg load......(1) Comparative Example 1 [Preparation of catalyst component] The experiment was conducted in the same manner as in Example 1, except that magnesium chloride was used instead of magnesium stearate. Summer. Note that the titanium content in the solid content at this time was 0.97% by weight.

[Polymerization] The polymerization was carried out in the same manner as in Example 1, except that 108.8 mg of triethylaluminum, 44.9 mg of ethyl P-toluate, and 0.92 mg of the above catalyst component as a titanium atom were used.

As a result, 1540 g of polymer was obtained per 1 g of catalyst component. Boil the solid part of this
- When extracted with heptane for 6 hours, the proportion of extraction residue was 90.3% by weight.

Comparative Example 2 14.2 g of anhydrous magnesium acetate, 40.8 g of aluminum triisopropoxide, and 50 ml of delicane were placed in a 200 ml round bottom flask under a nitrogen atmosphere, and a stirring contact reaction was carried out at 170 to 230°C for 10 hours. Summer. Thereafter, the solvent was removed and drying was performed under reduced pressure to obtain a solid powder. The obtained solid powder was dehydrated n-
After washing 10 times with 100 ml of heptane, remove the solvent and
Further drying under reduced pressure was performed to obtain a solid powder. Next, 80 ml of TiCl ₄ was added thereto, heated to 150° C., and a stirring contact reaction was carried out for 2 hours.

After the reaction was completed, the mixture was cooled to room temperature, left to stand, and the supernatant liquid was removed by decantation. Then dehydration
- Washing with 100 ml of heptane was repeated, and when chlorine was no longer detected in the washing solution, the washing was completed and used as a catalyst component. At this time, the solid and liquid in the catalyst component was separated and the content of titanium in the solid component was measured, and it was found to be 12.2% by weight.

During polymerization, the catalyst components obtained were 1.62 mg of titanium atoms, 109 mg of triethylaluminum,
An experiment was carried out in the same manner as in Example 1 by charging 35 mg of ethyl p-toluate. As a result, no polymer was obtained to the extent that the polymerization properties could be measured.

[Brief explanation of drawings]

FIG. 1 is a flowchart for explaining the present invention.

Claims (1)

[Claims] 1. A method for producing a catalyst component for polymerizing olefins, which comprises bringing (a) fatty acid magnesium into contact with (b) a titanium halide represented by the general formula TiX ₄ (wherein X is a halogen element). .