JPH06104686B2 - Method for producing catalyst component for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a catalyst component which, when subjected to the polymerization of olephins, has a high activity and can obtain a stereoregular polymer in a high yield. For more details on the manufacturing method, refer to the general formula MgX ₂
A compound obtained by pulverizing a magnesium compound represented by the formula (wherein X is a halogen element) (hereinafter sometimes simply referred to as “magnesium compound”) and an aromatic dicarboxylic acid diester in a temperature range of less than 0 ° C. The solid composition is brought into contact with a titanium halide represented by the general formula TiX ₄ (where X is a halogen element) (hereinafter sometimes simply referred to as “titanium halide”). The present invention relates to a method for producing a catalyst component for polymerization.

[Conventional technology]

Conventionally, solid titanium halides are well known and widely used as catalyst components for olefin polymerization.
Since the yield of the catalyst component and the polymer per titanium in the catalyst component (hereinafter simply referred to as the catalyst component and the polymerization activity per titanium in the catalyst component) is low, a so-called deashing step for removing the catalyst residue is unavoidable. It was. Since this deashing process uses a large amount of alcohol or a chelating agent, a recovery device or a regenerating device for them is indispensable, and there are many resources, energy, and other incidental problems, and a person skilled in the art can quickly solve them. This is an important issue that is desired. In order to eliminate this complicated deashing process, many studies have been made and proposed to increase the polymerization activity of the catalyst component, especially titanium per catalyst component.

In particular, as a recent tendency, when a transition metal compound such as titanium halide, which is an active ingredient, is supported on a carrier substance such as magnesium chloride and subjected to the polymerization of olefins, the polymerization activity per titanium in the catalyst component is significantly increased. There are many proposals to raise the price.

[Problems to be solved by the invention]

However, the conventionally proposed methods require very complicated steps such as dissolving magnesium chloride in alcohol, and while maintaining a high degree of stereoregular polymer yield with a simple method. No example can be found in which the polymerization activity per catalyst component is increased.

The present inventors have reached the present invention as a result of earnest research in order to solve the problems left over in the related art, and make a proactive proposal.

[Means for solving problems]

That is, the feature of the present invention is that (a) the general formula MgX ₂
A solid compound obtained by pulverizing a magnesium compound represented by the formula (wherein X is a halogen element) and (b) an aromatic dicarboxylic acid diester in a temperature range of less than 0 ° C. is (c) generally Contacting a titanium halide represented by the formula TiX ₄ (where X is a halogen element),
Another object of the present invention is to provide a method for producing a catalyst component for polymerizing olefins.

Examples of the magnesium compound used in the present invention include magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide and the like, and among them, magnesium chloride is preferable.

Formula TiX ₄ used in the present invention (wherein X is a halogen element.) TiCl ₄ as a titanium halide represented by, TiBr _4, TiI ₄ but like among them TiCl ₄
Is preferred.

After the contact between the solid composition produced in the present invention and the titanium halide, further contact with the titanium halide, or by washing with an organic solvent such as n-heptane, to further enhance the effect of the present invention Is also possible.

The use ratio of each of these components is arbitrary as long as it does not adversely affect the performance of the catalyst component to be produced, and is not particularly limited, but usually the aromatic dicarboxylic acid diester is 0.01 to 1 g per 1 g of the magnesium compound. Used at a rate of 1g.

The pulverization of the magnesium compound and the aromatic dicarboxylic acid diester in the present invention is usually carried out by a mechanical means, but generally, a ball mill, a vibration mill, a tower mill,
An impact crusher or the like is used. The crushing time varies depending on the performance of the equipment used, but is usually 1 to 500
It is a range of time. Further, the crushing temperature needs to be in a low temperature range of less than 0 ° C.

The contact between the titanium halide and the solid composition can be carried out by various methods, for example, in a vessel equipped with a stirrer, usually at room temperature to a temperature range up to the fluorine point of the titanium halide used. The contact time is arbitrary as long as the solid composition and titanium halide can be sufficiently contacted with each other, but is usually in the range of 10 minutes to 100 hours.

At this time, repeated contact with the titanium halide or washing with an organic solvent such as n-heptane is possible.

It is preferable that these series of operations in the present invention are performed in the absence of oxygen, water and the like.

The catalyst component produced as described above is combined with an organoaluminum compound to form a catalyst for olefin polymerization.
The organoaluminum compound used is used in a range of 1 to 1000 in terms of molar ratio per mole of titanium atom in the catalyst component.
In addition, addition of a third component such as an electron-donating substance during the polymerization does not interfere.

The polymerization can be carried out in the presence or absence of an organic solvent. Further, the olefin monomer can be used in either a gas or liquid state. Polymerization temperature is 20
0 ℃ or less, preferably 100 ℃ or less, the polymerization pressure is 100kg /
cm ² · G or less, preferably 50 kg / cm ² · G or less.

Olefins homopolymerized or copolymerized using the catalyst component produced by the present invention are ethylene, propylene,
1-butene, 4-methyl-1-pentene and the like.

〔The invention's effect〕

When olefins are polymerized using the catalyst component obtained according to the present invention, the catalyst residue in the produced polymer can be kept extremely low due to its high activity, and thus the produced polymer can be The influence of chlorine exerted can be reduced. Further, it also shows an extremely excellent effect on the yield of the stereoregular polymer.

Further, in the conventionally known highly active supported catalyst, the activity was greatly reduced as the polymerization proceeded, and it was practically impossible to use it for copolymerization and the like, but it was obtained by the present invention. When such a catalyst component is used, such a phenomenon can be suppressed to a very low level and can be sufficiently used for copolymerization.

〔Example〕

 The present invention will be specifically described below with reference to examples.

Example 1 [Preparation of catalyst component] 30 g of magnesium chloride and 7.2 ml of dipropyl phthalate
In a nitrogen gas atmosphere, insert a 25 mmφ stainless ball into a vibration mill pot with a capacity of 1.0 l filled with 4/5 of the total volume,
Pulverization was performed for 17 hours at a frequency of 1430 v.pm and a swing of 3.5 mm at -10 ° C.

Fully replaced by nitrogen gas, equipped with a stirrer, capacity 500m
200 ml of TiCl ₄ and 7 g of the solid composition obtained by the above-mentioned pulverization treatment were charged in a round-bottomed flask having a volume of 1 and the mixture was stirred at 110 ° C for 2 hours. After completion of the reaction, the mixture was left standing and the supernatant was removed by decantation, 200 ml of TiCl ₄ was newly added, and the mixture was kept at 110 ° C for 2 hours.
Reacted for hours. Then, washing with 100 ml of n-heptane was repeated, and when the chlorine was not detected in the washing solution, the washing was considered to be completed and the catalyst component was obtained. In addition,
At this time, the solid-liquid in the catalyst component was separated, and the titanium content in the solid was measured and found to be 2.54% by weight.

〔polymerization〕

700 ml of n-heptane was charged into an autoclave equipped with a stirrer and having an internal volume of 2.0 l which was completely replaced with nitrogen gas, and 300 mg of triethylaluminum, 62.7 mg of phenyltriethoxysilane and the above catalyst components were charged while maintaining a nitrogen gas atmosphere. 0.62 mg was charged as titanium atom. Then hydrogen gas 180m
While charging 1 liter and raising the temperature to 70 ° C and introducing propylene gas, 6
Polymerization was carried out for 2 hours while maintaining the pressure of kg / cm ² · G.

After the completion of the polymerization, the solid polymer obtained was separated, heated to 80 ° C. and dried under reduced pressure to obtain 260 g of a polymer. On the other hand, the liquid was condensed to obtain 3.2 g of a polymer. The MI in the solid was 6.1.

Example 2 When an experiment was conducted in the same manner as in Example 1 except that the polymerization time was 3 hours, 362 g of a solid polymer was obtained. The MI of the solid polymer was 6.8, and the polymer obtained by condensing the liquid was 6.4.

Example 3 Diptyl phthalate 10.2 instead of dipropyl phthalate
An experiment was conducted in the same manner as in Example 1 using ml. The titanium content in the solid component at this time was 2.71% by weight. After the completion of the polymerization, the solid polymer obtained was 267 g, and the polymer obtained by condensing the liquid was 3.5 g.

Example 4 An experiment was performed in the same manner as in Example 1 except that the reaction temperature with TiCl ₄ was 100 ° C. The titanium content in the solid content at this time was 2.72% by weight.

An experiment was conducted in the same manner as in Example 1 except that 52.5 mg of phenyltriethoxysilane was used in the polymerization. The obtained solid polymer was 278 g, and the polymer obtained by condensing the liquid was 4.3 g.

[Brief description of drawings]

FIG. 1 is a flow chart for explaining the present invention.

Claims (1)

[Claims] 1. A magnesium compound represented by the general formula MgX ₂ (where X is a halogen element), and (b)
A solid composition obtained by pulverizing an aromatic dicarboxylic acid diester in a temperature range of less than 0 ° C. is used to prepare a titanium halide represented by (c) a general formula TiX ₄ (wherein X is a halogen element). A method for producing a catalyst component for olefin polymerization, which comprises bringing them into contact with each other.