JPH0674291B2 - 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 is capable of obtaining a stereoregular polymer in a high yield. In more detail regarding the production method, a reaction product of diethoxymagnesium and an aromatic dicarboxylic acid diester and titanium tetrachloride and a solid composition obtained by pulverizing magnesium chloride at low temperature are further contacted with a titanium halide. The present invention relates to a method for producing a catalyst component for olefin polymerization, which is characterized in that

[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, the so-called deashing step for removing the catalyst residue is not possible. It was possible. 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) diethoxy magnesium, (b) a reaction product of an aromatic dicarboxylic acid diester and titanium tetrachloride, and (c) magnesium chloride are pulverized at a low temperature of 5 ° C. or lower. Another object of the present invention is to provide a method for producing a catalyst component for polymerization of olefins, which is prepared by bringing the solid product thus obtained into contact with titanium tetrachloride.

After contacting the solid composition produced in the present invention with titanium tetrachloride, further contact with titanium tetrachloride, or by washing with an organic solvent such as n-heptane,
It is also possible to further enhance the effect of the present invention.

The use ratio of each of these components is arbitrary as long as it does not adversely affect the performance of the catalyst component produced, and is not particularly limited, but the aromatic dicarboxylic acid is added to 1 g of the total amount of diethoxymagnesium magnesium chloride. The reaction product of diester, titanium and tetrachloride is used in a proportion of 0.01 to 2 g.

The reaction product of the aromatic dicarboxylic acid diester and titanium used in this case is obtained by reacting the two in a suitable solvent, washing the produced solid content, and drying.

The reaction product of diethoxymagnesium, an aromatic dicarboxylic acid diester and titanium tetrachloride in the present invention and the pulverization of magnesium chloride are generally carried out by mechanical means, but generally, a ball mill, a vibration mill, a tower type mill, An impact crusher or the like is used. The crushing time varies depending on the performance of the equipment used, but it is usually 1 to
The range is 500 hours. The crushing temperature needs to be 5 ° C or lower, preferably about -10 ° C.

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

At this time, it is possible to repeatedly make contact with titanium tetrachloride or wash with an organic solvent such as n-heptane.

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 the chlorine in the catalyst component can be suppressed. Due to the low content, the effect of chlorine on the polymers produced can be reduced to a negligible level. 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] TiCl ₄ and dibutyl phthalate were reacted in 25 g of magnesium chloride, 5 g of diethoxymagnesium and n-heptane, washed and dried to obtain 16 g of TiCl ₄ / dibutyl phthalate complex. In a gas atmosphere, insert 25 mmφ stainless steel balls into a vibrating mill pot with a volume of 1.0 liter filled with 4/5 of the total volume, and perform a crushing treatment for 20 hours at −10 ° C. with a frequency of 1430 v.pm and a swing of 3.5 mm. Natsuta.

Fully replaced by nitrogen gas, capacity 500m equipped with stirrer
200 ml of TiCl ₄ and 7.6 g of the solid composition obtained by the above-mentioned pulverization treatment were charged into a round-bottomed flask having a volume of 1 l, and stirred at 120 ° 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 reaction was carried out at 120 ° C. for 2 hours. Then, washing with 200 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. At this time, when the solid-liquid in the catalyst component was separated and the titanium content in the solid was measured, it was 2.24% by weight.

[Overlap]

700 ml of n-heptane was charged into an autoclave with an internal volume of 1.5 l, which was completely replaced with nitrogen gas, and 300 mg of triethylaluminum, 70 mg of diphenyldimethoxysilane and the above catalyst components were added to titanium while maintaining a nitrogen gas atmosphere. Charged 0.60 mg as an atom. Then 100 ml of hydrogen gas
6k while charging propylene gas and raising the temperature to 70 ° C and introducing propylene gas
Polymerization was carried out for 2 hours while maintaining the pressure of g / 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 289 g of a polymer. Meanwhile, the liquid was condensed to obtain 2.3 g of a polymer. The MI of the solid polymer is 2.9.
It was.

Example 2 When an experiment was conducted in the same manner as in Example 1 except that the polymerization time was 3 hours, 396 g of a solid polymer was obtained. The MI of the solid polymer was 3.1, and the polymer obtained by condensing the liquid was 2.8 g.

Example 3 Example 1 using 18 g of TiCl ₄ dibutyl phthalate complex
An experiment was conducted in the same manner as in. The titanium content in the solid component at this time was 2.51% by weight. The solid polymer obtained after the completion of the polymerization was 238 g, and the polymer obtained by condensing the liquid was 1.8 g. The MI of the solid polymer was 3.7.

Example 4 An experiment was conducted in the same manner as in Example 1 except that pulverization was performed at 0 ° C. for 30 hours. The titanium content in the solid content at this time was 2.19% by weight.

After the polymerization was completed, the solid polymer obtained was 281 g, and the polymer obtained by condensing the liquid was 2.2 g. The MI of the solid polymer was 5.0.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. A solid composition obtained by pulverizing (a) diethoxymagnesium, (b) a reaction product of an aromatic dicarboxylic acid diester and titanium tetrachloride, and (c) magnesium chloride at a low temperature of 5 ° C. or lower. A method for producing a solid catalyst component for olefin polymerization, which further comprises contacting titanium tetrachloride with the product.