JPS62205104A - Production of catalytic component for polymerizing olefin - Google Patents

Abstract

PURPOSE:To obtain a catalytic component which acts in high activity in the use of olefin polymerization and can produce a stereoregular polymer in high yield, by grinding specific three components at low temperature to give a solid composition and further bringing a titanium halide into contact with the solid composition. CONSTITUTION:(A) A magnesium halide (e.g., MgCl2, etc.), (B) a reaction product of an electron donor (e.g. aromatic dicarboxylic acid diester, etc.) and a titanium halide (e.g. TiCl4, TiBr4, etc.) and (C) a magnesium carbonate or a substance (e.g. MgCO3, hydrotalcite, etc.) in ratio of usually 0.1-2g component B and <=2g component C based on 1g component A are ground at <=5 deg.C low temperature to give a solid composition, which is further brought into contact with a titanium halide. The prepared catalytic component is combined with an organoaluminum compound and used as a catalyst for polymerizing an olefin.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides a catalyst component that has high activity when used in the polymerization of olefins and is capable of obtaining stereoregular polymers in high yield. More specifically regarding the production method, a solid composition obtained by pulverizing a reaction product of magnesium halide, an electron donating substance, and a titanium halide, and a carbonate of magnesium or a substance containing the carbonate at a low temperature. The present invention relates to a method for producing a catalyst component for polymerizing olefins, which comprises further contacting the catalyst with a titanium halide.

[Conventional technology]

Conventionally, solid titanium halides have been well known and widely used as catalyst components for polymerizing olefins.
Since the catalyst component and the polymer content per titanium in the catalyst component (hereinafter simply referred to as the catalyst component and the polymerization activity per titanium in the catalyst component) are low, a so-called deashing process is used to remove the catalyst residue. was inevitable. Since this deashing process uses a large amount of alcohol or chelating agent, recovery equipment or regeneration equipment for these is essential, and there are many resource, energy, and other related problems, and it is desirable for those skilled in the art to solve them as soon as possible. This was an important issue. In order to eliminate this complicated deashing process, many studies have been made and proposals have been made to increase the polymerization activity of catalyst components, especially titanium in the catalyst components.

In particular, there has been a recent trend in which transition metal compounds such as titanium halides, which are active ingredients, are supported on carrier materials such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity of the titanium in the catalyst component is reduced. There are many proposals that have dramatically improved this.

[Problem that the invention seeks to solve]

However, the methods proposed so far require very complicated steps such as dissolving magnesium chloride in alcohol, and it is possible to maintain a high yield of stereoregular polymers while maintaining the catalyst components using simple methods. No examples have been found in which the polymerization activity per unit was increased.

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 propose it to strings.

[Failure to solve the problem]

That is, the present invention is characterized by (a) magnesium no-logenide, (b) a reaction product of an electron donating substance and a titanium halide, and (c) a carbonate of magnesium or containing the carbonate. The solid composition obtained by grinding the material at low temperature is further contacted with a titanium halide and used as a catalyst component for the polymerization of olefins.

Magnesium chloride used in the present invention includes magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, and the like, with magnesium chloride being preferred.

As the electron donating substance used in the present invention, aromatic carboxylic acid esters are preferable, and aromatic dicarboxylic acid diesters are particularly preferable.

Examples of the titanium logide used in the present invention include TiCj4, TiBr4, TiI4, etc., and among them, Tick is preferable.

As the magnesium carbonate or the substance containing the carbonate used in the present invention, magnesium carbonate, basic magnesium carbonate, idrotalcite, etc. are preferable.

After contacting the solid composition produced in the present invention with a titanium halide, the effect of the present invention can be further enhanced by further contacting with a titanium halide or by washing with an organic solvent such as n-hebutane. It is also possible.

The ratio of each component to be used is arbitrary as long as it does not adversely affect the performance of the catalyst component produced, and is not particularly limited.
For 'f K, the reaction product of the electron donating substance and the titanium halide is 101 to 2F, and the carbonate of magnesium or the substance containing the carbonate is 5F or less, preferably 2 or less.

The reaction product of the electron donating substance and titanium halide used at this time is obtained by reacting the two in an appropriate solvent, and then
It is obtained by washing and drying the generated solids.

In the present invention, the reaction product of a magnesium halide, an electron-donating substance, and a titanium halide and a carbonate of magnesium or a substance containing the carbonate are usually pulverized by mechanical means, but generally a ball mill, Vibratory mills, base mills, impact mills, etc. are used.

The grinding time will of course vary depending on the performance of the equipment used, but is usually in the range of 1 to 500 hours. The grinding temperature may be as low as 10°C or lower, preferably 5°C or lower.

The contact between the titanium halide and the solid composition can be carried out using various methods, but for example, it is usually carried out in a container equipped with a stirrer at a temperature ranging from room temperature to the boiling point of the titanium halide used. . The contact time is arbitrary as long as the solid composition and the titanium halide can be brought into sufficient contact with each other, but the contact time is usually in the range of 10 minutes to 100 hours.

At this time, it is also possible to repeatedly contact the titanium halide or to wash using an organic solvent such as n-hebutane.

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

The catalyst component prepared as described above is combined with an organoaluminum compound to form an olefinic catalyst. The organoaluminum compound used is used in a molar ratio of 1 to 1000 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 organic solvents. In addition, the olefin monomer (RI can be used in either gas or liquid state. The polymerization temperature is 200°C or lower, preferably 100°C or lower, and the polymerization pressure is 100'kg/12·G or lower, preferably 50°C or lower. 1
7/Enemy・G or lower.

Olefins I which are homopolymerized or copolymerized using the catalyst components produced according to the invention! i! i is ethylene, phlopylene, 1-7''tene, 4-methyl-1-pentene, etc.

〔Effect of the invention〕

When polymerizing olefins using the catalyst component obtained by the present invention, the amount of catalyst residue in the resulting polymer can be kept extremely low due to its high activity, and the chlorine content in the catalyst component can be kept to an extremely low level. Because of the small amount, the influence of chlorine on the produced polymer can be reduced to a negligible level. Furthermore, it shows extremely excellent effects in terms of the yield of stereoregular polymers.

In addition, in conventionally known highly active supported catalysts, the activity drops sharply as the polymerization progresses, making it virtually impossible to use them in copolymerization, etc. When using catalyst components, such current
can be kept extremely low, and can be used sufficiently for copolymerization.

[Implementation row]

The present invention will be specifically explained below with reference to Examples.

Example 1 [Back side of catalyst component A] Magnesium chloride 25y', salt striped magnesium carbonate 5
TiCl2 and dibutyl phthalate were reacted in 1 and n-hebutane, washed and dried.

I'm happy with it'#:, TiC! 4 - Dibutyl phthalate complex 16y/I - A total volume of 415 stainless steel poles of 25flφ filled in a nitrogen gas atmosphere 1i 1.
Place the Ot vibration into the auxiliary mill pot and set the vibration frequency to 1420 r.
, ry, rr 1° photographing width 551 -10°
I did the time crushing process.

'54 After being sufficiently replaced with elementary gas, 'r1 (shim 200-
Solid composition 167 obtained by the above-mentioned pulverization process was charged, and a stirring reaction was carried out at 120° C. for 2 hours. After the reaction was completed, the mixture was allowed to stand and the supernatant was removed by decantation, and 2200 ml of TiC4 was added to the reaction mixture for 2 hours at 120°C. Next, washing with 200 ml of n-heptane was carried out repeatedly, and when chlorine was no longer detected in the washing solution, the washing was considered to be completed and used as a catalyst component. At this time, when the solid and liquid in the catalyst component was separated and the titanium content in the solid content was measured, it was found to be 2-86. It! 4)%.

[Overlapping]

700 rll of n-hebutane was completely replaced with nitrogen gas (contains 41.5 t of autoclave with stirring).
17 While maintaining the gas atmosphere, 3 oatpy of triethylaluminum, 9 phenyldimethoxysilane 6
4 As the gold and the catalyst component/t titanium atom, o, s
OrMi entered. After that, hydrogen gas 100- is charged and 7
6k while introducing propylene gas at external temperature of 70℃vC
g, 'cm'' The weight was applied for 2 hours at a pressure of 4 times.

After the completion of the polymerization, the resulting solid mixture was separated, heated to 80°C, and dried under reduced pressure to obtain a 2085' heavy solid. Obtained. On the other hand, the P solution was subjected to pseudo-condensation to obtain a 1'11 compound of 1.97. Further, the MI of the solid polymer was 7.6.

Example 2 An experiment was carried out in the same manner as in Example 1, except that the polymerization time was changed to 5 hours, and a solid polymer of 2852 was obtained. The MI of the solid polymer was 2.6, and the MI of the polymer obtained by substituting Solution F was 2.42.

Example 5 An experiment was conducted in the same manner as in Example 1 using 4 TiC4 dibutyl phthalates.

In addition, the titanium content in the solid component at this time was 502 times 1. Solid polymer obtained after polymerization route 9.・Yo1
952, the polymer obtained by condensing the p liquid was 1.6 t. Moreover, the MI of the solid polymer was 59.

Practical No. 1il14 A practical test was carried out in the same manner as in Example 1, except that the crushing was carried out at 0° C. for 30 hours. In this case, the solid condensate containing Ji Nung was 2.61% by weight.

After the polymerization was completed, the obtained solid polymer had 211 f.

The polymer obtained by condensing the P liquid was 2.1f. Moreover, the MI of the solid polymer? height! &, I got it by 1.

Claims (1)

[Claims] (1) (a) Magnesium halide, (b) reaction product of an electron donating substance and titanium halide, and (c
) A method for producing a catalyst component for polymerizing olefins, which comprises further contacting a solid composition obtained by pulverizing a magnesium carbonate or a substance containing the carbonate at a low temperature with a titanium halide.