JPH07108929B2 - 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 solid composition obtained by pulverizing magnesium chloride, a reaction product of an aromatic dicarboxylic acid diester and titanium tetrachloride and an oxide of an element of Group III of the periodic table at a low temperature, Further, the present invention relates to a method for producing a catalyst component for polymerizing olefins, which comprises contacting with titanium tetrachloride.

[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 polymerization activity per catalyst component and titanium in the catalyst component) is low, a so-called deashing step for removing the catalyst residue is unavoidable. Atsuta 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 the problem. This is an important issue that is desired. In order to omit this complicated deashing step, numerous 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) magnesium chloride, (b) aromatic dicarboxylic acid diester and (c)
Reaction products with titanium tetrachloride and (d) Periodic Table II
A method for producing a catalyst component for olefin polymerization, which comprises contacting a solid composition obtained by grinding an oxide of a Group I element in a low temperature range of 5 ° C or lower with titanium tetrachloride. is there.

As the oxide of the group III element of the periodic table used in the present invention, an oxide of aluminum or boron is preferable.

The use ratio of each of these components is arbitrary as long as it does not adversely affect the performance of the produced catalyst component, and is not particularly limited, but usually 1 g of magnesium chloride and aromatic dicarboxylic acid diester and tetrachloride are used. The reaction product with titanium is 0.01 to 2 g, the oxide of the group III element of the periodic table is 5 g
Below, it is preferably used in a proportion of 2 g or less.

The reaction product of the aromatic dicarboxylic acid diester and titanium tetrachloride used in this case can be obtained by reacting both in a suitable solvent, washing the formed solid content, and drying.

Grinding of the reaction product of magnesium chloride, an aromatic dicarboxylic acid diester and titanium tetrachloride and the oxide of an element of Group III of the periodic table in the present invention is usually carried out by mechanical means, but generally a ball mill, A vibration mill, a tower type grinder, an impact grinder, etc. are used. The crushing time varies depending on the performance of the apparatus used, but is usually in the range of 1 to 500 hours. The crushing temperature may be as low as 5 ° C or lower.

The contact between titanium tetrachloride and the solid composition can be carried out by using 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, repeated contact with the titanium halide or washing with an organic solvent such as n-heptane is also 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 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 aluminum oxide and n-heptane, washed and dried to obtain 16 g of TiCl ₄ / dibutyl phthalate complex, and nitrogen gas was added to the mixture. In the atmosphere, insert a 25 mmφ stainless steel ball into a vibration mill pot with a capacity of 1.0 liter filled with 4/5 of the total volume, with a frequency of 1430 v.pm and a swing of 3.5 mm at -10 ° C.
The crushing process was performed for 20 hours.

Fully replaced by nitrogen gas, equipped with a stirrer, capacity 500m
200 ml of TiCl ₄ and 7.6 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 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 liquid, the washing was considered to be completed and the catalyst component was used. In addition,
At this time, when the solid-liquid in the catalyst component was separated and the titanium content in the solid content was measured, it was 2.06% by weight.

〔polymerization〕

An autoclave with a stirrer and an internal volume of 1.5 l that was completely replaced with nitrogen gas was charged with 700 ml of n-heptane, and 300 mg of triethylaluminum, 64 mg of diphenyldimethoxysilane and the titanium component were added to the catalyst component while maintaining a nitrogen gas atmosphere. As a result, 0.62 mg was charged. After that, 80 ml of hydrogen gas was charged, the temperature was raised to 70 ° C., and 6 kg / cm was introduced while introducing propylene gas.
Line polymerization of 2 hours while maintaining the pressure of ² · G Natsuta.

After completion of the polymerization, the solid polymer obtained was separated, heated to 80 ° C. and dried under reduced pressure to obtain 269 g of a polymer. On the other hand, the liquid was condensed to obtain 2.2 g of a polymer. The MI of the solid polymer is 2.8.
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, 367 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 3.0 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 2.38% by weight. The solid polymer obtained after the completion of the polymerization was 251 g, and the polymer obtained by condensing the liquid was 2.0 g. The MI of the solid polymer was 3.9.

Example 4 An experiment was conducted in the same manner as in Example 1 except that the reaction temperature with TiCl ₄ was 110 ° C. The titanium content in the solid content at this time was 2.36% by weight.

An experiment was conducted in the same manner as in Example 1 except that 70 mg of diphenyldimethoxysilane was used for the polymerization. The obtained solid polymer was 275 g, and the polymer obtained by condensing the liquid was 2.6 g. The MI of the solid polymer was 4.5.

Example 5 An experiment was conducted in the same manner as in Example 1 except that boron oxide was used instead of aluminum oxide. The titanium content in the solid content at this time was 2.18% by weight.

After the completion of the polymerization, the amount of the obtained solid polymer was 272 g, and the amount of the polymer obtained by condensing the liquid was 2.2 g. The MI of the solid polymer was 2.8.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. (A) Magnesium chloride (a), (b) Reaction product of aromatic dicarboxylic acid diester and (c) Titanium tetrachloride, and (d) Oxide of Group III element. A method for producing a catalyst component for olefin polymerization, which comprises contacting the solid composition obtained by pulverizing in a low temperature range of 5 ° C. or lower with (c) titanium tetrachloride.