JPS6067510A - Production of catalyst components for olefin polymerization - Google Patents

Abstract

PURPOSE:Magnesium dialkoxide, an electron donor, a titanium halide and a specific composition are brought into contact together to give the titled component with reduced chlorine remaining for polymerization catalyst of high activity giving stereoregular polymer in high yield. CONSTITUTION:(A) magnesium dialkoxide, preferably magnesium diethoxide, (B) an electron donor, preferably ethyl benzoate, (C) a titanium halide of the formula: TiX4, preferably titanium tetrachloride and (D) a composition resulting from reaction between oxide or hydroxide of an element in group I -IV in the periodic table, preferably aluminum oxide and component C are brought into contact with one another to give the objective catalyst component. Usually, the resultant component is used in combination with an organoaluminum compound. EFFECT:The residual amount of the catalyst can be reduced.

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. More specifically, a composition obtained by reacting dialkoxymagnesium with an electron-donating substance, titanium/...logenide, and an oxide or hydroxide of an element of Groups ■ to ■ of the periodic table with said titanium...logenide. The present invention relates to a method for producing a catalyst component for polymerizing olefins, which comprises contacting with a catalyst component for polymerizing olefins.

Conventionally, solid titanium halides have been well known and widely used as catalyst components for polymerizing olefins, but the yield of polymer per catalyst component and titanium in the catalyst component (
Hereinafter, it will be referred to as the catalyst component and the polymerization activity per titanium in the catalyst component. ) was so low that a so-called deashing step was necessary to remove catalyst residues. Since this deashing process uses a large amount of alcohol or chelating agent, recovery equipment or regeneration equipment for these is indispensable, and there are many problems associated with resources, energy, etc., and those skilled in the art would like to solve them as soon as possible. This was an important issue. In order to eliminate this complicated deashing step, 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 chlorides, which are active ingredients, on a carrier material such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity of titanium in the catalyst component is reduced. There are many proposals that have dramatically improved this.

For example, in JP-A No. 50-126590, magnesium chloride as a carrier material is brought into contact with an aromatic carboxylic acid ester by mechanical means, and titanium tetrachloride is added to the obtained solid composition in a liquid phase. A method of contacting catalyst components is disclosed.

However, the chlorine contained in magnesium chloride, which is the predominant carrier material, has the disadvantage of having a negative effect on the polymer produced, and the activity is so high that the influence of chlorine can be virtually ignored. However, there remained unresolved issues such as the need to lower the concentration of magnesium chloride itself or the need to lower the concentration of magnesium chloride itself.

Therefore, 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 of the technical field of maintaining a high yield of stereoregular polymers. Nothing has been proposed.

In order to solve the problems remaining in the prior art, the present inventors have devised a method to reduce the residual chlorine in the produced polymer while maintaining a high degree of polymerization activity per catalyst component and the yield of stereoregular polymer. As a result of intensive research, we have arrived at the present invention and propose it to So.

That is, the features of the present invention are (a) dialkoxymagnesium, (b) electron-donating substance, and (C) general formula T.
i Titanium halide represented by X4 (wherein X is a halogen element) and (d) Periodic Table No. 1 to ■
The oxide or hydroxide of a group element is brought into contact with the composition obtained by reacting with the titanium halide and used as a catalyst component for the polymerization of olefins. Comparing the cases where oxides or hydroxides of elements of Groups 1 to Ⅰ of Table 1 are coexisting,
Extremely high catalytic performance can be obtained.

According to the present invention, it has become possible to suppress the chlorine content to an extremely low level, which is a problem that remains in the catalyst component with a magnesium chloride support, which has conventionally been the mainstream in this technical field.

Chlorine contained in the produced polymer not only causes corrosion of equipment used in processes such as granulation and molding, but also causes deterioration and yellowing of the produced polymer itself, and this has been reduced. has extremely important meaning for those skilled in the art.

Of course, it has been demonstrated that the method has extremely excellent effects on the yield of stereoregular polymers without sacrificing the intended purpose of polymerization activity.

When olefins are polymerized using the catalyst component obtained according to the present invention, the amount of catalyst residue in the produced polymer can be kept extremely low, and since the amount of residual chlorine is very small, there is no effect on the produced polymer. The influence of chlorine can be reduced. Furthermore, it shows extremely excellent effects in terms of the yield of stereoregular polymers.

Examples of the dialkoxymagnesium used in the present invention include jetoxymagnesium, dibut4-xymagnesium, diphenoxymagnesium, dipropoxymagnesium, di-5ec-ptoxymagnesium, di-tert-butoxymagnesium, diimpropoxymagnesium, etc. Among them, jetoxymagnesium and dipropoxymagnesium are preferred.

As the electron donating substance used in the present invention, aromatic carboxylic acid esters are preferred, and among these, ethyl benzoate, ethyl p-anisate, and ethyl p-toluate are particularly preferred.

The titanium halide represented by the general formula TiXn (wherein X is a halogen element) used in the present invention includes TiCl2. TiBr4. Examples include TiI4, among which 'piCt4 is preferred.

Examples of the oxides and hydroxides of elements in Groups ■ to ■ of the periodic table used in the present invention include sodium oxide, potassium oxide, calcium oxide, boron oxide, aluminum oxide, silicon oxide, magnesium hydroxide, and water. Examples include calcium oxide, among which magnesium oxide, aluminum oxide, silicon oxide, and magnesium hydroxide are preferred.

The ratio of each of these components used is arbitrary as long as it does not adversely affect the performance of the catalyst component produced, and is not particularly limited, but usually 0.0% of the electron donating substance is used per 1 mole of dialkoxymagnesium. 01 to 50 mol, preferably 0.1 to 5 mol, titanium...loginide is 0.01 mol
It is used in a range of 1 mole or more, preferably 1 mole or more.

In addition, a composition obtained by reacting an oxide or hydroxide of an element of groups R to II of the periodic table with a titanium chloride has a content of 0.01 to 12% of dialkoxymagnesium 12.
102, preferably in the range of 0.12 to 1.07.

Contact of the composition obtained by reacting the dialkoxymagnesium electron-donating substance in the present invention with the titanium halide, and the oxide or hydroxide of an element of Groups 1 to 2 of the Periodic Table. This is usually carried out 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 above-mentioned substances can sufficiently react, but the contact time is usually in the range of 10 minutes to 100 hours.

At this time, the method of contacting each component is not particularly limited, and an organic solvent such as a logenated hydrocarbon may also be allowed to coexist.

It is also possible to repeatedly contact the product obtained after the above-mentioned treatment with a titanium chloride, etc., and it is also possible to wash it 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 produced as described above is combined with an organoaluminum compound to form a catalyst for polymerizing olefins.

The organoaluminum compound used has a molar ratio of 1 to 1.00 per mole of titanium atoms in the catalyst component, preferably 1
It is used in the range of ~300. 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 20
The temperature is 0°C or lower, preferably 100°C or lower, and the polymerization pressure is 1
00 kgA4. G or less, preferably 50kg1c
tl・0 or less.

Olefins that can be homopolymerized or copolymerized using the catalyst component produced by the method of the present invention include ethylene, furopylene, 1-butene, 4-methyl-1-bentene, and the like.

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

Example 1゜[Preparation of catalyst components] A 20-volume tank sufficiently purged with nitrogen gas and equipped with a stirrer
5.02 ml of aluminum oxide and 450 ml of TiCt were placed in a 0-round bottom flask, and a stirring reaction was carried out at 100° C. for 1 hour. After the reaction was completed, the mixture was washed five times with 100 ml of n-hebutane, and then dried under reduced pressure to obtain a solid composition.

Next, the solid composition 12, jetoxymagnesium 52, ethyl benzoate 257 and methylene chloride 50 m/m were charged into a 200 ml round bottom flask which was sufficiently purged with nitrogen gas and equipped with a stirrer to form a suspension. , and stirred under reflux for 2 hours. This suspension was then transferred to TiCt4 at 0°C in a 500-capacity round bottom flask equipped with a stirrer.
After pressure-feeding the mixture into 200-degree C., the mixture was heated to 90.degree. C. and reacted for 2 hours with stirring. After the reaction is complete, add 200 ml of n-hebutane at 40°C.
- was washed 10 times with TiCl2200-, and the mixture was reacted with stirring at 90°C for 2 hours.

After the reaction was completed, it was cooled to 40'C, and then n-hebutane 2
007! The cleaning was repeated repeatedly, and when chlorine was no longer detected in the cleaning solution, the cleaning was completed and the catalyst component was used. At this time, when the solid and liquid in the catalyst component was separated and the titanium content outside the solid was measured, it was 3.38% by weight.

[Overlapping]

Internal volume completely replaced with nitrogen gas2. Charge n-hebutane 700- to an OL autoclave with a stirring device,
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
1~. p-) Ethyl ruylate 137 ~, then the above catalyst component was charged as titanium atoms. Thereafter, 300 ml of hydrogen gas was charged, the temperature was raised to 60°C, and while propylene gas was introduced, polymerization was carried out for 2 hours while maintaining a pressure of 5 kg/c, tl.G. After the polymerization was completed, the obtained solid polymer was separated, heated to 80° C., and dried under reduced pressure. On the other hand, P
The amount of polymer dissolved in the polymerization solvent after concentrating the liquid is (g), and the amount of solid polymer is (B). Further, the obtained solid polymer was extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and this amount was designated as C).

Express the polymerization activity (2) per catalyst component by the formula and the crystalline polymer yield (■) by the formula, and calculate the total crystalline polymer yield (g) from the formula % formula % () (b) 10) I met. Further, residual chlorine in the produced polymer is expressed as (G), and MI of the produced polymer is expressed as O. The results obtained are shown in Table 1.

Example 2 An experiment was carried out in the same manner as in Example 1, except that silicon oxide was used instead of aluminum oxide.

Note that the titanium content in the solid content at this time was 3.92% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 3 An experiment was conducted in the same manner as in Example 1 except that magnesium hydroxide was used instead of aluminum oxide. Note that the titanium content in the solid content at this time was 3.68% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are as shown in Table 1.

Comparative example]

11- [Preparation of catalyst components] MgCl2100S' and ethyl benzoate 31.52 mL were ground for 18 hours under a nitrogen gas atmosphere. Thereafter, the vaginal pulverization composition 1002 was collected, and the internal volume was 20% under a nitrogen gas atmosphere.
Pour into a 00-glass container and add 14500ml of TiC.
was added, and a stirring reaction was carried out at 65° C. for 2 hours. After the reaction was completed, the mixture was cooled to 40°C, left to stand, and the supernatant liquid was removed by decantation. Next, washing with n-heptane 1000 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 of the solid component was measured and found to be 1.28% by weight.

[Overlapping]

During polymerization, the catalyst component has a titanium atom of 1.0
(2) The procedure was carried out in the same manner as in Example 1, except that the following was used. The results obtained are as shown in Table 1.

12- Table 1 Patent applicant: Toho Titanium Co., Ltd.

Claims (1)

[Claims] (1) (a) dialkoxymagnesium, (b) electron donating substance, (c) general formula 'l'iX4 (wherein X is)
・It is a rogen element. ) and (d) an oxide or hydroxide of an element of Groups ■ to ■ of the Periodic Table are brought into contact with a composition obtained by reacting the titanium logenide with the titanium logenide. A method for producing a catalyst component for polymerizing olefins, characterized by: