JPS59142206A - Production of catalyst component for alpha-olefin polymerization - Google Patents

Abstract

PURPOSE:To produce the titled component capable of providing a stereoregular polymer in high yields, by suspending a specified dialkoxymagnesium and a carboxylic acid ester in an aromatic hydrocarbon, and contacting the resulting suspension with a titanium halide. CONSTITUTION:A suspension is prepared by adding (A) 1g of a dialkoxymagnesium of the formula Mg(OR)2 (wherein R is alkyl, cycloalkyl, or aryl) and 0.01- 2g of a carboxylic acid ester (e.g., methyl acetate) to (C) an aromatic hydrocarbon (e.g., toluene) and stirring the mixture for 100hr or shorter at a temperature of from room temperature to the b.p. of component (C). This suspension is contacted with at least 0.1g of (D) a titanium halide of the formula TiX4 (wherein X is a halogen) for 10min-10hr at a temperature of from -20 deg.C to the b.p. of component (D). The product is washed with an organic solvent such as n-heptane to obtain a catalyst component for alpha-olefin polymerization.

Description

[Detailed description of the invention] The present invention is applied to the polymerization of α-olefins.

A method for producing a high-performance catalyst component that acts with high activity and can obtain a stereoregular polymer in high yield. The present invention relates to a method for producing a catalyst component for polymerizing α-olefins, which comprises suspending the catalyst component in a titanium halide and then bringing it into contact with a titanium halide.

Conventionally, solid titanium halides have been well known and widely used as catalyst components for the polymerization of α-olefins. Since the polymerization activity per titanium is low, a so-called demineralization step to remove catalyst residues was unavoidable. Because the deashing process uses a large amount of alcohol or chelating agents, recycling equipment is not necessary for the recovery equipment source, and there are many resource, energy, and other problems associated with it, and it is difficult for operators to This was an important issue that needed to be resolved as soon as possible. In order to eliminate this complicated deashing process, many studies have been conducted and proposals have been made to increase the polymerization activity per titanium in the catalyst component, especially the titanium halogen active component. There have been many proposals for dramatically increasing the polymerization activity per titanium in the catalyst component when a transition metal compound such as a compound is supported on a carrier material such as magnesium chloride and used for the polymerization of α-olefins.

For example, in JP-A-50-126590.

A method is disclosed in which a catalyst component is obtained by contacting magnesium chloride as a carrier material with an aromatic carboxylic acid ester by mechanical means, and contacting the obtained solid composition with titanium tetrachloride in a liquid phase. There is.

However, the chlorine contained in magnesium chloride may cause deterioration and yellowing of the produced polymer, granulation, etc.
It also causes corrosion of equipment used in processes such as molding, and therefore high activity is required to the extent that the effects of chlorine can be virtually ignored. In the catalyst components used,
The current situation is that nothing showing sufficient performance has been obtained to date.

Therefore, attempts have been made to use substances other than magnesium chloride in order to obtain higher performance.

For example, Tokukai Akira! No. 56-166205 describes Mg (
OF2) nX2-n (R' is an alkyl group having 1 to 10 carbon atoms.

It represents a cycloalkyl group, an aryl group, or an aralkyl group, X represents a halogen atom, and n represents 10 to 2.0. ) is disclosed. However, in this method, Ti(OR2)4(R2i[prime number 1
~10 alkyl, cycloalkyl, aryl or aralkyl groups. ) is required, and in terms of performance, no one has been obtained that satisfies the requirements of the technical field.

Still, JP-A-57-40510 discloses a method for obtaining a catalyst component by reacting metal magnesium, tetraalcoquine titanium, alcohol, an electrodynamic compound, and titanium halide;
It is necessary to start the reaction from titanium, and the use of tetraalkoxytitanium is also an essential requirement, and it does not show sufficient performance values.

Furthermore, in Japanese Patent Application Laid-open No. 57-65509, 9M
g(OF2)2'(R' is an alkyl group having 1 to 20 carbon atoms.

cycloalkyl group, aryl group, or aralkyl group. ) is brought into contact with an electron-donating compound.

Next, Ti(OR”)nX, -n (R2 is a carbon number of 1 to 1
0 represents an alkyl group, cycloalkyl group, aryl group, alkenyl group or aralkyl group, n is a real number of 0 or more and less than 4, and ■ represents a ).rogen atom. ) has been disclosed, but it has not yet reached the point where it can fully satisfy the requirements of the technical field in terms of single polymerization characteristic values, etc. In addition,
There is also a description that an aliphatic hydrocarbon such as hexane or heptane can be added as a solvent when bringing the Mg(OF2)2 into contact with an electron-donating compound, but as shown in the comparative example below, sufficient This cannot be said to indicate performance.

As a result of intensive research to solve the problems remaining in the prior art, the present inventors found that the general formula Mg(OR)2 (wherein R is an alkyl group, a cycloalkyl group, or an aryl group). dialkoxymagnesium represented by in the presence of a carboxylic acid ester.

suspended in an aromatic hydrocarbon and then formed with the general formula TiX
, (in the formula, X is a halogen element)...
Catalytic performance can be dramatically improved by bringing it into contact with titanium halogenide. As a result, the amount of chlorine contained in the catalyst component and the amount of chlorine in the produced polymer can be reduced to a completely negligible level.

Further, as an accompanying effect, the produced polymer has a substantially spherical shape, a narrow particle size distribution, and a large particle size. This has made it extremely easy to handle the produced polymer, such as transporting it to post-processing equipment.

Currently, there is an urgent need in the industry to omit the granulation step in the industrial production process of α-olefin polymers, but the granulation step can be omitted by using the catalyst component obtained by the present invention. It can be said that the possibility of doing so has been opened.

In addition, in the industrial production of α-olefin polymers, it is common to allow hydrogen to coexist during polymerization from the viewpoint of MI control, but the catalyst components that use magnesium chloride as a carrier are had the disadvantage that the activity and stereoregularity were greatly reduced in the presence of hydrogen. However, when α-olefins are polymerized using the catalyst components obtained according to the present invention, the activity and stereoregularity hardly decrease even if hydrogen is present during the first polymerization.

Such an effect is of great benefit to those skilled in the art.

Examples of dialkoxymagnesium used in the present invention include jetoxymagnesium, dibutoxymagnesium, and diphenoxymagnesium.

Dipropoquinomagnesium, di-5ee-butoxymagnesium, di-tert-butoxymagnesium.

Examples include diimpropoxymagnesium.

The carboxylic acid ester used in the present invention includes ethyl acetate. Examples include aliphatic carboxylic acid esters such as methyl methacrylate, aromatic carboxylic acid esters such as ethyl toluate, ethyl anisate, and ethyl benzoate, among which aromatic carboxylic acid esters are preferred. It is.

Aromatic hydrocarbons used in the present invention include benzene, toluene, xylene and the like.

The titanium halides represented by the general formula TiX4 (in the formula or a halogen element) used in the present invention include TiO4, TIB, r4. TiI4
Among them, Tict is preferable.

The ratio of each component used in the present invention is arbitrary as long as it does not adversely affect the performance of the catalyst component produced, and is not particularly limited, but usually alkoxymagnesium 1 1
f, carboxylic acid esters are 001 to 22. Preferably, the amount is in the range of o1 to 12, and the amount of monocogenated titanium is 0.11 or more, preferably 1 g or more. Further, the aromatic hydrocarbon can be used in any proportion as long as it can form a suspension.

In the present invention, suspension of alkoxymagnesium in an aromatic hydrocarbon in the presence of a carboxylic acid ester is carried out at a temperature ranging from usually room temperature to the boiling point of the aromatic hydrocarbon used.
It is carried out within a range of 00 hours or less, preferably 10 hours or less. At this time, it is necessary that the suspension does not become a uniform solution.

Still, the contact between the suspension and titanium halide is usually 1-2.
From 0℃ to the boiling point of the titanium chloride used,
Preferably at a temperature of -10°C to 100°C for 10 minutes to 1
It is carried out in the range of 0 hours. At this time, it is preferable to add the suspension to the titanium halide.

The means for contacting each component in the present invention is not particularly limited as long as it is a method that allows sufficient contact between each component.

This is usually carried out while stirring using a container equipped with a stirrer.

In the present invention, it is also possible to suspend alkoxymagnesium in an aromatic hydrocarbon solvent in the presence of a carboxylic acid ester, then contact it with a titanium halide, and then wash it with an organic solvent such as n-heptane. , even more...
There is no hindrance to repeated contact with titanium halide.

These series of operations of 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 α-olefins. The organoaluminum compound used has a molar ratio of 1 to 1000.0% per mole of titanium atoms in the catalyst component. It is preferably used in the range of 1 to 300. Furthermore, it is not prohibited to add 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 α-olefin monomer can be used in either gas or liquid state. The polymerization temperature is 200°C or less, preferably 100°C or less, and the polymerization pressure is 100 kg/c4-o or less, preferably 100 kg/c4-o or less.
K9/cd-G or lower.

The α-olefins to be homopolymerized or copolymerized using the catalyst component produced by the method of the present invention are propylene, 1
-7'tene, 4-methyl-1-pe/tene, etc., and copolymerization of α-olefins and ethylene is also possible.

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
Jetoxymagnesium 51 in a 0 ml round bottom flask
．． Ethyl benzoate2. Od and 25 ml of toluene were charged to form a suspension, and the mixture was stirred at 70°C for 1 hour. This suspension was then poured into a 500 m7 volume equipped with a stirrer. TiC at 0°C in a round bottom flask of! After the mixture was pumped into a 74,200 ml vessel, the temperature was raised to 70°C, and the mixture was stirred for 2 hours to react from the beginning. After the reaction was completed, it was washed 6 times with 30 rows of n-hebutane at 40°C.
50 ml of TiC4+ was newly added and reacted at 70°C for 2 hours with stirring. After the reaction was completed, the mixture was cooled in a trench at 40°C and washed repeatedly with 200 ml of n-hebutane. When chlorine was no longer detected in the washing solution, the washing was completed and the catalyst component was removed. At this time, when the solid and liquid in the catalyst component was separated and the titanium content of the solid was measured, it was found to be 5.89 by weight.

[Overlapping]

700 - of n-hebutane was charged into an autoclave with an internal volume of 2.0 t and equipped with a stirring device, which was completely purged with nitrogen gas.
Triethyl aluminum 30 while maintaining nitrogen gas atmosphere
1~. P-) 137 m@ of ethyl ruylate, and then 1.0 μm of the above catalyst component as titanium atoms were charged. After that, 500 dl of hydrogen gas was charged, the temperature was raised to 60℃, and while propylene gas was introduced, 6 Kg/c++! Polymerization was carried out for 2 hours while maintaining the pressure of -G. After completion of polymerization, the obtained solid polymer was separated into E.

The amount of polymer dissolved in the polymerization solvent after heating to 80° C. and drying under reduced pressure, and concentrating the filtrate, is defined as (A), and the amount of solid polymer is defined as (B). The obtained isopolymer was extracted with boiling n-hebutane for 6 hours to obtain a polymer insoluble in n-hebutane, and this amount was designated as (C).

The polymerization activity (D) per catalyst component was expressed by the formula, and the yield (E) of the crystalline polymer was expressed by the formula, and the yield (F) of the total crystalline polymer was determined from the formula. There is still residual chlorine in the produced polymer (G).

The M process of the produced polymer is represented by ()1). The results obtained are:

As shown in Table 1.

Example 2 An experiment was carried out in the same manner as in Example 1 except that 30-ethyl benzoate was used. Incidentally, the titanium content in the solid content at this time was 3.60% 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 6 An experiment was conducted in the same manner as in Example 1 except that the temperature of TiCL was set to room temperature when the suspension was pumped.

Incidentally, the titanium content in the solid content at this time was 3.26% 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 4 Jetoxymagnesium 52 and ethyl benzoate 2.0y
d.) An experiment was carried out in the same manner as in Example 1, except that the suspension of toluene 25- was stirred and the subsequent reaction with TiC44 was carried out at 80°C.

Incidentally, the titanium content in the solid content at this time was 681% by weight. During the polymerization, an experiment was carried out in the same manner as in Example 1, except that 0.5 mg of titanium atoms were used as the catalyst component. The results obtained are shown in Table 1.

Example 5 An experiment was conducted in the same manner as in Example 1 except that an O-kiln was used instead of toluene. Incidentally, the titanium content in the solid content at this time was 622% by weight. During polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that n-hebutane was used instead of toluene. In addition.

The titanium content of the solid fraction at this time was 256% by weight.

' For polymerization, an experiment was conducted in the same manner as in Example 1. The results obtained are shown in Table 1.

Comparative Example 2 Capacity 20 fully purged with nitrogen gas and equipped with a stirrer
Jetoxymagnesium 51.0- in a round bottom flask. 201 d of ethyl benzoate and 425 ml of TiCA were charged and reacted at 70° C. for 1 hour with stirring. Then the capacity 501] m7 equipped with a stirrer! 0°C in a round bottom flask of
After pumping into 200 ml of TiO4.

The temperature was raised to 70° C., and the reaction was allowed to proceed with stirring for 2 hours.

After the reaction was completed, it was cooled to 40°C and then diluted with 20% of rhobutane.
0m7! The cleaning was repeated, and when chlorine was no longer detected in the cleaning solution, the cleaning was completed and the catalyst component was used. Incidentally, when the titanium content of the solid agglomerate was measured, it was found to be 399% by weight.

During polymerization, an experiment was conducted in the same manner as in Example 1.

The results obtained are shown in Table 1.

Claims (1)

[Scope of Claims] (F) (a) Dialkoxymagnesiramura represented by the general formula Mg (OR)2 (in the formula, R is an alkyl group, a cycloalkyl group or an aryl group), (b) a carboxylic acid (C) suspended in an aromatic hydrocarbon in the presence of an ester;
A method for producing a catalyst component for polymerizing α-olefins, which is then brought into contact with (d) a titanium halide represented by the general formula T1X4 (wherein X is a halogen element).