JPH0340045B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a high-performance catalyst component that acts with high activity when subjected to the polymerization of olefins and can obtain a stereoregular polymer in high yield. More specifically, the present invention relates to a method for producing a catalyst component for polymerizing olefins, which involves contacting fatty acid magnesium, an aromatic carboxylic acid ester, and a titanium halide represented by the general formula TiX ₄ (wherein X is a halogen element). Conventionally, solid titanium halides have been well known and widely used as catalyst components for the polymerization of olefins. Because of the low polymerization activity (per unit polymerization activity), a so-called deashing step to remove catalyst residues was unavoidable. This deashing process uses a large amount of alcohol or chelating agent, so recovery or regeneration equipment is essential, and resources and
There are many energy and other related problems, and it is an important problem that those skilled in the art would like to solve as soon as possible. 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 halides, which are active ingredients, on carrier materials such as magnesium chloride, and when used in the polymerization of olefins, the polymerization activity per titanium in the catalyst component can be dramatically increased. I've seen many suggestions for increasing it. For example, in JP-A-50-126590, magnesium chloride as a carrier material is brought into contact with an aromatic carboxylic acid ester by mechanical means, and titanium tetrahalide is added to the resulting solid composition in a liquid phase. A method of contacting catalyst components is disclosed. However, the chlorine contained in magnesium chloride, which is the main carrier material, has the disadvantage of having an adverse effect on the produced polymer, and therefore requires high activity to the extent that the influence of chlorine can be virtually ignored. However, there were still unresolved issues, such as 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 in the technical field of maintaining a high yield of stereoregular polymers. has not been proposed. As an example, in JP-A-49-120980, a catalyst component is obtained by reacting magnesium acetate with an aluminum compound, and then contacting the reaction product with titanium tetrahalide in a liquid phase. Although a method for polymerizing olefins has been disclosed, it is not applicable to propylene polymerization, which requires a high yield of stereoregular polymers, as in the present invention. This fact is also demonstrated in the comparative examples described below. In order to solve the problems remaining in the prior art, the present inventors, in Japanese Patent Application No. 56-156162,
After bringing (a) fatty acid magnesium and (b) an electron donating substance into contact in (c) an organic solvent, the obtained solid composition is mixed with (d) the general formula TiX ₄ (wherein X is a halogen We have proposed a method for producing a catalyst component for polymerizing α-olefins, which is characterized by bringing the catalyst into contact with a titanium halide represented by the following elements. The present inventors have conducted further intensive research to solve the problems remaining in the prior art, and as a result, they have arrived at the present invention, and hereby propose it. That is, the present invention is characterized by (a) fatty acid magnesium, (b) aromatic carboxylic acid ester, and
(c) General formula TiX ₄ (X in the formula is a halogen element.)
In a method for producing a catalyst component for polymerizing olefins, which contacts a titanium halide represented by
In the presence of an organic solvent, the fatty acid magnesium and the titanium halide, or the aromatic carboxylic acid ester and the titanium halide are brought into contact with each other, and then brought into contact with the aromatic carboxylic acid ester or the fatty acid magnesium, respectively. mosquito,
Alternatively, a catalyst component for the polymerization of olefins is obtained by simultaneously bringing the magnesium fatty acid, the aromatic carboxylic acid ester, and the titanium halide into contact with each other. According to the present invention, it has become possible to further reduce the chlorine content, 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. 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 resulting polymer can be kept extremely low, and the amount of residual chlorine is very small. The influence of chlorine on the polymer can be reduced. Furthermore, it shows extremely excellent effects in terms of the yield of stereoregular polymers. The fatty acid magnesium used in the present invention includes magnesium palmitate, magnesium stearate, magnesium behenate, magnesium acrylate, magnesium adipate,
Magnesium acetylene dicarboxylate, Magnesium acetoacetate, Magnesium azelaate, Magnesium citrate, Magnesium glyoxylate, Magnesium glutarate, Magnesium crotonate, Magnesium succinate, Magnesium isovalerate, Magnesium isobutyrate, Magnesium octoate, Magnesium valerate, Magnesium decanoate, magnesium nonanoate, magnesium docosenoate, magnesium undecenoate, magnesium elaidate, magnesium linolenate,
Magnesium hexanoate, Magnesium heptanoate, Magnesium myristate, Magnesium laurate, Magnesium butyrate, Magnesium oxalate, Magnesium tartrate, Magnesium suberate, Magnesium sebacate, Magnesium sorbate, Magnesium tetrolate, Magnesium hydroacrylate, Pimelic acid magnesium,
Examples include magnesium pyruvate, magnesium fumarate, magnesium propionate, magnesium maleate, magnesium malonaldehyde, magnesium malonate, etc. Among them, saturated fatty acid magnesium is preferred, and magnesium stearate, magnesium octoate, magnesium decanoate, and laurin Particularly preferred are magnesium oxides. Note that it is preferable to use the fatty acid magnesium in a form with as much moisture removed as possible. Examples of aromatic carboxylic acid esters used in the present invention include ethyl toluate, ethyl anisate, ethyl benzoate, among which ethyl benzoate, ethyl p-anisate, and ethyl p-toluate are particularly preferred. preferable. The organic solvent used in the present invention is 10
The organic compound is selected from organic compounds which are liquid at 1 atm at a temperature of 1 atm, preferably aliphatic and aromatic hydrocarbons having 5 to 10 carbon atoms. More specifically, n-pentane, n-hexane, n-heptane, benzene,
Examples include toluene. The general formula TiX ₄ used in the present invention (in the formula
is a halogen element. Examples of the titanium halide represented by ) include TiCl ₄ , TiBr ₄ , TiI ₄ and the like, with TiCl ₄ being particularly preferred. The catalyst component produced in the present invention is further n-
It is also possible to further enhance the effects of the present invention by washing with an organic solvent such as heptane. 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 the aromatic carboxylic acid ester is 0.01 to 1 mole of magnesium fatty acid. The titanium halide is used in an amount of 50 mol, preferably 0.1 to 5 mol, particularly preferably 0.3 to 2 mol, and 0.01 mol or more, preferably 1 mol or more. The method and temperature for contacting each substance in the present invention are not particularly limited, but the contact is usually carried out using a container equipped with a stirrer at a temperature ranging from room temperature to the boiling point of the titanium halide and the boiling point of the organic solvent. The contact time is also not particularly limited, but is usually 1 minute to 100 hours, preferably 10 hours.
The duration ranges from minutes to 10 hours. It is also possible to wash the composition obtained after the treatment using an organic solvent such as n-heptane. 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 is used in a molar ratio of 1 to 1000, preferably 1 to 300, 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 an organic solvent, and the 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 100Kg/cm ² ·G or less, preferably 50Kg/cm ² ·G or less. Olefins homopolymerized or copolymerized using the catalyst component produced by the method of the present invention include ethylene, propylene, 1-butene, 4-methyl-1
-Pentene etc. The present invention will be specifically explained below using Examples and Comparative Examples. Example 1 [Preparation of catalyst component] Commercially available magnesium stearate was prepared at 110°C.
10g vacuum baked for 1 hour, ethyl benzoate 1.6
ml, 30 ml of TiCl ₄ and 20 ml of toluene were placed in a glass container with an internal volume of 200 ml under a nitrogen atmosphere, and a stirring reaction was carried out at 65° C. for 2 hours. After the reaction was completed, the mixture was cooled to 45°C, left to stand, and the supernatant liquid was removed by decantation. Next, washing with 100 ml of n-heptane 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, when the solid and liquid in the catalyst component was separated and the titanium content in the solid was measured, it was 2.82% by weight. [Polymerization] Add 500 ml of n-heptane to an autoclave with a stirring device and a capacity of 1.5 that was completely purged with nitrogen gas.
was charged, and while maintaining a nitrogen gas atmosphere, 13.6 mg of triethylaluminum was charged, followed by 1.14 mg of the catalyst component as titanium atoms. Thereafter, the temperature was raised to 60°C, and polymerization was carried out for 2 hours while maintaining a pressure of 4 kg/cm ² ·G while introducing propylene gas. After the polymerization was completed, the obtained solid polymer was separated, heated to 80°C, and dried under reduced pressure. On the other hand, the amount of polymer dissolved in the polymerization solvent after concentrating the liquid is (A), 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). The polymerization activity (D) per catalyst component is expressed by the formula (D)=[(A)+(B)](g)/Amount of catalyst component (g). In addition, the yield (E) of crystalline polymer is expressed by the formula (E)==(C)/(B)×100(%), and the yield (F) of the total crystalline polymer is expressed by the formula (F)= Calculated from (C)/(A)+(B)×100(%). In addition, residual chlorine (G) in the produced polymer was measured by bomb combustion method. The results obtained are the first
As shown in the table. Example 2 Commercially available magnesium stearate at 110°C
10g vacuum baked for 1 hour, ethyl benzoate 2.0
ml, 30 ml of TiCl ₄ and 20 ml of toluene were placed in a glass container with an internal volume of 200 ml under a nitrogen atmosphere, and heated to 65°C.
A stirring reaction was carried out for 2 hours. 45℃ after completion of reaction
The mixture was cooled to a temperature of 100 mL, left to stand, and the supernatant liquid was removed by decantation. Next, washing with 100 ml of n-heptane was carried out repeatedly, and when chlorine was no longer detected in the washing solution, the washing was 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 2.42% by weight. The polymerization was carried out 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 the reaction temperature was 75°C. Note that the titanium content in the solid content at this time was 2.79% by weight. The polymerization was carried out in the same manner as in Example 1. The results obtained are shown in Table 1. Comparative Example 1 [Preparation of catalyst component] 100 g of MgCl ₂ and 31.5 g of ethyl benzoate are pulverized for 18 hours under a nitrogen gas atmosphere. Thereafter, 100 g of the pulverized composition was taken out and the internal volume was
The mixture was placed in a 2000 ml glass container, 500 ml of TiCl ₄ was added thereto, 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. Then n-heptane
Washing with 1000 ml 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, when the solid and liquid in the catalyst component was separated and the titanium content in the solid was measured, it was 1.28% by weight.
It was hot. [Polymerization] The polymerization was carried out in the same manner as in Example 1, except that 20.4 mg of triethylaluminum and 0.71 mg of the catalyst component as titanium atoms were used. The results obtained are shown in Table 1. Comparative Example 2 14.2 g of anhydrous magnesium acetate, 40.8 g of aluminum triisopropoxide, and 50 ml of decalin were placed in a 200 ml round bottom flask under a nitrogen atmosphere, and a stirring reaction was carried out at 170 to 230°C for 10 hours. Ta. Thereafter, the solvent was removed and drying was performed under reduced pressure to obtain a solid powder. The obtained solid powder was washed 10 times with 100 ml of dehydrated n-heptane, the solvent was removed, and the powder was further dried under reduced pressure to obtain a solid powder. Next, 80 ml of TiCl ₄ was added thereto, the mixture was heated to 150°C, and a stirring reaction was carried out for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, left to stand, and the supernatant liquid was removed by decantation. Then dehydration
- Washing with 100 ml of heptane was carried out repeatedly, and when chlorine was no longer detected in the washing solution, the washing was completed and used as a catalyst component. At this time, the solid and liquid in the catalyst component was separated and the content of titanium in the solid component was measured, and it was found to be 12.2% by weight. During polymerization, the catalyst components obtained were 1.62 mg of titanium atoms, 109 mg of triethylaluminum,
An experiment was carried out in the same manner as in Example 1 by charging 35 mg of ethyl p-toluate. The results are shown in Table 1, but no polymer was obtained whose polymerization characteristic values could be measured. Example 4 An experiment was carried out in the same manner as in Example 1, using 10 g of magnesium octoate vacuum baked at 70° C. for 7 hours. Note that the titanium content in the solid content at this time was 2.71% by weight. The polymerization was carried out in the same manner as in Example 1. The results obtained are shown in Table 1. 【table】

[Brief explanation of drawings]

FIG. 1 is a flowchart for explaining the present invention.

Claims (1)

[Claims] 1. A catalyst component for polymerizing olefins that is brought into contact with (a) magnesium fatty acid, (b) aromatic carboxylic acid ester, and (c) titanium halide represented by the general formula TiX ₄ (wherein X is a halogen element). In the production method, after contacting the fatty acid magnesium and the titanium halide, or the aromatic carboxylic acid ester and the titanium halide, in the presence of an organic solvent, the aromatic carboxylic acid ester or the fatty acid magnesium or said fatty acid magnesium,
A method for producing a catalyst component for polymerizing olefins, which comprises simultaneously bringing the aromatic carboxylic acid ester and the titanium halide into contact with each other.