JPH0442408B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a catalyst component that exhibits high activity when subjected to the polymerization of olefins and can obtain a stereoregular polymer in high yield. The present invention relates to a method for producing a catalyst component for polymerizing olefins, which comprises contacting magnesium with a titanium halide in the presence of an aromatic carboxylic acid ester, and contacting the obtained solid composition with a titanium halide. Conventionally, solid titanium halides have been well known and widely used as catalyst components for the polymerization of olefins. It is called the polymerization activity per titanium inside.)
Because of the low carbon content, a so-called deashing step to remove catalyst residues was unavoidable. Since this deashing process uses a large amount of alcohol or chelating agent, a recovery device or a regeneration device for the same is indispensable, and there are many resource, energy, and other related problems that should be resolved immediately by those skilled in the art. This was an important issue that needed to be addressed. In order to eliminate this complicated deashing process, many studies have been made and proposals have been made to increase the polymerization activity per titanium in the catalyst component, particularly in the catalyst component. In particular, a recent trend is that when transition metal compounds such as titanium halides, which are active ingredients, are supported on carrier materials such as magnesium chloride and used for polymerization of olefins, the polymerization activity per titanium in the catalyst component can be dramatically increased. There are many proposals for increasing the number of targets. 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 magnesium chloride is the only material that can effectively act as a carrier material. Attempts have also been made to use Furthermore, attempts have been made to use various diluents and the like in order to alleviate the adverse effects of magnesium chloride. However, the methods proposed so far do not sufficiently meet the demands of the technical field, which require not only increasing the polymerization activity per catalyst component but also maintaining a high yield of stereoregular polymers. No gains are suggested. For example, according to the method disclosed in JP-A-16986, sodium carbonate, calcium sulfate,
Alternatively, boron oxide or the like is added during the grinding process of the complex of magnesium chloride and titanium halide with an electron donating substance. However, even if such a carrier is mixed, if titanium halide is used in the form of a complex with an electron-donating substance, it will not be possible to achieve sufficiently satisfactory values not only in terms of polymerization activity but also in the yield of stereoregular polymers. It cannot be said that it is shown. Japanese Patent Publication No. 56-39767 exemplifies the use of B ₂ O ₃ in Example 11,
There is no specific teaching on the appropriate range of its usage and usage conditions, and under the conditions taught in the publication, the polymerization activity per catalyst component is extremely low, and the yield of total crystalline polymer is low. However, there are still problems such as not being in a satisfactory state. The present inventors have arrived at the present invention as a result of intensive research in order to solve the problems remaining in the prior art, and hereby propose the present invention. That is, the feature of the present invention is that (a) boron oxide which has been vacuum-calcined in advance and (b) magnesium halide are mixed in an amount of 0.1 to 10 g, preferably 0.5 to 10 g, of the magnesium halide per 1 g of the boron oxide. 5g
The solid composition obtained by contacting (c) the aromatic carboxylic ester in the presence of (d) the general formula
It is used as a catalyst component for the polymerization of olefins by contacting it with a titanium halide represented by TiX ₄ (wherein X is a halogen element). According to the present invention, it has become possible to further suppress residual chlorine, which has been a problem with catalyst components with magnesium chloride supports, which have 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 by the present invention, the amount of catalyst residue in the resulting polymer can be kept extremely low, and since the amount of residual chlorine is very small, The influence of chlorine on coalescence can be reduced. Furthermore, it shows extremely excellent effects in terms of the yield of stereoregular polymers. As the boron oxide used in the present invention, commercially available boron oxides can be appropriately selected and used, but it is preferable to vacuum bake the boron oxide before use. Magnesium halides used in the present invention include magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, and the like, with magnesium chloride being preferred. Examples of aromatic carboxylic acid esters used in the present invention include ethyl toluate, ethyl anisate, and ethyl benzoate. 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. After contacting the solid composition produced in the present invention with the titanium halide, the effect of the present invention can be further enhanced by further washing with an organic solvent such as n-heptane. 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, but usually 0.01 g of magnesium halide is used for 1 g of boron oxide.
Above, it is preferably used in the range of 0.1 to 10 g,
If the amount of magnesium halide used is less than 0.1 g, the activity of the catalyst will decrease, which is undesirable.
If the amount exceeds g, the halogen contained in the magnesium halide, especially chlorine, will have an adverse effect on the produced polymer, which is not preferable. In addition, aromatic carboxylic acid ester is present in the solid composition obtained by contacting boron oxide and magnesium halide.
It is used in a proportion of 50% by weight, preferably 5 to 30% by weight. In the present invention, the contact between boron oxide, magnesium halide, and aromatic carboxylic acid ester is usually carried out by mechanical means, and generally a ball mill, a vibration mill, a column-type mill, an impact mill, etc. are used. . The contact time naturally varies depending on the performance of the equipment used, but is usually 1.
Ranges from ~500 hours. Further, the contact temperature is not particularly limited, and may be within a contactable range. The catalyst component of the present invention is obtained by contacting the solid composition thus obtained with a titanium halide and then washing with an organic solvent as required. The contact between the titanium halide and the solid composition can be carried out using various methods, but for example, it is carried out in a container equipped with a stirrer at a temperature ranging from usually 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. The composition obtained after the above treatment is optionally treated with n-
Wash using an organic solvent such as heptane. At this time, the cleaning is considered to be completed when no halogen element is detected in the cleaning solution, and the solid and liquid are separated and dried, or an appropriate amount of organic solvent is added to form a slurry, and the method of the present invention can be carried out as it is. Used as a method for producing a catalyst component for polymerizing olefins. 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 in a molar ratio of 1 per mole of titanium atoms in the catalyst component.
-1000, preferably 1-300.
Further, it is not prohibited to add a third component such as an aromatic carboxylic acid ester during the polymerization. Polymerization can be carried out in the presence or absence of organic solvents. Further, the olefin monomer can be used in either a 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 to be homopolymerized or copolymerized using the catalyst component produced according to the present invention include ethylene, propylene, 1-butene, 4-methyl-1-
Penten et al. The present invention will be specifically explained below using Examples and Comparative Examples. Example 1 [Preparation of catalyst components] 10 g of commercially available boron oxide calcined in vacuum at 250°C for 5 hours, 20 g of magnesium chloride, and 6 ml of ethyl benzoate were mixed into a 25 mm diameter stainless steel ball in a nitrogen gas atmosphere with 4/5 of the total volume. It was placed in a filled vibrating mill pot with a capacity of 1.0, and pulverization was carried out at room temperature for 17 hours at a vibration frequency of 1430 v.pm and a shaking width of 3.5 mm. 50 ml of TiCl ₄ and 10 g of the solid composition obtained by the above pulverization treatment were charged into a 200 ml round bottom flask that was sufficiently purged with nitrogen gas and equipped with a stirrer.
The reaction was stirred at ℃ for 2 hours. 40 minutes after the reaction
The mixture was cooled to ℃, allowed 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 liquid, the washing was deemed to have been 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 content was measured, it was 1.08% by weight. [Polymerization] Add 500 ml of n-heptane to an autoclave with a stirring device and an internal volume of 1.5 that was completely purged with nitrogen gas.
13.6 mg of triethylaluminum and 0.57 mg of the catalyst component as titanium atoms were charged while maintaining a nitrogen gas atmosphere. 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 completion of polymerization, separate the obtained solid polymer and heat at 80℃.
and dried under reduced pressure. On the other hand, the amount of polymer dissolved in the polymerization solvent after concentrating the liquid is defined as (A), and the amount of solid polymer is defined as (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). The polymerization activity (E) per chlorine contained in the catalyst component is expressed by the formula (E)={(A)+(B)}(g)/amount of chlorine in the catalyst component (g). Furthermore, the yield (F) of crystalline polymer is expressed by the formula (F)=(C)/(B)×100(%), and the yield (G) of total crystalline polymer is expressed by the formula (G)=( Calculated from C)/(A)+(B)×100(%). The results obtained are shown in Table 1. Example 2 An experiment was conducted in the same manner as in Example 1, except that the reaction temperature after adding TiCl ₄ was changed to 75°C. In addition,
The titanium content in the solid content at this time was 0.94% by weight. The results obtained are shown in Table 1. Example 3 An experiment was conducted in the same manner as in Example 1, except that 6 g of commercially available boron oxide calcined in vacuum at 250° C. for 5 hours and 24 g of magnesium chloride were used. In addition,
The titanium content in the solid content at this time was 1.12% by weight. The results obtained are shown in Table 1. Example 4 Example 1 except that 12 g of commercially available boron oxide vacuum-calcined at 250°C for 5 hours, 18 g of magnesium chloride and 6.0 ml of ethyl benzoate were used, and the reaction temperature after adding TiCl ₄ was 85°C. The experiment was conducted in the same manner. Note that the titanium content in the solid content at this time was 1.03% by weight. Triethylaluminum is used during polymerization.
An experiment was conducted in the same manner as in Example 1, except that 108.8 mg, 39 mg of ethyl p-toluate, and 0.91 mg of titanium atoms were used as the catalyst component. The results obtained are shown in Table 1. Example 5 Example except that 15 g of commercially available boron oxide vacuum-calcined at 250°C for 5 hours, 15 g of magnesium chloride and 5.0 ml of ethyl benzoate were used, and the reaction temperature after adding TiCl ₄ was 136°C. The experiment was conducted in the same manner as in 1. Note that the titanium content in the solid content at this time was 1.30% by weight. Triethylaluminum 134.6 during polymerization
An experiment was conducted in the same manner as in Example 1, except that 55.6 mg of ethyl p-toluate and 1.14 mg of titanium atoms as the catalyst component were used. The results obtained are the first
As shown in the table. Comparative Example 1 An experiment was carried out in the same manner as in Example 1 except that 25 g of magnesium chloride and 7.5 ml of ethyl benzoate were used without using boron oxide. In addition,
The titanium content in the solid content at this time was 1.27% by weight. The polymerization was conducted in the same manner as in Example 1. The results obtained are shown in Table 1. Comparative Example 2 54 g of B ₂ O ₃ and 4.5 g of MgCl ₂ without vacuum firing based on Example 11 of the above-mentioned Japanese Patent Publication No. 56-39767.
The same experiment as in Example 4 of the present invention was conducted except that . The titanium content in the solid content at this time was 0.36% by weight. The polymerization was conducted in the same manner as in Example 4. The results obtained are shown in Table 1.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a flowchart showing the catalyst preparation process of the present invention.

Claims (1)

[Claims] 1. (a) Boron oxide which has been vacuum-fired in advance and (b) magnesium halide in a ratio of 0.1 to 10 g of the magnesium halide per 1 g of the boron oxide,
(c) The solid composition obtained by contacting the aromatic carboxylic acid ester in the presence of (d) the general formula TiX ₄ (in the formula
is a halogen element. ) A method for producing a catalyst component for polymerizing olefins, which comprises contacting with a titanium halide represented by: 2. Claim 1, wherein the ratio of the boron oxide and the magnesium halide is 0.5 to 5 g of the magnesium halide per 1 g of the boron oxide.
The method for producing the catalyst component for polymerizing olefins described above.