JPH0350765B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing a catalyst in which titanium halide is supported on magnesium halide. Conventionally, when producing polyolefins by industrially polymerizing olefins such as ethylene and propylene, a method was developed to improve the catalytic activity by supporting the titanium component of the Ziegler-Natsuta catalyst on a carrier, and this method has become popular as an ethylene polymerization catalyst. used in However, in the case of α-olefins such as propylene and butene, it is necessary to sterically control alkyl groups such as methyl groups and ethyl groups to form an isotactic structure in order to obtain useful crystalline polymers. In addition to improving the activity compared to the case of , it is important to control the stereoregularity of the resulting polymer. Regarding the control of stereoregularity, it has been proposed to improve the stereoregularity of the polymer produced by adding a catalyst consisting of a titanium compound supported on magnesium halide, organoaluminium, and a specific electron-donating compound as a third component. There is (Tokuko Showa 39-
12105 Special Publication No. 52-39431 and Special Publication No. 52-36153, etc.). However, the method of adding a third component has limitations, and it is necessary to improve the supported catalyst itself. As a result of various studies, the present inventors discovered that it is possible to further improve the performance of the catalyst by carrying out a specific method, and completed the present invention. An object of the present invention is to provide a method for providing a supported catalyst in which the amount of polyolefin obtained per supported catalyst is high and the stereoregularity of the obtained polyolefin is high. The present invention is for use in olefin polymerization, characterized in that magnesium halide containing an organic compound containing at least a C-O or C-N bond is contacted with liquid titanium halide, and then washed with an aromatic hydrocarbon compound. The present invention relates to a method for producing a solid catalyst component. That is, the present invention is characterized in that a more excellent supported catalyst is produced by supporting titanium halide through contact treatment with liquid titanium halide and then washing with an aromatic hydrocarbon compound. In the present invention, the magnesium halide containing an organic compound containing at least a C-O or C-N bond can be produced by various methods, and known magnesium halides and C-
A method of co-pulverizing organic compounds containing O or C-N bonds, in which magnesium halide is solubilized in a hydrocarbon compound with a suitable organic compound such as alcohol or ether, and then with silicon halide, titanium halide, alkyl aluminum, etc. Magnesium halide obtained by precipitation or a method in which other C-O or C-N bond-containing compounds are co-present during solubilization, or magnesium halide obtained by precipitation is further processed. It can also be obtained by contact treatment with a compound containing a C-O or C-N bond. Co-pulverization is preferred. Compounds containing C-O or C-N bonds include ethers, esters, orthoesters, orthosilicate esters, amines, amides, phosphate esters, alkoxy silicon compounds, etc. at least before use. used. In the present invention, following the above operation, the composition is treated with liquid titanium halide. The liquid titanium halide is preferably titanium tetrachloride, and titanium trichloride liquefied with ether or the like can also be used. The contact treatment temperature is from room temperature to 150°C, preferably from 50 to 100°C, and preferably under good stirring. In the present invention, excess titanium halide is then removed by filtration or decantation,
The solid components obtained are washed with aromatic hydrocarbons. Examples of aromatic hydrocarbons that can be used include benzene, toluene, xylene, ethylbenzene, cumene, chlorobenzene, O-dichlorobenzene, etc. The cleaning temperature may be around room temperature, and it may not be particularly hot or cold. There is no need to do so.
Washing may be carried out until the amount of titanium halide not supported on magnesium halide is approximately 1/100 or less of the amount of titanium halide supported.
The number of times varies depending on the method. By carrying out the method of the present invention, it is possible to produce a supported catalyst with a high amount of polyolefin obtained per supported catalyst and a high stereoregularity of the obtained polyolefin, which is industrially significant. The supported catalyst obtained by the method of the present invention is
In addition, by combining with organoaluminum compound stereoregularity improver, propylene, butene-
It can be used for the purpose of producing α-olefins such as 1 and hexene-1 alone or copolymers with each other or copolymers with ethylene. EXAMPLES The present invention will be explained in more detail below with reference to Examples. Example 1 (A) 20 g of magnesium chloride, 1 ml of ethyl orthoacetate, and 4 ml of 1,2-dichloroethane were placed in a 600 ml grinding pot containing 80 steel balls with a diameter of 12 mm prepared in a vibration mill under a nitrogen atmosphere. add
Grind for 40 hours. 10 g of the above pulverized product and 50 ml of titanium tetrachloride were added to a 200 ml round bottom flask and stirred at 80° C. for 2 hours, and then the supernatant liquid was removed by decantation. Next, 100 ml of toluene was added, the mixture was stirred at room temperature for 15 minutes, and the supernatant liquid was removed by decantation. The washing operation was repeated 7 times, and then another 100 ml of toluene was added to obtain an activated titanium component slurry. . When a portion of this slurry was sampled, toluene was evaporated, and analyzed, the Ti content in the supported catalyst was 1.68%. (B) Internal volume 5 which has been thoroughly dried and replaced with nitrogen.
50ml of toluene in a SUS-32 autoclave.
A catalyst mixture in which 30 mg of the above carrier catalyst component, 0.20 ml of toluethylaluminum, 0.14 ml of p-ethyl toluate, and 0.24 ml of diethylaluminum chloride were dissolved and dispersed was charged, and then 1.5 kg of liquid propylene was charged. Further, 1.6Nl of hydrogen was charged and the autoclave was heated with hot water to raise the internal temperature to 75°C, and polymerization was carried out at 75°C for 3 hours. After the polymerization was completed, unreacted propylene was discharged to obtain white polyperopylene. After drying under reduced pressure at 60℃, weigh it and calculate the yield and activity per catalyst.
Intrinsic viscosity and boiling n- of tetralin solution at 135℃
The ratio of the extracted residue to the weight before extraction when extracted with heptane for 10 hours was determined. The results are shown in the table. Examples 2 to 4, Comparative Examples 1 and 2 Example 1 except that the solvents shown in the table for washing and catalyst dispersion were replaced with toluene.
The experiment was carried out in the same manner. The results are also shown in the table. Example 5, Comparative Example 3 4 ml of 1,2-dichloroethane in Example 1
Example 5 was the same as Example 1, except that 1 ml of tetraethoxysilane was used instead of 1 ml of tetraethoxysilane, and in addition, the cleaning solvent and toluene in Example 1 were replaced with n-heptane. Comparative Example 3 is the case where The results are also shown in the table. 【table】

[Brief explanation of drawings]

FIG. 1 is a flowchart to aid in understanding the present invention.

Claims (1)

[Claims] 1. A magnesium halide containing an organic compound containing at least a C-O or C-N bond is contacted with liquid titanium halide, and then washed with an aromatic hydrocarbon compound. A method for producing a solid catalyst component for olefin polymerization. 2 Magnesium halide containing an organic compound containing at least a C-O or C-N bond is obtained by co-pulverizing magnesium halide and an organic compound containing at least a C-O or C-N bond. A method according to claim 1.