JPH0348211B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, poly-α-
This invention relates to a method for producing olefins. Conventionally, when industrially polymerizing olefins such as ethylene and propylene, a method has been developed to improve the catalytic activity by supporting the titanium component of the Ziegler-Natsuta catalyst on a carrier, and various improvements have been made since Japanese Patent Publication No. 12105/1983. Methods for producing catalysts have been proposed, and it is known that in the polymerization of olefins using these catalysts, polyolefins can be obtained in extremely high yields per catalyst. However, in the case of polymerization of α-olefins such as propylene and budene-1, in order to obtain useful crystalline polymers, the coordination of alkyl groups such as methyl groups and ethyl groups must be sterically controlled to create an isotactic structure. However, compared to the case of ethylene polymerization, the performance of the catalyst is still insufficient. As a result of various studies, the present inventors discovered that the performance of the catalyst could be improved by carrying out a specific method, and completed the present invention. An object of the present invention is to provide a method for polymerizing α-olefins with a high yield of polyolefins per catalyst. The present invention provides at least ethers, esters, orthoesters, orthosilicate esters, amines,
Magnesium chloride containing one or more compounds selected from amides, phosphate esters, and alkoxy silicon compounds is heated and contacted with a mixture of 5 to 80 vol% of a hydrocarbon compound and titanium tetrachloride, and the solid portion of the treated product is Separate and further divide this into 0~
α characterized by using a catalyst consisting of a solid catalyst component obtained by heating contact treatment with a mixture of 80 vol% of a hydrocarbon compound and titanium tetrachloride, and then washing the solid content with a hydrocarbon compound, and an organoaluminum compound. - A method for polymerizing olefins. That is, the present invention is characterized in that the yield of poly-α-olefin per solid catalyst is increased by using a solid catalyst component obtained by a special method. In the present invention, magnesium chloride containing at least one compound selected from ethers, esters, orthoesters, orthosilicate esters, amines, amides, phosphate esters, and alkoxy silicon compounds can be produced by various methods. A method of co-fractionation of magnesium chloride and at least one or more compounds selected from ethers, esters, orthoesters, orthosilicate esters, amines, amides, phosphate esters, and alkoxy silicon compounds, which is possible and known, When solubilizing a hydrocarbon compound with a suitable organic compound such as alcohol or ether and then precipitating magnesium halide with silicon halide, titanium chloride, alkyl aluminum, etc., ether, ester, orthoester is used. , a method in which one or more compounds selected from orthosilicate esters, amines, amides, phosphate esters, and alkoxysilicon compounds are present in the coexistence; It may be treated with one or more compounds selected from acid esters, amines, amides, phosphoric acid esters, and alkoxy silicon compounds. Preferably, it is obtained by co-pulverization. In the present invention, the magnesium chloride containing at least one compound selected from ether, ester, orthoester, orthosilicate ester, amine, amide, phosphoric acid ester, and alkoxy silicon compound obtained by the above operation is ~80vol
% hydrocarbon compound and titanium tetrachloride, and the solid part of this treated product is separated,
This is further heated and contacted with a mixture of 0 to 80 vol% of a hydrocarbon compound and titanium tetrachloride. 1
The second heating contact treatment is characterized by using a mixture of 5 to 80 vol% of a hydrogen carbonate compound and titanium tetrachloride. The hydrocarbon compounds used here are:
Saturated hydrocarbon compounds such as n-hexane and n-heptane, or aromatic hydrocarbon compounds such as benzene and toluene are used. activity is poor, and 80vol%
Even above, the activity is poor. The heating contact treatment is performed at 30 to 140℃, preferably 50 to 100℃, for 10 minutes to 4 minutes while stirring.
Time is enough. Following this heating contact treatment, the solid portion is separated. This separation is carried out by decantation or filtration, but it is not necessary to completely separate the liquid portion. This solid portion is then heated and contacted with titanium tetrachloride or a mixture of titanium tetrachloride and up to 80 vol% of a hydrocarbon compound. If the mixture contains more than 80 vol% of hydrocarbon compounds based on the total amount, the activity will be poor. The hydrocarbon compound used here and the conditions for the heat contact treatment are the same as those described above. It is of course possible to repeat the second heating contact treatment. Following the heating contact treatment, the solids are washed with a hydrocarbon compound. As the hydrocarbon compound used here, the above-mentioned compounds are preferably used, and there are no particular limitations on the washing temperature, as long as it is carried out at room temperature to 100°C, and the number of washings depends on the supported titanium. It is preferable to carry out the cleaning until the amount of titanium is less than 1/100, which is determined by the cleaning method. The organoaluminum compounds used in the present invention include trialkylaluminum such as triethylaluminum, tripropylaluminum, tributylaluminum, and trihexylaluminum, and dialkylaluminum chloride such as diethylaluminum chloride, dipropylaluminum chloride, and dibutylaluminum chloride. used in combination or in mixtures. The catalyst of the present invention is used for polymerization or copolymerization of α-olefins such as propylene, butene-1, and hexene-1, and further for copolymerization with ethylene. Preferably, C-O or C-
It is possible to further stably enhance the stereoregularity of the poly-α-olefin obtained by using an organic compound having an N bond, which is more preferable. By using the method of the present invention, polyolefins can be obtained in high yield per catalyst, and the present invention has great industrial significance. EXAMPLES The present invention will be explained in more detail with reference to Examples below. 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 equipped with a vibration mill and containing 80 steel balls with a diameter of 12 mm, under a nitrogen atmosphere. add
Grind for 40 hours. Into a 200 ml round bottom flask were added 10 g of the above pulverized product and 50 ml of an 8:2 mixture of titanium tetrachloride and n-hexane, and after stirring at 80°C for 2 hours, the supernatant liquid was removed by decantation. 8 of titanium chloride and n-hexane:
After adding 50 ml of the two mixtures and stirring at 80°C for 2 hours, the supernatant was removed by decantation. Next, 100 ml of n-heptane was added, and after stirring at room temperature for 15 minutes, the supernatant was removed by decantation. The washing operation to remove
- 100 ml of heptane was added to form a solid catalyst component slurry. Sample a portion of this slurry and
When heptane was evaporated and analyzed, the Ti content in the solid catalyst component was 1.38 wt%. (B) Inside volume 5 which has been thoroughly dried and replaced with nitrogen.
n-heptane in SUS-32 autoflave
50ml, 30mg of the above solid catalyst component, 0.20ml of triethyaluminum, 0.14ml of methyl p-toluate,
A catalyst mixture in which 0.24 ml of diethylaluminum chloride was dispersed was charged, then 1.5 kg of liquid propylene and 1.6 N of hydrogen were charged, and the internal temperature was raised to 75°C by heating the autoclave with hot water. Polymerization was carried out for 3 hours. After the polymerization was completed, unreacted propylene was discharged to obtain platinum polypropylene. After drying under reduced pressure at 60℃, weigh it to calculate the yield and activity per catalyst, and then dry at 135℃.
The results of determining the intrinsic viscosity of the tetralin solution and the ratio of the extracted residue to the weight before extraction when extracted with boiling n-heptane for 10 hours are shown in the table. Examples 2-6 Comparative Examples 1-2 The same procedure as in Example 1 was carried out except that the heating contact treatment was carried out under the conditions shown in the table. The results are shown in the table.

【table】

【table】 [Brief explanation of drawings]

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

Claims (1)

[Claims] 1 At least ether, ester, orthoester, orthosilicate ester, amine, amide,
Magnesium chloride containing one or more compounds selected from phosphate esters and alkoxy silicon compounds is heated and contacted with a mixture of 5 to 80 vol% of a hydrocarbon compound and titanium tetrachloride, and the solid portion of this treated product is separated. This is further heated and contacted with titanium tetrachloride or a mixture of titanium tetrachloride and a hydrocarbon compound of 80 vol% or less, and then the solid content is washed with a hydrocarbon compound to obtain a solid catalyst component and an organoaluminum compound. A method for polymerizing α-olefin, characterized by using a catalyst. 2. The method according to claim 1, wherein the α-olefin is propylene, propylene and other higher α-olefins, or those to which ethylene is further added.