JPH0333133B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a linear α-olefin, and more specifically, a method for producing a linear α-olefin by oligomerizing ethylene, which includes:
The present invention relates to a method for producing oligomers of α-olefin with high purity and improving the yield of middle distillates. [Prior Art] Linear α-olefins are useful as modifying comonomers in the field of producing polyolefins, or as plasticizers and surfactants when alcoholized. Such linear α-olefins are generally produced by oligomerizing ethylene in the presence of a catalyst. As the catalyst used at this time, for example, a two-component catalyst consisting of titanium tetrachloride and ethylaluminum dichloride is known. On the other hand, in recent years, a two-component catalyst using a zirconium (Zr) compound instead of the titanium compound has been proposed as a catalyst with even higher activity. For example, JP-A-58-109428, JP-A-58-30042, and JP-A-58-201729 each disclose a two-component catalyst containing a Zr compound and an Al compound; Publication No. 113138
Two-component catalysts each containing a Zr compound and a Zn compound are disclosed. [Problems to be Solved by the Invention] However, when oligomerizing ethylene using a two-component catalyst containing the above-mentioned Zr compound, the final product contains a very large amount of wax. Or, the yield of only oligomers with a small number of carbon atoms, for example, oligomers with 4 carbon atoms, will be high, and the obtained α-
Problems arise such as the purity of the olefin itself being extremely low. [Means for Solving the Problems] The present invention solves the conventional problems and provides a method for producing linear α-olefins by oligomerizing ethylene in the presence of a catalyst.
The yield of the middle distillate is high, and the obtained α
- The purpose of the present invention is to provide a method that allows high purity olefin and further reduces the amount of wax that ultimately remains. As a result of extensive research to achieve the above object, the present inventors have found that a novel three-component catalyst, which is made by adding a third component to be described later to a Zr compound and an Al compound, exhibits excellent effects. The present invention was completed after confirming that the following could be obtained. That is, the method for producing a linear α-olefin of the present invention has the following formula: ZrXaAb (1) (wherein, X and A may be the same or different and each represents Cl, Br or I). .
In addition, a and b are both integers of 0 to 4, and a number satisfying a+b=4) with zirconium halide; ~20 alkyl group, Q represents Cl, Br or I, c and d
are selected from 1, 1.5 and 2, respectively, and represent a number satisfying c+d=3); and a halogenated alkylalumium compound selected from the group consisting of methyl disulfide, thiophene, aniline and thiourea. It is characterized in that a gas containing ethylene is polymerized in the presence of a mixture with one type of compound. [Specific Description] The method of the present invention is characterized by using the novel three-component catalyst described above. First, the first component, zirconium halide, is not particularly limited as long as it satisfies the conditions shown in formula (1) above, but ZrCl ₄ is particularly preferred. . Then, the second
The alkylaluminum halide compound which is a component is represented by the above formula (2). In formula (2), R and Q are not particularly limited as long as they are listed above, but among them, R is preferably an ethyl group, propyl group, or butyl group, and Q is preferably Cl. preferable. Specifically, diethylaluminum chloride is preferred. Furthermore, as a third component, methyl disulfide ((CH ₃ ) ₂ S ₂ ), thiophene (C ₄ H ₄ S), aniline (C ₆ H ₅ NH ₂ ) and thiourea ((NH ₂ ) ₂ CS) One or more compounds selected from: In addition, in such a three-component catalyst, the blending amount of each component is not particularly limited, but is set so that the molar ratio of alkyl aluminum halide to zirconium halide (Al/Zr) is 1 to 5. It is preferable. Furthermore, this catalyst can also be used diluted with chlorobenzene or the like. Next, the linear α of the present invention using the above catalyst
- Describe the method for producing olefin. first,
Approximately 100% of the above catalyst or catalyst solution was added to the reaction vessel.
Activation treatment is performed by heating for 30 minutes to 2 hours until the temperature reaches ℃. Thereafter, high purity ethylene gas is introduced into the reaction vessel to effect oligomerization. The temperature at this time is 50℃ or higher, preferably
100-150℃, pressure is 5Kg/cm2 ^or more, preferably 25
Kg/cm ² or more, and the reaction time is set to 5 minutes to 2 hours, preferably 15 minutes to 1 hour. [Example] Preparation example (preparation of catalyst solution) A slurry solution in which the indicated amount (mmol) of the indicated zirconium compound was added to 100 ml of dry chlorobenzene was placed in an autoclave with an inner volume of 2 and equipped with a stirrer in the presence of dry Ar gas. It was introduced in On the other hand, the indicated amounts (mmol) of the aluminum compound and the third component were added to 150 ml of dry chlorobenzene, stirred at room temperature for 10 minutes, and introduced into the above autoclave to obtain a catalyst solution. Examples 1 to 9 and Comparative Examples 1 to 3 Linear α-olefins were produced using each of the catalyst solutions obtained above. That is, first, activation treatment was carried out by heating the catalyst solution in an autoclave for 1 hour to 100° C. while stirring. When the temperature reached 100°C, high purity ethylene gas was rapidly blown into the autoclave until the pressure reached 35 kg/cm ² . Thereafter, the necessary ethylene to maintain this pressure in the autoclave continued to be introduced. The reaction was continued under these reaction conditions for about 30 minutes, and then a methanol solution containing sodium hydroxide was injected into the autoclave to deactivate the catalyst and terminate the reaction. In the post-treatment process, in order to reduce the loss of _C4 to _C6 light components, _C4 is removed during autoclave depressurization.
The ~ _C6 reaction product was trapped in a dry ice-methanol bath. Regarding other reaction products, first, the wax content was filtered out using filter paper, and then the filtrate was washed twice with 500 ml of pure water, and then dried over potassium carbonate. The clear solution thus obtained was analyzed by gas chromatography. On the other hand, the filtered wax was air-dried, dried in a vacuum dryer at a pressure of 20 mmHg, and then weighed. The composition ratio (wt%) and purity (wt% of linear α-olefin in each fraction) of each fraction of α-olefin obtained by the above process and the composition ratio (wt%) of wax are shown in the table. Also listed.

【table】

[Table] [Effects of the Invention] As is clear from the above explanation, in the method of the present invention, since the novel three-component catalyst as described above is used, the C The yield of middle distillates from ₆ to _C20 is high,
Moreover, it was confirmed that the purity of the linear α-olefin in each fraction was high, and the composition ratio of the produced wax was reduced. Therefore, its usefulness in the polymer chemical industry is extremely large.

Claims (1)

[Claims] Primary formula: ZrX _a A _b (1) (wherein, X and A may be the same or different and represent Cl, Br or I, respectively.
In addition, a and b are both integers of 0 to 4, and a number satisfying a+b=4); With zirconium halide represented by the following formula: AlR _c Q _d (2) (wherein, R is represents an alkyl group having 1 to 20 carbon atoms, Q represents Cl, Br or I, c and d
is selected from 1, 1.5 and 2, respectively, and represents a number satisfying c+d=3); and an alkyl aluminum halide compound selected from the group consisting of methyl disulfide, thiophene, aniline and thiourea. A method for producing a linear α-olefin, which comprises polymerizing a gas containing ethylene in the presence of a mixture with one or more compounds. 2. The method according to claim 1, wherein the zirconium halide is zirconium tetrachloride. 3. Claim 1, wherein the alkylaluminum halide is diethylaluminum chloride.
The method described in section.