JPH06104627B2 - Method for producing linear α-olefin - Google Patents

Description

TECHNICAL FIELD The present invention relates to an improvement in a method for producing a linear α-olefin. More specifically, the present invention provides a linear α-olefin useful as a raw material for a polyolefin modifying comonomer, a plasticizer, a surfactant, etc., with a highly active and highly stable catalyst to achieve high product purity. In addition, the present invention relates to a method for producing so as to obtain an optimum product distribution (high yield of useful linear α-olefin having 6 to 18 carbon atoms).

[Prior Art] Conventionally, linear α-olefins are known to be useful, for example, as a comonomer for modifying polyolefins or as a raw material for plasticizers, surfactants, and the like, and particularly have 6 to 18 carbon atoms. The linear α-olefins are useful and widely used.

Such linear α-olefins are usually produced by catalytically oligomerizing ethylene in the presence of a Ziegler catalyst. As the catalyst, various ones are known, for example, titanium tetrachloride is used as a transition metal compound, and a two-component catalyst composed of this and ethylaluminum dichloride, or this system for improving the selectivity is used. A catalyst formed by adding a third component to the above has been proposed.

However, in systems using these titanium compounds, the catalytic activity and selectivity are not always sufficient.
The problem is that it is not satisfactory.

On the other hand, various catalyst systems using zirconium compounds as transition metal compounds have been disclosed (JP-B-50-30042, JP-A-58-109428, JP-A-58-113138, and JP-A-58-113138). 58-201729). However, in the system using these zirconium compounds, although the catalytic activity is higher than that in the system using the titanium compound, an extremely large amount of wax is produced (Japanese Patent Laid-Open No. 58-109).
No. 428, JP-A-58-113138) or an extremely high yield of an oligomer having four carbon atoms and a low purity of α-olefin (JP-A-58-201729). There are drawbacks.

[Problems to be Solved by the Invention] The present invention improves the drawbacks of the catalyst in the conventional method for producing a linear α-olefin, uses a catalyst having high activity and excellent stability, The object of the present invention is to provide a method for producing a linear α-olefin having a product distribution (high yield of useful linear α-olefin having 6 to 18 carbon atoms) and having high product purity. Is.

[Means for Solving the Problem] The present inventors have found that the linear α- which has high activity and excellent stability.
As a result of earnest research on olefin production catalysts,
A specific zirconium halide and two alkylaluminum compounds are used to define the order of their use,
In addition, a catalyst is formed at a predetermined temperature and time, and by using this catalyst, oligomerization of ethylene is carried out in the presence of a specific ligand, resulting in high activity, excellent stability, and optimum product distribution. It was found that a linear α-olefin with high product purity can be easily obtained, and the present invention has been completed based on this finding.

That is, the present invention provides (A) a general formula ZrXaA _4- a (wherein X and A may be the same or different and each represents a chlorine atom, a bromine atom or an iodine atom, and a is 0 or Zirconium halide represented by the formula: (B) a General formula AlR _1.5 Q _1.5 (wherein R is an alkyl group having 1 to 20 carbon atoms, Q is a chlorine atom, a bromine atom or iodine). An alkylaluminum compound represented by the formula (A), R and Q may each be a combination of two or more kinds, and (B) a general formula AlR'bQ'3 _- b (wherein R'is the number of carbon atoms). 1 to 20 alkyl groups, Q'represents a chlorine atom, a bromine atom or an iodine atom, R'and Q'may each be a combination of two or more kinds, and b is an integer of 1 to 3.) A catalyst consisting of a mixture of alkylaluminum compounds represented by Method for producing a linear α-olefin by oligomerizing a gas containing ethylene in the presence of a ligand composed of one or more compounds selected from sulfur compounds, phosphorus compounds and nitrogen compounds In preparing the catalyst in (1), (1) the zirconium halide concentration of the component (A) is
40 to 140 mmol / solvent 1 (2) The catalyst preparation temperature is 40 to 75 ° C when an aromatic hydrocarbon is used as a solvent, and 50 when an alicyclic hydrocarbon is used.
˜100 ° C., (3) Catalyst preparation time is 10 minutes to 8 hours, (4) Catalyst is charged in the order of (A) component zirconium halide, and (B) B component. The method for producing a linear α-olefin, characterized in that the preparation is carried out by satisfying the condition that the alkylaluminum compound of (1) is added, and then the alkylaluminum compound of the component (B) is added (hereinafter referred to as the first invention). Second)
In the invention of (1), the catalyst is added in the order of (4) described above, after the zirconium halide of the component (A) is added, and then the alkylaluminum compound of the component (B) and the alkylaluminum compound of the component (B) are added. The method for producing a linear α-olefin according to the third aspect of the present invention is characterized in that the order of introducing the catalyst of (4) in the first aspect of the invention is (B) the alkylaluminum compound of the component and (B) A method for producing a linear α-olefin, characterized in that the component (A), an alkylaluminum compound, is added, and then the (A) component, a zirconium halide compound, is added, and the fourth invention is the first invention. In the invention, the order of introducing the catalyst of (4) is as follows: (B) After the alkylaluminum compound of the component (b) is added, the halogenated zirconium compound of the component (A) is added. It is a method for producing a linear α-olefin, which comprises charging and then charging the alkylaluminum compound of the component (B).

Hereinafter, the present invention will be described in detail.

The catalyst used in the method of the present invention is formed from zirconium halide as the component (A) and two kinds of alkylaluminum compounds as the component (B).

Here, the zirconium halide as the component (A) has a structure represented by the general formula ZrXaA _4- a (I) (wherein X, A and a in the formula are the same as above), and X in the formula is And A may be the same or different from each other. Examples of such a zirconium halide include ZrCl ₄ ,
Examples thereof include ZrBr ₄ , ZrI ₄ , ZrBrCl ₃ and ZrBr ₂ Cl ₂ , and among these, ZrCl ₄ is preferable. The zirconium halide may be used alone or in combination of two or more.

Next, the alkylaluminum compound as the component (B) is
General formula AlR _1.5 Q _1.5 (II) (wherein R and Q are the same as defined above), and the alkyl group R has 1 to 20 carbon atoms. The formula (II) is Al ₂ R ₃ Q
It can also be represented by ₃ . Examples of such an alkylaluminum compound include Al ₂ (CH ₃ ) ₃ Cl ₃ , Al ₂ (CH ₃ ) ₃ Br ₃ , Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ , Al ₂ (C ₂ H ₅ ). ₃ Br ₃ , Al ₂ (C ₂ H ₅ ) ₃ I ₃ , Al ₂ (C ₂ H ₅ ) ₃ BrCl ₂ , Al ₂ (C ₃ H ₇ ) ₃ Cl ₃ , Al ₂ (iso-C ₃ H ₇ ) ₃ Cl ₃ , Al ₂ (C ₄ H ₉ ) ₃ Cl ₃ , Al ₂ (iso-C ₄ H ₉ ) ₃ Cl ₃ , Al ₂ (C ₅ H ₁₁ ) ₃ Cl ₃ , Al ₂ (C ₈ H ₁₇ ) ₃ Cl ₃ , Al ₂ (C ₂ H ₅ ) ₂ (CH ₃ ) Cl _{3 and the} like. Among these, those having a methyl group, an ethyl group, a propyl group or a butyl group as R are preferable, and those having an ethyl group are particularly preferable. A chlorine atom is preferable as Q. Preferable examples of such alkylaluminum include ethylaluminum sesquichloride [Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ ]. These alkylaluminum compounds may be used alone or in combination of two or more.

In addition, the alkyl aluminum compound (B) (b) is
It has a structure represented by the general formula AlR'bQ'3 _- b ... (III) (R ', Q'and b in the formula are the same as described above), and the number of carbon atoms of the alkyl group R'is 1
~ 20 things. Examples of such an alkylaluminum compound include Al (CH ₃ ) ₃ , Al (C ₃ H) ₃ , Al (C ₃ H ₇ ) ₃ , ,, Al (iso-C ₃ H ₇ ) ₃ , Al (C ₄ H ₉ ) ₃ ,, Al (iso-C ₄ H ₉ ) ₃ ,, Al (C ₅ H ₁₁ ) ₃ ,, Al (C ₆ H ₁₃ ) ₃ ,, Al (C ₄ H ₁₇ ) ₃ ,, Al (C ₂ H ₅ ) ₂ Cl, Al (C ₂ H ₅ ) ₂ Br, Al (C ₂ H ₅ ) ₂ I, Al (C ₂ H ₅ ) Cl ₂ , Al (C ₂ H ₅ ) Br ₂ , Al (C ₂ H ₅ ) I _{2 and the} like. Of these, R'is preferably an ethyl group, a propyl group, a butyl group or an isobutyl group,
Particularly, an ethyl group is preferable, a chlorine atom is preferable as Q ', and b is preferably 2 or 3. Specific examples of such substances include triethylaluminum and diethylaluminum chloride. These alkylaluminum compounds may be used alone or in combination of two or more.

In the present invention, the above-mentioned catalyst is prepared by using a negatively active solvent such as aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, ethylbenzene, dichlorobenzene, chlorotoluene or halogen substituted compounds thereof; pentane, hexane, heptane, octane, It is carried out using a solvent such as aliphatic paraffins such as nonane and decane; alicyclic hydrocarbons such as cyclohexane and decalin; haloalkanes such as dichloroethane and dichlorobutane.

The temperature at the time of preparing the catalyst is selected in the range of 40 to 75 ° C., preferably 50 to 70 ° C. when an aromatic hydrocarbon is used as a solvent, and when the alicyclic hydrocarbon is used as a solvent. 50
To 100 ° C, preferably 60 to 80 ° C. If this temperature is lower than the lower limit temperature, the product purity of the obtained linear α-olefin may be low, and if it is higher than the upper limit temperature, heavy components such as wax having 20 or more carbon atoms tend to increase. The catalyst preparation time is selected in the range of 10 minutes to 8 hours, preferably 30 minutes to 3 hours. Further, the concentration of zirconium halide as the component (A) during the preparation of the catalyst is 40 to 40 from the viewpoint of product distribution, catalytic activity, and catalyst stability.
140 mmol / solvent 1, preferably 60-120 mmol /
It is selected within the range of solvent 1. If this concentration is less than 40 mmol / solvent 1, the catalytic activity tends to economically decrease and the light content tends to increase. If it exceeds 140 mmol / solvent 1, the catalytic activity decreases with time and the heavy content is extremely heavy. Only quality product distribution can be obtained.

Regarding the order of adding each component when preparing the catalyst, there are four modes as in the first to fourth inventions. The first is a method in which zirconium halide as the component (A) is charged into a solvent, then an alkylaluminum compound as the component (B) is charged, and then an alkylaluminum compound as the component (B) is charged. 2 is a method in which after the zirconium halide as the component (A) is charged, the alkylaluminum compound as the component (B) and the alkylaluminum compound as the component (B) are simultaneously charged, and the third is the component (B) Is a method of adding the alkylaluminum compound of (B) and the alkylaluminum compound of (B), and then adding the zirconium halide compound of (A). Then, the zirconium halide compound as the component (A) is added, and then the alkylaluminium compound as the component (B) is added. A method for introducing arm compound.

In the third method, the order of adding the (B) a component and the (B) b component is arbitrary, and the (B) a component may be added first, or the (B) b component may be added first. You may
Alternatively, a method in which the component (B) and the component (B) are added at the same time may be used. However, if the catalyst is prepared in a charging order other than the above order, only a catalyst having low activity can be obtained.

The reason why the order of adding the catalyst components is limited can be explained as follows. That is, the reaction active point is on the ZrCl ₄ side of the transition metal, and the activity is exhibited only after forming a complex with the alkylaluminum compound. in this case,
The catalytic activity is higher when the transition metal of the component (B) of the alkylaluminum compound is more coordinated.

The coordination ability of the alkylaluminum compound to the transition metal is (B) b >> (B) a, and the transition metal compound zirconium halide compound is added to the binary mixture of (B) b and (B) b. When added or vice versa, no reduction in catalyst activity is seen. However, when the zirconium halide compound which is a transition metal compound and the component (B) are brought into contact with each other independently, the coordination of the component (B) is suppressed even if the component (B) is added thereafter, and the catalytic activity of the component (B) is suppressed. You can only get a low price.

As described above, when the catalyst is prepared in an order other than the above-mentioned four kinds of order, only a catalyst having low activity can be obtained.

Next, the usage ratio of the (A) component and the (B) component is usually Al / Z.
The r molar ratio is selected to be in the range of 1 to 15, and the ratio of the B component to the B component used in the (B) component is usually in the range of 2 to 10 B component / B component (molar ratio). To be chosen.

In the present invention, ethylene is oligomerized using the catalyst thus prepared, and at this time, at least one compound selected from sulfur compounds, phosphorus compounds and nitrogen compounds is used as a ligand. Is used.

Here, the sulfur compound is not particularly limited, but usually, for example, dimethyl sulfide, diethyl sulfide, dipropyl sulfide,
Thioethers such as dihexyl sulfide, dicyclohexyl sulfide, diphenyl thioether; dialkyl disulfide compounds such as dimethyl disulfide, diethyl disulfide, dipropyl disulfide, dibutyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, ethylmethyl disulfide; thiophene, 2
-Methylthiophene, 3-methylthiophene, 2,3-dimethylthiophene, 2-ethylthiophene, thiophenes such as benzothiophene; Tetrahydrothiophene, thiopyran and other heterocyclic sulfur compounds; Diphenylsulfur,
Aromatic sulfur compounds such as diphenyl disulfide, methylphenyl disulfide, and methylphenyl sulfur; thioureas; sulfides such as methyl sulfide, ethyl sulfide, and butyl sulfide are preferably used.

Next, the phosphorus compound is not particularly limited, but usually, for example, phosphines such as triphenylphosphine, triethylphosphine, tributylphosphine, tripropylphosphine, trioctylphosphine, tricyclohexylphosphine and the like are preferably used.

Further, the nitrogen compound is not particularly limited, but usually, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, decylamine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, Dibutylamine, diphenylamine, methylphenylamine, trimethylamine, triethylamine, tributylamine, triphenylamine,
Organic amines such as pyridine and picoline are preferably used.

Among these sulfur compounds, phosphorus compounds and nitrogen compounds, dimethyl disulfide, thiophene, thiourea, triphenylphosphine, tributylphosphine, trioctylphosphine and aniline are particularly preferably used. The above compounds may be used alone or in combination of two or more.

When a sulfur compound is used as the ligand, the amount of this ligand is usually in the range of 1 to 20 mol per 1 mol of the zirconium halide as the component (A), and a phosphorus compound or a nitrogen compound is used. In this case, it is usually selected in the range of 0.5 to 10 mol per 1 mol of zirconium halide as the component (A).

The oligomerization of ethylene in the process of the present invention is carried out using the above catalyst in the presence of a ligand, and an organic solvent is also usually used in that case. As the organic solvent, those mentioned at the time of preparing the catalyst can be used. The ethylene oligomerization reaction is usually carried out at a temperature of 100 to 150 ° C. under a pressure of 25 kg / cm ² -G or more. The reaction time depends on the temperature and pressure and cannot be determined unconditionally, but 15 minutes to 1 hour is usually sufficient.

Regarding the treatment of the reaction product liquid, after the unreacted ethylene dissolved therein is vaporized by adiabatic flash,
The catalyst was deactivated and deashed, then solvent and α
The olefin is separated by distillation. The recovered unreacted ethylene and solvent are recycled to the reaction system. α
-Olefin is produced as a mixture of various α-olefins having 4 or more carbon atoms by the polymerization reaction of ethylene, but various α-olefins can be respectively obtained by multistage distillation, and desired by selecting reaction conditions. It is possible to obtain a large amount of α-olefin having a carbon number of.

According to the method of the present invention, a highly active and highly stable catalyst can be prepared by defining the order of adding the component (A), the component (B) and the component (B) and the catalyst preparation conditions. Moreover, it is possible to produce a linear α-olefin having an optimum product distribution.

FIGS. 1 to 6 show flowcharts of different examples of Ziegler type catalysts used in the present invention.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The invention is not limited by these examples.

Example 1 (1) Preparation of catalyst solution In a flask with a stirrer having an internal volume of 1000 ml, 50 mmol of anhydrous zirconium tetrachloride and 500 ml of dried benzene were introduced and stirred for 10 minutes. Triethylaluminum [(C ₂ H ₅ ) ₃ Al] 41.7 mmol was added to this, and after stirring for about 10 minutes, ethylaluminum sesquichloride [(C ₂ H ₅ ) ₃ Al ₂ Cl ₃ ] 208.3 mmol, Al / Zr A molar ratio of 5, [(C ₂ H ₅ ) ₃ Al ₂ Cl ₃ / (C ₂ H ₅ ) ₃ Al molar ratio of 5] was added, and a complex was formed while stirring at 60 ° C. for 30 minutes.

Next, in a 500 ml three-necked flask, benzene 250 ml and the complex solution were added with 0.05 mM ZrCl ₄ under an argon atmosphere.
(C ₂ H ₅ ) ₃ Al ₂ Cl ₃ was introduced at 0.21 mmol and (C ₂ H ₅ ) ₃ Al was introduced at 0.04 mmol, and the mixture was stirred at room temperature for 10 minutes to prepare a catalyst solution.

(2) Production of linear α-olefin In the autoclave equipped with a stirrer under a dry argon atmosphere, the catalyst solution prepared in (1) above was introduced by pressure-feeding with argon, and then 0.30 mmol of thiophene was added. . At this time, the temperature of the autoclave is 50
It was kept at ~ 60 ° C. After the addition of the catalyst and thiophene was completed, stirring was started, high-purity ethylene gas was rapidly blown into the autoclave until the pressure reached 65 kg / cm ² -G, and then the temperature was raised to 120 ° C. Ethylene continued to be introduced in the amount required to maintain the pressure. After continuing the reaction for 30 minutes while maintaining these reaction conditions, the catalyst was deactivated by injecting an aqueous sodium hydroxide solution into the autoclave to terminate the reaction. The post-treatment process is as follows.

First, 20 g of undecane for gas chromatography internal standard was added to the reaction product, and then the wax component was filtered off using a filter paper. The wax component on the filter paper was thoroughly washed with benzene, and the light component in the wax was dropped into the filtrate. The reaction product of the filtrate was washed twice with 500 ml of pure water and then dried over anhydrous potassium carbonate.

The transparent reaction product thus obtained was analyzed by gas chromatography. The yield of the product was determined by the internal standard method.

On the other hand, the wax component separated by filtration was air-dried and then dried in a vacuum drier having a pressure of 20 mmHg, and then the weight thereof was measured.

The yield of the C _{4 to} C ₈ fraction was estimated from the Schultz-Flory distribution because loss inevitably occurs in operation.

The above results are shown in Table 1.

Example 2 The procedure of Example 1 was repeated, except that the complex preparation time was 120 minutes. The results are shown in Table 1.

Example 3 The procedure of Example 1 was repeated, except that the amounts of catalyst component and ligand used in the reaction were changed as shown in Table 1. The results are shown in Table 1.

Example 4 The procedure of Example 2 was repeated, except that the amounts of catalyst component and ligand used in the reaction were changed as shown in Table 1. The results are shown in Table 1.

Example 5 The procedure of Example 1 was repeated, except that the complex preparation conditions were 70 ° C. and 120 minutes. The results are shown in Table 1.

Comparative Example 1 The procedure of Example 1 was repeated, except that the temperature for preparing the complex was 20 ° C. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 1 was repeated, except that the complex preparation temperature was 80 ° C. The results are shown in Table 1.

Comparative Example 3 The procedure of Example 3 was repeated, except that the preparation temperature of the complex was 25 ° C. The results are shown in Table 1.

Example 6 In Example 1, in the preparation of the complex, after the addition of ZrCl ₄ ,
(C ₂ H _{5) 3} Al and (C ₂ H _{5) 3} Al ₂ Cl ₃ and except that the added simultaneously was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 In Example 1, in the preparation of the complex, after adding ZrCl ₄ ,
(C ₂ H _{5) 3} Al ₂ a Cl ₃ was added, was carried out in the same manner as in Example 1 except thereafter (C ₂ H _{5) 3} that the addition of Al. The results are shown in Table 1.

Example 7 In Example 1, (C ₂ H ₅ ) ₃ Al ₂ Cl was used during the preparation of the complex.
Example 3 was carried out in the same manner as in Example 1 except that ₃ and (C ₂ H ₅ ) ₃ Al were simultaneously added, and then ZrCl ₄ was added. The results are shown in Table 1.

Example 8 The procedure of Example 2 was repeated, except that the complex preparation temperature was changed to 50 ° C. The results are shown in Table 1.

Example 9 The procedure of Example 8 was repeated, except that the complex preparation time was 240 minutes. The results are shown in Table 1.

Example 10 In Example 1, the ZrCl ₄ concentration during the preparation of the complex was 70 mmol / solvent 1, and after the catalyst was prepared, it was cooled to room temperature.
It carried out like Example 1 except having used the catalyst after the required number of days. The results are shown in Table 2.

Example 11 The procedure of Example 1 was repeated, except that after the catalyst was prepared, it was cooled to room temperature and the catalyst was used after the required number of days. The results are shown in Table 2.

Comparative Example 5 In Example 1, the ZrCl ₄ concentration at the time of preparing the complex was set to 30 mmol / solvent 1, and the catalyst was cooled to room temperature after preparation.
It carried out like Example 1 except having used the catalyst after the required number of days. The results are shown in Table 2.

Comparative Example 6 In Example 1, the ZrCl ₄ concentration during the preparation of the complex was 150 mmol / solvent 1, and the catalyst was cooled to room temperature after preparation.
It carried out like Example 1 except having used the catalyst after the required number of days. The results are shown in Table 2.

Example 12 In Example 1, cyclohexane was used as a solvent for the catalyst preparation, and the Al / Zr molar ratio was 7, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ / (C ₂ H ₅ ) ₃
The Al molar ratio was 3.5, the complex preparation conditions were a temperature of 70 ° C., a time of 180 minutes, a ZrCl ₄ concentration of 100 mmol / solvent 1, and the temperature was adjusted to room temperature after preparation of the catalyst. It carried out like Example 1. The results are shown in Table 3.

Example 13 In Example 12, the preparation temperature of the complex was 60 ° C and the preparation time was
It carried out like Example 12 except having set it as 30 minutes. The results are shown in Table 3.

In the case of a cycloxane solvent, when a complex is prepared at a low temperature, it takes time for the catalyst to stabilize after the catalyst is prepared from the complex. Therefore, it is desirable to prepare the complex at a higher temperature than in the case of benzene.

Example 14 In Example 1, cyclohexane was used as a solvent at the time of catalyst preparation, Al / Zr molar ratio was 8, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ / (C
₂ H ₅ ) ₃ Al molar ratio is 3.5 and the complex preparation conditions are temperature 70
The same procedure as in Example 1 was repeated except that the temperature was 30 ° C. and the temperature was 30 minutes. The results are shown in Table 4.

Example 15 Example 14 was repeated except that (C ₂ H ₅ ) ₃ Al and (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ were simultaneously added during the preparation of the complex, and then ZrCl ₄ was added. Performed as in Example 14. The results are shown in Table 4.

Example 16 Example 14 was repeated except that ZrCl ₄ was added after the addition of (C ₂ H ₅ ) ₃ Al in the preparation of the complex, and then (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ was added. Performed as in Example 14. The result is the fourth
Shown in the table.

Comparative Example 7 In Example 14, when the complex was prepared, (C ₂ H ₅ ) ₃ Al ₂ Cl _{3 was used.}
Was added, then ZrCl ₄ was added, and then (C ₂ H ₅ ) ₃ Al was added, and the same procedure as in Example 14 was performed. The results are shown in Table 4.

In Example 17 Example 14, was added _{(C 2 H 5) 3 Al} (C 2 H 5) after the addition of ₃ Al ₂ Cl ₃ in the preparation of the complexes, except that then the addition of ZrCl ₄ implementation Performed as in Example 14. The results are shown in Table 4.

Example 18 In Example 14, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ was used during the preparation of the complex.
Was added, and then (C ₂ H ₅ ) ₃ Al was added, and then ZrCl ₄ was added, and the same procedure as in Example 14 was performed. The result is the fourth
Shown in the table.

[Effect of the Invention] According to the method of the present invention, a catalyst having high activity and excellent stability can be prepared. By using this catalyst, ethylene is oligomerized in the presence of a specific ligand. ,
It is possible to efficiently produce a linear α-olefin having an optimum distribution (the yield of useful linear α-olefin having 6 to 18 carbon atoms is high) and having a high product purity.

The linear α-olefin obtained by the method of the present invention is suitably used, for example, as a modified comonomer for polyolefin, or as a raw material for a plasticizer or a surfactant.

[Brief description of drawings]

1 to 6 are flowcharts of different examples of the Ziegler-based catalyst used in the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08F 10/00 MFG

Claims (4)

[Claims] (A) General formula ZrXaA _4- a (wherein X and A may be the same or different and each represents a chlorine atom, a bromine atom or an iodine atom, and a is 0 or 1). Is an integer of 4), (B) a general formula AlR _1.5 Q _1.5 (wherein R is an alkyl group having 1 to 20 carbon atoms, Q is a chlorine atom, a bromine atom or an iodine atom). And R and Q may each be a combination of two or more kinds.) And (B) a general formula AlR'bQ'3 _- b (wherein R'is one having 1 carbon atom). To 20 alkyl groups, Q'represents a chlorine atom, a bromine atom or an iodine atom, R'and Q'may each be a combination of two or more kinds, and b is an integer of 1 to 3.). A catalyst comprising a mixture of the alkylaluminium compounds represented, and sulfurization Compound, a phosphorus compound and a nitrogen compound, in the presence of a ligand composed of one or more compounds selected from the above, a gas containing ethylene is oligomerized to produce a linear α-olefin. In preparing the catalyst in (1), (1) the zirconium halide concentration of the component (A) is
40 to 140 mmol / solvent 1 (2) The catalyst preparation temperature is 40 to 75 ° C when an aromatic hydrocarbon is used as a solvent, and 50 when an alicyclic hydrocarbon is used.
˜100 ° C., (3) Catalyst preparation time is 10 minutes to 8 hours, (4) Catalyst is charged in the order of (A) component zirconium halide, and (B) B component. The method for producing a linear α-olefin, characterized in that the preparation is carried out by satisfying the condition that the alkylaluminum compound of (1) is added, and then the alkylaluminum compound of the component (B) is added. 2. The catalyst preparation according to claim 1, wherein (A)
After adding zirconium halide as a component, (B)
The alkylaluminum compound as the component (a) and the alkylaluminum compound as the component (b) are added at the same time.
A method for producing the described linear α-olefin. 3. In the catalyst preparation according to claim 1, (A) is added after the component (B) an alkylaluminum compound as the component (A) and the component (B) as an alkylaluminum compound as the component (B).
The method for producing a linear α-olefin according to claim 1, wherein a zirconium halide compound as a component is added. 4. After the addition of the alkylaluminum compound (B) (b) in the catalyst preparation according to claim 1, (A)
The method for producing a linear α-olefin according to claim 1, wherein the zirconium halide compound as a component is added, and then the alkylaluminum compound as the component (B) is added.