JP5475314B2 - Complex catalyst and method for producing linear α-olefin using the same - Google Patents

Description

  The present invention relates to a complex catalyst used when a linear α-olefin is produced by an oligomerization reaction of ethylene and a method for producing a linear α-olefin using the same.

Industrial production of α-olefins by oligomerization of ethylene uses a complex catalyst such as Ni or Zr, or a catalyst such as triethylaluminum. In this reaction, in addition to the α-olefin in which ethylene is oligomerized, a small amount of a solid polymer is produced as a by-product, which may cause clogging of the reactor, piping and the like, resulting in a great trouble in operation.
There is a method of performing the reaction at a low temperature by taking measures against this solid polymer by-product. However, such low temperature reaction significantly reduces the catalytic activity. Another measure is to make the catalyst homogeneous. For example, when ZrCl ₄ is used as a transition metal compound, a heteroatom-containing organic compound is added to make a uniform system. However, in order to obtain a homogeneous system, it is necessary to use an aromatic solvent such as benzene. However, this aromatic solvent reacts with the α-olefin of the product, and alkylbenzene is by-produced to be mixed into each α-olefin. Product quality was deteriorating.

For example, Patent Document 1 discloses that an oligomerization reaction of ethylene is performed using an aromatic solvent in a reaction using a complex catalyst obtained by adding organoaluminum to a transition metal complex obtained by adding acetal and ketal to a Zr-based transition metal compound. Is described. In such a method, since an aromatic solvent is used as a reaction solvent, a Friedel-Craft reaction between the aromatic solvent and the generated α-olefin occurs, and a large amount of alkylbenzene is by-produced.
For example, when benzene is used as a solvent, alkylbenzene is mixed into a C10 or higher α-olefin, and when o-xylene is used as a reaction solvent, it is mixed into a C12 or higher α-olefin, thereby deteriorating the product quality.

In Patent Document 2, a non-aromatic solvent is used as a reaction solvent, but an aromatic solvent is used when a complex is prepared by adding an acetal and a ketal to ZrCl ₄ .
This method uses a small amount of the aromatic solvent used in the reaction system, but in this case as well, the solvent used in a small amount reacts with the α-olefin to produce by-produced alkylbenzene, which deteriorates the product quality.
In addition, although the low temperature reaction is more advantageous for reducing polymer by-products, the acetal and ketal added to the catalyst system in Patent Document 2 have low catalytic activity and high catalyst costs, resulting in high production costs. There is a problem.

In Patent Document 3, an organic compound such as ester, ketone, ether, nitrile, amine, acid anhydride, amide or aldehyde is added to zirconium halide to dissolve most of the zirconium halide, and this catalyst is used in a toluene solvent. Discloses the oligomerization reaction of ethylene.
Here, it is described that the catalyst system is made homogeneous in order to suppress the formation of inconvenient solid polymers. However, in order to obtain a homogeneous system, it is necessary to use an aromatic solvent, particularly when a halide of Zr is used.

  Patent Document 1 discloses a method of removing alkylbenzenes by-produced by ethylene oligomerization reaction. In this method, since an alkylbenzene is by-produced because an aromatic solvent is used as a solvent, a heavy alkylbenzene is obtained by further subjecting an α-olefin fraction containing the alkylbenzene to a Friedel-Craft reaction in the presence of a solid acid. And the alkylbenzenes are removed by distilling off the heavy side in a distillation column. However, this method complicates the apparatus, increases loss, and increases manufacturing costs.

  As described above, in the oligomerization reaction of ethylene, how to suppress the by-product of solid polymer or how to suppress the by-product of alkylbenzene has become a major issue. And in order to suppress a polymer byproduct and to enable continuous operation, a catalyst capable of reacting at a relatively low temperature with a homogeneous catalyst has been demanded. Furthermore, there has been a demand for a catalyst capable of obtaining a product distribution with a large effective fraction.

Japanese Patent Laid-Open No. 10-244162 Japanese Patent Laid-Open No. 06-166638 Japanese Patent Laid-Open No. 01-063532 WO2007107202

  In view of the above problems, an object of the present invention is to provide a highly active complex catalyst capable of suppressing polymer by-product and alkylbenzenes by-product when producing a linear α-olefin.

According to the present invention, the following complex catalyst and method for producing a linear α-olefin are provided.
1. A complex catalyst comprising a transition metal compound represented by the formula (I) and a diether organic compound represented by the formula (II).
ZrX _x (OR ¹ ) _y (I)
(In formula (I), X represents a halogen atom, R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms, x and y are integers of 0 to 4, and x + y = 4.)
R ² CH (OR ³ ) (OR ⁴ ) (II)
(In Formula (II), R ² represents a hydrocarbon group having 1 to 6 carbon atoms, and R ³ and R ⁴ each represent a hydrocarbon group having 1 to 30 carbon atoms.)
2. 2. The complex catalyst according to 1, wherein the complex catalyst further comprises an alkylaluminum compound represented by formula (III), or a mixture of an alkylaluminum compound represented by formula (III) and an alkylaluminum compound represented by formula (IV).
R ⁵ ₃ Al ₂ Cl ₃ (III)
(In formula (III), R ⁵ represents a hydrocarbon group having 1 to 12 carbon atoms.)
R ⁶ ₃ Al (IV)
(In formula (IV), R ⁶ represents a hydrocarbon group having 1 to 12 carbon atoms.)
3. The complex catalyst according to 1 or 2, wherein X in the formula (I) is a chlorine atom, and R ¹ is a hydrocarbon group having 2 to 4 carbon atoms.
4). The complex catalyst according to any one of 1 to 3, wherein R ³ and R ^{4 in} the formula (II) are each a hydrocarbon group having 1 to 6 carbon atoms.
5. The complex catalyst according to any one of 2 to 4, wherein the alkylaluminum compound of the formula (III) is ethylaluminum sesquichloride and the aluminum compound of the formula (IV) is triethylaluminum.
6). The complex catalyst according to any one of 1 to 5, wherein a molar ratio ((II) / (I)) of the diether organic compound of the formula (II) and the transition metal compound of the formula (I) is larger than 1.0.
7). The molar ratio (((III) + (IV)) / (I)) of the sum of the alkylaluminum compound of formula (III) and the alkylaluminum compound of formula (IV) to the transition metal compound of formula (I) is Any one of 2 to 6, wherein the molar ratio ((III) / (IV)) of the alkylaluminum compound of the formula (III) and the alkylaluminum compound of the formula (IV) is 1-100. The complex catalyst described.
The manufacturing method of the linear alpha olefin which carries out the oligomerization reaction of ethylene using the complex catalyst in any one of 8.1-7.
9. 9. The solvent added to the alkylaluminum compound of the formula (III) or the formula (III) and the formula (IV) and the solvent used for the oligomerization reaction of ethylene are saturated aliphatic hydrocarbons or naphthenic hydrocarbons. A method for producing a linear α-olefin.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a highly active complex catalyst which can suppress the byproduct of a polymer byproduct and alkylbenzenes, and a linear alpha olefin can be provided. The present invention can solve the conventional problems and has great industrial significance.

The complex catalyst of the present invention comprises a transition metal compound represented by the formula (I) and a diether organic compound represented by the formula (II).
ZrX _x (OR ¹ ) _y (I)
(In formula (I), X represents a halogen atom, R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms, x and y are integers of 0 to 4, and x + y = 4.)
R ² CH (OR ³ ) (OR ⁴ ) (II)
(In formula (II), R ² represents a hydrocarbon group having 1 to 6 carbon atoms, R ³ and R ⁴ represent a hydrocarbon group having 1 to 30 carbon atoms, and R ³ and R ⁴ are the same. May be different.)

X in the above formula (I) is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. y is preferably 0.
R ¹ is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 2 to 4 carbon atoms.
Examples of the transition metal compound represented by the formula (I) include ZrCl ₄ , Zr (OEt) ₄ , Zr (OEt) ₂ Cl ₂ , Zr (OPr) ₄ , Zr (OPr) ₂ Cl ₂ , preferably ZrCl ₄ , Zr (OEt) ₄ , and Zr (OPr) ₄ .

R ^{2 in the} above formula (II) is preferably a hydrocarbon group having 2 to 3 carbon atoms. R ³ and R ⁴ are preferably each a hydrocarbon group having 1 to 6 carbon atoms.
Examples of the diether organic compound represented by the formula (II) include 1,1-dimethoxypropane, 1,1-dimethoxybutane, 1,1-dimethoxypentane, 1,1-dimethoxyhexane, 1,1-dimethoxyheptane, 1, 1-dimethoxyoctane, 1,1-diethoxypropane, 1,1-diethoxybutane, 1,1-diethoxypentane, 1,1-diethoxyhexane, 1,1-diethoxyheptane, 1,1-diethoxy Ethoxyoctane, 1,1-dipropoxypropane, 1,1-dipropoxybutane, 1,1-dipropoxypentane, 1,1-dipropoxyhexane, 1,1-dipropoxyheptane, 1,1-dipropoxyoctane 1,1-dibutoxypropane, 1,1-dibutoxybutane, 1,1-dipentyloxypropane, 1,1-dipentyl Kishibutan, 1,1-hexyl oxy propane, 1,1-hexyl oxy-butane, dimethyl acetal, and the like.

The diether organic compound may be used alone or in a mixed system.
Addition of these diether organic compounds increases the activity of the catalyst. Since it is highly active, the reaction can be carried out at a lower temperature. For this reason, a linear α-olefin having a high product purity can be obtained while suppressing solid polymer by-product. In addition, a distribution with a relatively large effective fraction can be obtained.

The molar ratio ((II) / (I)) of the diether organic compound of formula (II) to the transition metal compound of formula (I) is preferably greater than 1.0, more preferably greater than 1 and less than or equal to 10 More preferably, it is more than 1 and 5 or less, and particularly preferably more than 1 and 2 or less. When ((II) / (I)) is greater than 1.0, by-products of alkylbenzenes can be suppressed when an aromatic compound is used as a solvent in the reaction.
If ((II) / (I)) is greater than 10, the catalytic activity may be reduced. In the case of 1 or less, alkylbenzenes may be by-produced and mixed into the product.

The complex catalyst of the present invention preferably further comprises an alkylaluminum compound represented by formula (III) or a mixture of an alkylaluminum compound represented by formula (III) and an alkylaluminum compound represented by formula (IV).
R ⁵ ₃ Al ₂ Cl ₃ (III)
(In formula (III), R ⁵ represents a hydrocarbon group having 1 to 12 carbon atoms.)
R ⁶ ₃ Al (IV)
(In formula (IV), R ⁶ represents a hydrocarbon group having 1 to 12 carbon atoms.)

R ^{5 in the} above formula (III) is preferably a hydrocarbon group having 2 to 4 carbon atoms.
The alkylaluminum compound of formula (III) is preferably ethylaluminum sesquichloride.
R ^{6 in the} above formula (IV) is preferably a hydrocarbon group having 2 to 4 carbon atoms.
The alkylaluminum compound of formula (IV) is preferably triethylaluminum.

When the alkylaluminum compound of the above formula (III) and the alkylaluminum compound of the above formula (IV) are mixed and used, the molar ratio ((III) / (IV)) is preferably 1 to 100, preferably 2 -80, more preferably 3-30.
If the amount of the alkylaluminum compound of the formula (IV) is too large, the amount of polymer by-products increases and not only the oligomer yield decreases but also the continuous operation becomes difficult due to the blockage of the reactor and piping by the polymer. There is a fear.

The molar ratio (((III) + (IV)) / (I)) of the sum of the alkylaluminum compound of the above formula (III) and the alkylaluminum compound of the above formula (IV) and the transition metal compound of the above formula (I) is , Preferably it is 1-100, More preferably, it is 2-80, More preferably, it is 3-30.
If (((III) + (IV)) / (I)) is greater than 100, the catalyst activity not only reaches its peak, but also the lightness increases, and in particular, the production of 1-butene may increase. On the other hand, if it is smaller than 1, not only the catalytic activity is lowered, but also the heavy component is increased, and the yield of the effective fraction may be lowered.

  The product distribution and catalytic activity differ depending on the type of Zr compound, diether organic compound, alkylaluminum compound, the solvent used, and the mixing ratio. The product distribution is Schulz-Flory distribution, but the product distribution can be changed by changing the molar ratio (((III) + (IV)) / (I)) or molar ratio ((III) / (IV)). be able to. By optimizing these molar ratios, the effective fraction can be increased and the catalytic activity can be made high.

In the method of the present invention, ethylene is oligomerized using the above complex catalyst to produce a linear α-olefin. Examples of the linear α-olefin obtained by oligomerizing ethylene include 1-hexene and 1-octene.
In the method of the present invention, for example, first, a transition metal compound of the formula (I) and a diether organic compound of the formula (II) are mixed with a solvent to prepare a first catalyst solution, and the formula (III) or the formula ( III) and an alkylaluminum compound of formula (IV) are mixed with a solvent to prepare a second catalyst solution, and then the first catalyst solution, the second catalyst solution and ethylene are added to the reaction solvent. React.
When preparing the first catalyst solution, when the diether organic compound of formula (II) is added to the transition metal compound of formula (I) under an aromatic solvent such as benzene, the transition metal is colored yellow to brown. It can be seen that the diether organic compound is coordinated to the compound.

In the method of the present invention, a non-aromatic solvent can be used as the solvent and reaction solvent of the second catalyst solution. Examples of the non-aromatic solvent include aliphatic hydrocarbons and naphthenic hydrocarbon solvents. Saturated aliphatic hydrocarbons or naphthenic hydrocarbons are preferred.
Examples of the aliphatic hydrocarbon include pentane, heptane, nonane, undecane, and the like, and examples of the naphthenic hydrocarbon solvent that can be separated from the product α-olefin such as cyclohexane and ethylcyclohexane.
In the method of the present invention, since the aromatic solvent to be used can be limited to that used in the first catalyst solution, the amount of by-produced alkylbenzenes can be suppressed.

  The reaction conditions for the oligomerization reaction are not particularly limited and can be set as appropriate. For example, the reaction temperature is 40 to 120 ° C., the reaction time is 0.5 to 3 hours, and the reaction pressure is 0.5 to 5 MPa.

Example 1
(1) Preparation of catalyst solution A In a 100 ml Schlenk tube A containing a stirrer in a dry nitrogen atmosphere, 0.702 g (3 mM) of zirconium tetrachloride (ZrCl ₄ ) and 45 ml of dry o-xylene were placed.
A total amount of a solution prepared by dissolving 0.59 g (4.5 mM) of 1,1-diethoxypropane (1,1-DEP) as a diether organic compound in 5 ml of dry o-xylene is added from Schlenk tube B to Schlenk tube A And stirred at room temperature. Several minutes later, the solution turned from yellow to brown, and it was confirmed that 1,1-DEP was coordinated to ZrCl ₄ .
At this time, the Schlenk tube A contains ZrCl ₄ 3 mM, 1,1-DEP _4.5 mM, and o-xylene 50 ml.

(2) Preparation of catalyst solution B In a 100 ml Schlenk tube C under a dry nitrogen atmosphere, 48.5 ml of dry cyclohexane, 0.14 ml (1 mM) of triethylaluminum (TEA) and 1.36 ml (6 mM) of ethylaluminum sesquichloride (EASC) were added. I put it in.

(3) Oligomerization reaction To a 1 L autoclave equipped with a stirrer and a thermocouple, 300 ml of dry cyclohexane was added, and 1 ml of catalyst solution A and 2.14 ml of catalyst solution B were added. The catalyst used in the reaction was Zr 0.06 mM, 1,1-DEP 0.09 mM, EASC 0.257 mM and TEA 0.043 mM. At this time, the catalyst composition was Al / Zr = 5 (molar ratio), EASC / TEA = 6. (Molar ratio) and 1,1-DEP / Zr = 1.5 (molar ratio). After the addition of the catalyst and the solvent, the temperature was raised to 80 ° C., and when the temperature reached 80 ° C., the supply of ethylene was started to raise the ethylene pressure to 4 MPa and the reaction was started. Stirring was continued under the conditions of 80 ° C. and 4 MPa, and the reaction was performed for 2 hours. After 2 hours, about 30 ml of methanol was put in an autoclave as a deactivator and deactivated. After stirring at 80 ° C. for about 10 minutes, stirring was stopped and the temperature was lowered to room temperature. After cooling to room temperature, the pressure was released and the atmosphere was replaced with nitrogen. Thereafter, the autoclave was opened, the contents were extracted, and the state of polymer adhesion to the reactor and the stirring blade was observed.

Moreover, 3.7 g of undecane as a gas chromatography (GC) internal standard solution was added to the extracted content, and solid content was filtered by suction filtration. The filtrate after filtration was subjected to GC analysis under the following conditions to determine the yield and product distribution.
Column: Ultra II (25m × 0.2m × 0.33μm)
Carrier gas: He (1.1 c / min)
Inj. Temp. : 270 ° C
Det. Temp. : 270 ° C
Col. Temp. : 35-280 ° C (0.5-1.5 ° C / min)

The results are shown below.
Catalytic activity: 1800 (g / mM · Zr)
α value: 0.75
C4 production: 10.0 (wt%)
AB by-product / C14: 1 ppm or less No polymer adhesion to the reactor and stirring blade after the reaction was observed.

  In the oligomerization reaction, when o-xylene is used as the aromatic compound (solvent), various alkylbenzenes are mixed in the C12 or higher α-olefin. It is the amount of (AB).

In addition, the α value is the α value of the following Schulz-Flory distribution formula. When the α value is large, the heavy component increases, and when the α value is small, the light component increases.
Schulz-Flory distribution formula Mp = P × α (P-2) × (1-α) 2 / (2-α)
Mp: weight fraction (wt%) P: degree of polymerization (−) α: Kp / ((Kp + Ktr) (−)
Kp: Growth reaction rate constant (m ³ / h · kg-Cat) Ktr: Chain transfer rate constant (m ³ / h · kg-Cat)

Example 2
The diether organic compound of catalyst solution A was 1,1-dimethoxyheptane (1,1-DMH), the amount added in catalyst solution A was 0.72 g (4.5 mM), and 1,1-dimethoxyheptane used in the reaction was used. The reaction was performed and evaluated in the same manner as in Example 1 except that DMH was changed to 0.014 g (0.09 mM). The results are shown below.
Catalytic activity: 1500 (g / mM · Zr)
α value: 0.60
C4 production: 22.9 (wt%)
AB by-product / C14: 1 ppm or less No adhesion of polymer to the reactor and stirring blade after the reaction was observed.

Example 3
The diether organic compound of catalyst solution A was 1,1-dimethoxypropane (1,1-DMP), the addition amount in catalyst solution A was 0.47 g (4.5 mM), and 1,1-dimethoxypropane used in the reaction was used. The reaction was performed and evaluated in the same manner as in Example 1 except that DMP was changed to 0.009 g (0.09 mM). The results are shown below.
Catalytic activity: 1100 (g / mM · Zr)
α value: 0.65
C4 production: 18.1 (wt%)
AB by-product / C14: 1 ppm or less No adhesion of polymer to the reactor and stirring blade after the reaction was observed.

Example 4
The diether organic compound of catalyst solution A was 1,1-dimethoxyethane (1,1-DME), and the amount added in catalyst solution A was 0.406 g (4.5 mM). The reaction was performed and evaluated in the same manner as in Example 1 except that DME was changed to 0.008 g (0.09 mM). The results are shown below.
Catalytic activity: 1300 (g / mM · Zr)
α value: 0.70
C4 production: 13.5 (wt%)
Alkylbenzene by-product amount: 1 ppm or less No polymer adhesion to the reactor and stirring blade after the reaction was observed.

Example 5
1,1-diethoxypropane (1,1-DEP) was used as the diether organic compound in catalyst solution A, and the added amount in catalyst solution A was 0.793 g (6 mM), and 1,1-DEP used in the reaction The reaction was performed and evaluated in the same manner as in Example 1 except that 0.016 g (0.12 mM) was used. The results are shown below.
It was 1,1-DEP / Zr: 2.0 (molar ratio).
Catalytic activity: 1700 (g / mM · Zr)
α value: 0.70
C4 production: 13.5 (wt%)
Alkylbenzene by-product amount: 1 ppm or less No polymer adhesion to the reactor and stirring blade after the reaction was observed.

Example 6
The reaction was performed and evaluated in the same manner as in Example 1 except that the reaction temperature was 70 ° C. The results are shown below.
Catalytic activity: 1400 (g / mM · Zr)
α value: 0.70
C4 production: 13.5 (wt%)
Alkylbenzene by-product amount: 1 ppm or less No polymer adhesion to the reactor and stirring blade after the reaction was observed.

Example 7
The reaction was performed and evaluated in the same manner as in Example 1 except that the reaction temperature was 90 ° C. The results are shown below.
Catalytic activity: 2370 (g / mM · Zr)
α value: 0.775
C4 production: 8.3 (wt%)
Alkylbenzene by-product amount: 1 ppm or less No polymer adhesion to the reactor and stirring blade after the reaction was observed.

Example 8
The reaction was conducted and evaluated in the same manner as in Example 1 except that the amount of catalyst solution B added during the reaction was 4.2 ml and Al / Zr = 10 (molar ratio). The results are shown below.
Catalytic activity: 3800 (g / mM · Zr)
α value: 0.65
C4 production: 18.1 (wt%)
Alkylbenzene by-product amount: 1 ppm or less No polymer adhesion to the reactor and stirring blade after the reaction was observed.

Example 9
Catalyst solution B was prepared as follows, and reacted and evaluated in the same manner as in Example 1 except that the amount of catalyst solution B added during the reaction was 6.42 ml.
In a 100 ml Schlenk tube C under a dry nitrogen atmosphere, 48.58 ml of dry cyclohexane, 0.23 ml (1.75 mM) of triethylaluminum (TEA) and 1.19 ml (5.25 mM) of ethylaluminum sesquichloride (EASC) were added to form a catalyst solution. B.
The catalyst composition used at this time was Al / Zr = 15 (molar ratio) and EASC / TEA = 3 (molar ratio).
The results are shown below.
Catalytic activity: 4300 (g / mM · Zr)
α value: 0.70
C4 production: 13.5 (wt%)
Alkylbenzene by-product amount: 1 ppm or less No polymer adhesion to the reactor and stirring blade after the reaction was observed.

Example 10
Catalyst solution B was prepared as follows, and the reaction was performed and evaluated in the same manner as in Example 1 except that the amount of catalyst solution B added during the reaction was 4.28 ml.
In a dry nitrogen atmosphere, 48.42 ml of dry cyclohexane and 1.58 ml (7 mM) of ethylaluminum sesquichloride (EASC) were placed in a 100 ml Schlenk tube C to prepare catalyst solution B. TEA was not added.
The catalyst composition used at this time was Al / Zr: 10 (molar ratio).
The results are shown below.
Catalytic activity: 2100 (g / mM · Zr)
α value: 0.60
C4 production: 22.9 (wt%)
Alkylbenzene by-product amount: 1 ppm or less No polymer adhesion to the reactor and stirring blade after the reaction was observed.

Example 11
The reaction was conducted in the same manner as in Example 1 except that the amount of 1,1-DEP in catalyst solution A was 0.39 g (3 mM) and the amount of 1,1-DEP used in the reaction was 0.06 mM. Made and evaluated. The results are shown below.
1,1-DEP / Zr = 1.0 (molar ratio).
Catalytic activity: 1700 (g / mM · Zr)
α value: 0.70
C4 production: 13.5 (wt%)
Alkylbenzene by-product amount: 80 ppm or less No polymer adhesion to the reactor and stirring blade after the reaction was observed.

Comparative Example 1
Catalyst solution A, catalyst solution B, and the solvent used for the reaction are all o-xylene, the diether organic compound of catalyst solution A is 2,2-dimethoxypropane (2,2-DMP), and the addition in catalyst solution A The reaction was conducted and evaluated in the same manner as in Example 1 except that the amount was 0.312 g (3 mM) and 2,2-DMP used in the reaction was 0.006 g (0.06 mM). The results are shown below.
Catalytic activity: 800 (g / mM · Zr)
α value: 0.50
C4 production: 33.3 (wt%)
Alkylbenzene byproduct: 3% (30000ppm)
Polymer adhesion to the reactor and the stirring blade after the reaction was not observed.

Comparative Example 2
The reaction was conducted and evaluated in the same manner as in Example 11 except that o-xylene was used as the solvent for the catalyst solution A, and cyclohexane was used as the solvent for the catalyst solution B and the reaction. The results are shown below.
Catalytic activity: 780 (g / mM · Zr)
α value: 0.50
C4 production: 33.3 (wt%)
Alkylbenzene by-product amount: 100ppm
Polymer adhesion to the reactor and the stirring blade after the reaction was not observed.

Comparative Example 3
The diether organic compound of catalyst solution A was 2,2-diethoxypropane (2,2-DEP), the addition amount in catalyst solution A was 0.397 g (3 mM), and 2,2-DEP used in the reaction The reaction was conducted and evaluated in the same manner as in Example 11 except that 0.008 g (0.06 mM) was used. The results are shown below.
Catalytic activity: 700 (g / mM · Zr)
α value: 0.60
C4 production: 22.9 (wt%)
Alkylbenzene by-product amount: 120ppm
Polymer adhesion to the reactor and the stirring blade after the reaction was not observed.

Comparative Example 4
The diether organic compound of catalyst solution A was dimethoxymethane (DMM), the addition amount in catalyst solution A was 0.228 g (3 mM), and the DMM used in the reaction was 0.005 g (0.06 mM). The reaction was conducted in the same manner as in Example 11 and evaluated. The results are shown below.
Catalytic activity: 400 (g / mM · Zr)
α value: 0.60
C4 production: 22.9 (wt%)
Alkylbenzene by-product amount: 200ppm
Polymer adhesion to the reactor and the stirring blade after the reaction was not observed.

Comparative Example 5
The diether organic compound of catalyst solution A is 1,1-dimethoxyoctane (1,1-DMO), the amount added in catalyst solution A is 0.523 g (3 mM), and 1,1-DMO used in the reaction is The reaction was performed and evaluated in the same manner as in Example 11 except that the amount was 0.011 g (0.06 mM). The results are shown below.
Catalytic activity: 100 (g / mM · Zr)
α value: 0.625
C4 production: 20.5 (wt%)
Alkylbenzene byproduct: 750 ppm
Polymer adhesion to the reactor and the stirring blade after the reaction was not observed.

Comparative Example 6
The diether organic compound of catalyst solution A is 1,2-dimethoxypropane (1,2-DMP), the addition amount in catalyst solution A is 0.312 g (3 mM), and 1,2-DMP used in the reaction is The reaction was performed and evaluated in the same manner as in Example 11 except that the amount was 0.006 g (0.06 mM). The results are shown below.
Catalytic activity: 20 (g / mM · Zr)
α value: 0.50
C4 production: 33.3 (wt%)
Alkylbenzene by-product amount: 1200ppm
Polymer adhesion to the reactor and the stirring blade after the reaction was not observed.

Comparative Example 7
The diether organic compound of catalyst solution A was 2,2-dimethoxypropane (2,2-DMP), and the amount added in catalyst solution A was 0.469 g (4.5 mM). The reaction was performed and evaluated in the same manner as in Example 11 except that DMP was changed to 0.009 g (0.09 mM). The results are shown below.
Catalytic activity: 700 (g / mM · Zr)
α value: 0.625
C4 production: 20.5 (wt%)
Alkylbenzene by-product amount: 1 or less Polymer adhesion to the reactor and stirring blade after the reaction was not observed.

The following can be understood from the above-mentioned Examples and Comparative Examples.
[Effects of diether organic compound species]
A homogeneous complex can be synthesized by mixing a diether organic compound having an R ² CH (OR ³ ) (OR ⁴ ) structure with a Zr compound. When this complex is used, there are many effective fractions, Even at low temperature reaction, high activity is obtained and by-product of solid polymer can be suppressed.
When a diether ligand (2,2-isomer, 1,2-isomer, etc.) is used, not only the distribution of light components is increased, but also the catalytic activity is reduced (Comparative Examples 1 to 5). Moreover, even if it is a 1, 1-form, if a long-chain diether body is used, activity will become low.

[Effect of amount of diether organic compound]
An aromatic solvent is generally used to obtain a homogeneous complex catalyst by adding a diether organic compound. In this case, the produced α-olefin reacts with the aromatic solvent to produce alkylbenzene as a by-product, resulting in product quality. Worsen.
At this time, the diether organic compound is used in a predetermined amount or more (added amount larger than 1.0 mol with respect to 1 mol of the Zr compound) to reduce the use amount of the aromatic solvent (non-aromatic in the catalyst solution B and the reaction solvent). By using a group-based solvent), by-products of alkylbenzene can be suppressed.
For example, when all the solvents are aromatic solvents and the reaction is carried out at a diether organic compound / Zr compound molar ratio of 1, alkylbenzene is produced as a by-product, for example, 3% (30000 ppm) of alkylbenzene in the C14 fraction. Mixed (Comparative Example 1). Even if the aromatic solvent is reduced as much as possible, if the molar ratio of diether organic compound / Zr compound is set to 1, alkylbenzene in the C14 fraction is mixed in several tens to several thousand ppm (Example 11, Comparative Examples 4 and 5). ).
When this molar ratio (diether-based organic compound / Zr compound) is a ratio larger than 1, by-production of alkylbenzene can be completely suppressed. This is considered that the diether organic compound suppresses the Friedel-Craft reaction.

[Effect of catalyst composition]
When a diether-based organic compound having an R ² CH (OR ³ ) (OR ⁴ ) structure is mixed with a Zr compound, the ratio of alkylaluminum / transition metal compound (Al / Zr ratio) compared to the organic compound added to the catalyst system of the prior art ) And the ratio of the two organoaluminium ratios ((EASC / TEA ratio)) can be reduced, and therefore high catalytic activity can be obtained.
Moreover, a desired product distribution can be obtained by changing the Al / Zr ratio or the two kinds of alkylaluminum EASC / TEA ratios (Examples 1 and 8 and 9).
Thus, products according to demand can be obtained, and industrial significance is great.

  The complex catalyst of the present invention and the method for producing a linear α-olefin using the complex catalyst can be used for producing a linear α-olefin used for a comonomer, an alcohol raw material for a plasticizer, a surfactant raw material, or the like.

Claims (9)

A complex catalyst for producing a linear α-olefin, comprising a transition metal compound represented by formula (I) and a diether organic compound represented by formula (II).
ZrX _x (OR ¹ ) _y (I)
(In formula (I), X represents a halogen atom, R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms, x and y are integers of 0 to 4, and x + y = 4.)
R ² CH (OR ³ ) (OR ⁴ ) (II)
(In Formula (II), R ² represents a hydrocarbon group having 1 to 6 carbon atoms, and R ³ and R ⁴ each represent a hydrocarbon group having 1 to 30 carbon atoms.) The wire according to claim 1, wherein the complex catalyst further comprises an alkylaluminum compound represented by formula (III), or a mixture of an alkylaluminum compound represented by formula (III) and an alkylaluminum compound represented by formula (IV). Complex catalyst for producing α-olefin.
R ⁵ ₃ Al ₂ Cl ₃ (III)
(In formula (III), R ⁵ represents a hydrocarbon group having 1 to 12 carbon atoms.)
R ⁶ ₃ Al (IV)
(In formula (IV), R ⁶ represents a hydrocarbon group having 1 to 12 carbon atoms.) The complex catalyst for producing a linear α-olefin according to claim 1 or 2, wherein X in the formula (I) is a chlorine atom, and R ¹ is a hydrocarbon group having 2 to 4 carbon atoms. The complex catalyst for producing a linear α-olefin according to any one of claims 1 to 3, wherein R ³ and R ^{4 in} the formula (II) are each a hydrocarbon group having 1 to 6 carbon atoms.   The complex catalyst for producing linear α-olefin according to any one of claims 2 to 4, wherein the alkylaluminum compound of the formula (III) is ethylaluminum sesquichloride and the aluminum compound of the formula (IV) is triethylaluminum. .   The line according to claim 1, wherein the molar ratio ((II) / (I)) of the diether organic compound of formula (II) and the transition metal compound of formula (I) is greater than 1.0. Complex catalyst for producing α-olefin.   The molar ratio (((III) + (IV)) / (I)) of the sum of the alkylaluminum compound of formula (III) and the alkylaluminum compound of formula (IV) to the transition metal compound of formula (I) is The molar ratio ((III) / (IV)) of the alkylaluminum compound of the formula (III) and the alkylaluminum compound of the formula (IV) is 1 to 100. A complex catalyst for producing a linear α-olefin according to claim 1.   The manufacturing method of the linear alpha olefin which carries out the oligomerization reaction of ethylene using the complex catalyst for linear alpha olefin manufacture in any one of Claims 1-7. The complex catalyst includes an alkylaluminum compound represented by the following formula (III), or a mixture of an alkylaluminum compound represented by the formula (III) and an alkylaluminum compound represented by the following formula (IV):
9. The solvent added to the alkylaluminum compound of the formula (III) or the formula (III) and the formula (IV) and the solvent used for the oligomerization reaction of ethylene are saturated aliphatic hydrocarbons or naphthenic hydrocarbons. A method for producing a linear α-olefin as described in 1. above.
R ⁵ ₃ Al ₂ Cl ₃ (III)
(In formula (III), R ⁵ represents a hydrocarbon group having 1 to 12 carbon atoms.)
R ⁶ ₃ Al (IV)
(In formula (IV), R ⁶ represents a hydrocarbon group having 1 to 12 carbon atoms.)