JPH0446929B2 - - 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, in a method for producing a linear α-olefin in which ethylene is oligomerized using a halogen-containing catalyst, a nitrogen-containing compound is Production of linear α-olefin that suppresses halogen addition to α-olefin and efficiently produces high-purity α-olefin by adding a deactivator to deactivate the catalyst after adding α-olefin. Regarding the method. [Prior Art and its Problems] 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, and halogen-containing catalysts are known as catalysts used at this time. Water, alcohol, carboxylic acid, phenols, etc. are known as deactivating agents used to deactivate this catalyst (Japanese Patent Application Laid-Open No. 109428-1983).
(see publication). However, these deactivators do not allow the halogen contained in the catalyst to be used as the final product, α-
Addition to olefins cannot be suppressed. Therefore, in the conventional production method, halogens such as chlorine are added to α-olefin, resulting in a decrease in the quality of α-olefin, and there is a problem in that highly pure α-olefin cannot be produced. . Further, such halogen compounds become catalyst poisons when synthesizing α-olefin derivatives, so there is a problem that the α-olefin derivatives cannot be synthesized efficiently. [Object of the Invention] This invention has been made based on the above circumstances. That is, an object of the present invention is to solve such conventional problems and to provide a method for producing linear α-olefins by oligomerizing ethylene in the presence of a halogen-containing catalyst, in which the resulting α-olefins have high purity. A further object of the present invention is to provide a method for producing a linear α-olefin in which less substances are produced as catalyst poisons when a derivative is synthesized from the α-olefin. As a result of intensive research to achieve the above object, the inventors discovered that an excellent effect can be obtained by adding a nitrogen-containing compound, which will be described later, when deactivating the catalyst. It was completed. [Means for solving the above problems] The outline of the present invention for solving the above problems is as follows: ZX _a A _4-a [1] (wherein, Z represents zirconium, and X and A
may be the same or different, and each represents Cl, Br, or I. Also, a is 0
Represents an integer from ~4. ) [hereinafter sometimes referred to as component [A]]; Following formula: AlR _1.5 Q _1.5 [2] (wherein, R represents an alkyl group having 1 to 20 carbon atoms; , Q represents Cl, Br, or I. However,
R and Q may be the same or different. Note that the second formula is
It can also be represented by Al ₂ R ₃ Q ₃ . ) [hereinafter, this may be referred to as component B-1]. ] or an alkyl aluminum compound represented by the above formula [2], and/or the following formula: AlR′ _b Q′ _3-b [3] (wherein R′ and Q′ are the above R and the above Q, respectively) It represents the same meaning. Also, b is 1 to 3
represents an integer. However, R' and Q' may be the same or different. ) (hereinafter, this may be referred to as component B-2). Further, the B-1 component and this B-2 may be collectively referred to as a B component. ] When an olefin-containing gas is polymerized in the presence of a halogen-containing catalyst obtained from This is a method for producing a linear α-olefin, which is characterized by adding a compound. Furthermore, in this invention, the above-mentioned [A] component, [B] component, and at least one compound selected from the group consisting of sulfur compounds, phosphorus compounds, and nitrogen compounds (hereinafter, these compounds are referred to as [C] component) It is preferable to use the one obtained from As the component [A], the metal halide compound represented by the formula [1] is not particularly limited as long as it satisfies the formula [1], and examples thereof include ZrCl ₄ , ZrBr ₄ , ZrI ₄ , ZrBrCl ₃ , ZrBr ₂ Cl and the like. Among these, especially
_ZrCl4 is preferred. In addition, these may be used individually by 1 type, or may be used in combination of 2 or more types. The component [B] is an alkyl aluminum compound [B-1] represented by the formula [2], an alkyl aluminum compound [B-2] represented by the formula [3], and an alkyl aluminum compound [B-2] represented by the formula [3]. The alkylaluminum compound [B-1] represented by the formula [B-1] and the alkylaluminum compound [B-1] represented by the formula [3]
2], or a mixture thereof. The component [B-1] is not particularly limited as long as R and Q each satisfy the above conditions in the formula [2], and specific examples include, for example, 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 , Al ₂ (C ₈ H ₁₇ ) ₃ Cl ₃ , Al ₂ (C ₂ H ₅ ) ₂ (CH ₃ ) Examples include _Cl3 . Among these, R is preferably a methyl group, an ethyl group, a propyl group, a butyl group, etc., and an ethyl group is particularly preferred. As Q, Cl is preferable. Specifically, ethylaluminum sesquichloride [Al(C ₂ H ₅ ) _1.5
Cl _1.5 , ie Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ ] may be mentioned as suitable. Note that these alkylaluminum compounds may be used alone or in combination of two or more. The alkylaluminum compound represented by the formula [3] used as the component [B-2] is not particularly limited as long as R' and Q' in the formula [3] satisfy the above conditions. For example, Al(CH ₃ ) ₃ , Al(C ₂ H ₅ ) ₃ , Al(C ₃ H ₇ ) ₃ , Al(iso−C ₃ H ₇ ) ₃ , Al(C _4H9 ) ₃ , Al(iso- _C4H9 ) _{3 ,} Al( _{C5H11 ) 3} , _{Al ( C6H13} ) ₃ , Al( _{C8H17 ) 3} , Al( _{C2H5 )} ) 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 etc. However, among the compounds represented by the above formula [3], those in which b is 3 or 2 are preferred. In formula [3], R' is preferably an ethyl group, a propyl group, a butyl group, an isobutyl group, etc.
Particularly preferred is ethyl group. As Q', Cl is preferable. Specifically, for example, triethylaluminum and diethylaluminum chloride can be mentioned as suitable examples. Note that these alkylaluminum compounds can be used alone or in combination of two or more as the [B-2] component. In addition, when the [B-1] component and this [B-2] component are used together, the ratio of the [B-1] component and the [B-2] component is usually adjusted to the [B-2] component. ] component is desirably set to 50 mol% or less (based on Al), preferably 30 mol% or less (based on Al). A sulfur compound used as the component [C],
The phosphorus compound and nitrogen compound are not particularly limited as long as they are an organic sulfur compound, an organic phosphorus compound, or an organic nitrogen compound, but those shown below can usually be suitably used. That is, the sulfur compounds include, for example, thioethers such as dimethyl sulfide, diethyl sulfide, bipropyl sulfide, dihexyl sulfide, dicyclohexyl sulfide, and diphenylthioether; dimethyl disulfide [(CH ₃ ) ₂ S ₂ ], diethyl disulfide, Dialkyl disulfide compounds such as dipropyl disulfide, dibutyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, ethylmethyl disulfide; thiophene, 2
-methylthiophene, 3-methylthiophene,
Thiophenes such as 2,3-dimethylthiophene, 2-ethylthiophene, and benzothiophene; heterocyclic sulfur compounds such as tetrahydrothiophene and thiopyran; aromatic sulfur compounds such as diphenyl sulfur, diphenyl disulfide, methylphenyl disulfide, and methylphenyl sulfur. ; Thiourea [(NH ₂ ) ₂ CS]; Sulfides such as methyl sulfide, ethyl sulfide, butyl sulfide; and the like. Examples of the phosphorus compound include phosphines such as triphenylphosphine, triethylphosphine, tributylphosphine, tripropylphosphine, trioctylphosphine, and tricyclohexylphosphine. Examples of the nitrogen compounds include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, silulohexylamine, octylamine, decylamine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, and diphenylamine. , methylphenylamine, trimethylamine, triethylamine, tributylamine, triphenylamine, pyridine,
Organic amines such as picoline can be mentioned. Among the various sulfur compounds, phosphorus compounds, and nitrogen compounds, for example, dimethyl disulfide, thiophene, thiourea, triphenylphosphine, tributylphosphine, trioctylphosphine,
One or more compounds selected from aniline and the like can sometimes be used publicly. Further, these compounds may be used alone or in combination of two or more. Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, ethylbenzene, dichlorobenzene, and chlorotoluene, or halogen-substituted products thereof;
Aliphatic paraffins such as pentane, hexane, heptane, octane, nonane, and decane; Naphthenic paraffins such as cyclohexane and decalin;
Examples include haloalkanes such as dichloroethane and dichlorobutane. Among these, benzene, chlorobenzene, and heptane are preferred, and benzene is particularly preferred. These solvents can be used alone or in combination of two or more. The olefin-containing gas is preferably a gas containing ethylene, such as an inert gas containing ethylene, purified ethylene gas for polymerization,
Examples include ethylene gas for polymerization such as high-purity ethylene. Among these, high purity ethylene is particularly preferred. It goes without saying that the olefin may be, for example, propylene, butene-1, etc. in addition to ethylene. An important point in the production method of the present invention is that when deactivating the catalyst using a deactivator, the nitrogen-containing compound is added to the mixture of the catalyst, the hydrocarbon solvent, and the produced α-olefin. It is. In principle, there are no restrictions on the order in which the deactivator and the nitrogen-containing compound are added to the mixture.
That is, the catalyst, the hydrocarbon solvent and the product α
- the order of first adding the nitrogen-containing compound and then adding the deactivator to the mixture with the olefin;
Examples of the addition order include adding the deactivator and then adding the nitrogen-containing compound, or adding the nitrogen-containing compound and the deactivator simultaneously. . However, the above order is preferred. Examples of the nitrogen-containing compound include ammonia, methylamine, ethylamine, propylamine, butylamine, pentylamine,
Hexylamine, cyclohexylamine, octylamine, decylamine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, diphenylamine,
Examples include amines such as methylphenylamine, trimethylamine, triethylamine, tributylamine, triphenylamine, pyridine, and picoline. These compounds may be used alone or in combination of two or more. The deactivator is an agent that deactivates the polymerization activity of the catalyst, and specifically includes water, alcohol (monohydric alcohol, polyhydric alcohol, cyclic alcohol, acyclic alcohol, aliphatic alcohol, aromatic alcohol). ), carboxylic acids, phenols, etc. (Those described in JP-A-58-109428 can be used.). When preparing a catalyst using the [A] component, the [B] component, and the [C] component, there are no particular restrictions on the order and method of blending the above-mentioned components and the solvent, but for example, the [A] component and [B] component, respectively or simultaneously, to prepare a catalyst preparation solution by dissolving them in an appropriate amount of a catalyst preparation solvent, and then, prior to polymerization, combine the catalyst preparation solution, [C] component, and the solvent. A method of preparing a catalyst solution by mixing them is preferably used. When preparing this catalyst preparation solvent or catalyst solution, an appropriate temperature (usually
For example, it is desirable to activate the catalyst by heating at a temperature lower than the polymerization reaction temperature. Note that the solvent for preparing the catalyst is usually
Inert solvents such as the above-mentioned solvents can be suitably used. During polymerization, the catalyst solution can be further mixed with the solvent as required to adjust the concentration before use. After bringing the catalyst or catalyst solution prepared in this manner into contact with the olefin-containing gas in the presence of the solvent at a predetermined reaction temperature and reaction pressure, the nitrogen-containing compound and the deactivator are brought into contact with each other. By adding it, the polymerization activity of the solvent is lost, so that the polymerization (oligomerization) of ethylene can be carried out efficiently. The reaction temperature during polymerization is usually 50 to 200℃,
Preferably it is 100-150°C. The reaction pressure is
Usually 5Kg/cm ² (gauge pressure) or more, preferably
25Kg/cm ² (gauge pressure) or more. Note that all operations from preparation of the catalyst to completion of the polymerization reaction are preferably performed while avoiding air and moisture. Preferably, the catalyst is prepared under an atmosphere of an inert gas such as nitrogen or argon. Further, it is desirable that catalyst preparation raw materials, solvents, reaction raw materials, etc. be sufficiently dried. However, the coexistence of trace amounts of moisture and air may increase catalyst activity and product selectivity. Below, an example of the method for producing a linear α-olefin of the present invention will be described in more detail. That is, in a container equipped with a stirrer, under an atmosphere of an inert gas such as argon or nitrogen, a mixture of the component [A] such as zirconium tetrachloride and the component [B] such as ethylaluminum sesquichloride is mixed with benzene, etc. After dissolving in the above solvent, the catalyst preparation solution is prepared by heating at 60 to 80°C for 10 to 120 minutes while stirring. A portion of this catalyst preparation solution is introduced into another container equipped with a stirrer under the inert gas atmosphere, diluted with the solvent such as benzene, and the [C] component such as thiophene is added at around room temperature, Stir to prepare catalyst solution. By preparing the catalyst in this manner, a complex catalyst of a metal halide compound such as zirconium tetrachloride and an alkyl aluminum compound is formed. Next, under an inert gas atmosphere, add 50% of the catalyst solution.
The catalyst solution is introduced into a reactor maintained at ~60° C. by pressure conveying, and while stirring the catalyst solution, a gas containing ethylene such as high purity ethylene is introduced to oligomerize under the above reaction conditions. After a predetermined period of time has elapsed, the nitrogen-containing compound such as ammonia, triethylamine, methylamine, etc. is added to the reaction system, and then water, water, etc.
Addition of the halogen in the catalyst to the linear α-olefin can be controlled by adding the catalyst deactivator such as alcohol to terminate the reaction. In this way, when a deactivator is added after adding a nitrogen-containing compound, the halogen in the catalyst becomes linear α-
The reason why addition to olefin can be suppressed is not clear at this stage, but it can be considered as follows. In other words, most of the organic halogen compounds that can be used as linear α-olefins have a halogen added to the end of the linear α-olefin, and this is because the alkyl group coordinated to the catalyst separates during polymerization and forms a linear α-olefin. It is thought that the halogen of the catalyst is added to the terminal when forming α-olefin. Therefore, if nitrogen-containing compounds such as amines and ammonia are present at this time, these nitrogen-containing compounds coordinate with the metal halide of the catalyst and suppress the addition of halogen to the linear α-olefin. It is considered that [Effects of the Invention] According to the present invention, the following effects can be achieved. In this invention, a nitrogen-containing compound such as ammonia, triethylamine, methylamine, etc. is added when adding a deactivator to a mixture of a catalyst, a hydrocarbon solvent, and the produced α-olefin to terminate the reaction. It is possible to suppress the addition of the halogen compound to the linear α-olefin. Therefore, according to the method of the present invention, it is possible to produce a linear α-olefin that does not contain a halogen compound, so it can be used as a comonomer for producing various copolymers, and as a raw material for plasticizers, surfactants, etc. Linear α that can be suitably used in various industrial fields etc.
- A method for producing olefin can be provided. Furthermore, if certain halogen-containing catalysts are used,
The catalytic activity for oligomerization of olefins is high, and highly pure linear α-olefins can be obtained more efficiently.Even when the reaction is carried out at high temperatures, there is little wax by-product, and the operability of the process is significantly improved. , Therefore, long-term continuous operation is possible. That is, according to the present invention, it is possible to provide a method for producing a middle distillate linear α-olefin by oligomerizing an olefin, which is industrially significantly superior to conventional methods. [Example] Examples 1 to 12 Catalyst Preparation Example (Preparation of Catalyst Solution) In a 1000 ml flask with a stirrer, under an argon atmosphere, 50 mmol of anhydrous zirconium tetrachloride and
472 ml of dry benzene was introduced and stirred for 30 minutes. To this, the alkylaluminum compounds shown in Table 1 are added in a molar ratio calculated from the indicated amounts to zirconium tetrachloride (for example, since the molar ratio Al/Zr is 5.0,
210 mmol of ethylaluminum sesquichloride and 40 mmol of triethylaluminum were added. ) and stirred at 60°C for 30 minutes to prepare a catalyst preparation solution. Next, predetermined amounts of benzene dried under an argon atmosphere and the catalyst preparation solution were introduced into a 500 ml three-necked flask, and zirconium tetrachloride, the ethylaluminum compound shown in Table 1, and
The amount of benzene was adjusted to the amount shown in Table 1. To this, 0.30 mmol of thiophene was added as a third component, and the mixture was stirred at room temperature for 10 minutes to prepare a catalyst solution. Production Example of α-Olefin (Ethylene Oligomerization) In a dry argon atmosphere, the catalyst solution prepared in the above catalyst preparation example was introduced into the autoclave equipped with a stirrer in step 1 by pumping argon. At this time, the temperature of the autoclave is 50 to 60
It was kept at ℃. After charging the catalyst solution, stirring was started, and high purity ethylene gas was rapidly blown into the autoclave until the pressure reached the indicated reaction pressure, and then the temperature was raised to the indicated reaction temperature. Ethylene continued to be introduced in the amount necessary to maintain the pressure. After continuing the reaction for 1 hour while maintaining these reaction conditions, the inside of the autoclave was depressurized and cooled to the temperature shown in Table 2. ) was added using a pump while stirring. Thereafter, the amount of deactivator indicated in Table 2 was added to deactivate the catalyst. Furthermore, after washing with water, the chlorine ion concentration of the oil layer (mixture of the solvent benzene and the produced linear α-olefin) was measured, and the amount of chlorine with respect to the produced linear α-olefin was determined. The results are shown in Table 2. The post-treatment steps for the reaction product are as follows. First, 20 g of undencane for gas chromatography internal standard was added to the reaction product, and then the wax content was filtered out using filter paper. The wax on the filter paper was thoroughly washed with benzene, and the light components in the wax were 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 clear reaction product solution thus obtained was analyzed by gas chromatography. The yield of the product was determined by the internal standard method. On the other hand, the filtered wax is air-dried and then
After drying in a vacuum dryer at 20 mmHg, the weight was measured. Note that the yield of the C ₄ to _{C 8} fraction was estimated from the Schulz-Flory distribution since operational losses are unavoidable. The results are summarized in Table 1. Comparative Examples 1 to 8 As shown, experiments were carried out in the same manner as in the examples without using a nitrogen-containing compound. However, the usage amount of each component, reaction conditions, etc. are as indicated. The results are summarized in Table 1.

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Claims (1)

[Claims] Primary formula: ZX _a A _4-a [1] (wherein, Z represents zirconium, and X and A
may be the same or different, and each represents Cl, Br, or I. Also, a is 0
Represents an integer from ~4. ) and a metal halide represented by the following formula: AlR _1.5 Q _1.5 [2] (wherein, R represents an alkyl group having 1 to 20 carbon atoms, and Q represents Cl, Br, or I. However,
R and Q may be the same or different. Note that the second formula is
It can also be expressed by Al ₂ R ₃ Q ₃ . ) or the alkyl aluminum compound represented by the formula [2] above, and/or the following formula: AlR′ _b Q′ _3-b [3] (wherein, R′ and Q′ are each It represents the same meaning as the above R and the above Q. Also, b is 1 to 3
represents an integer. However, R' and Q' may be the same or different. ), an olefin-containing gas is polymerized in the presence of a hydrocarbon solvent and a halogen-containing catalyst obtained from an alkyl aluminum compound represented by 1. A method for producing a linear α-olefin, which comprises adding a nitrogen-containing compound during the process. 2. The method for producing a linear α-olefin according to claim 1, wherein the nitrogen-containing compound is ammonia or an amine. 3. The linear α according to claim 1 or 2, wherein the Q and/or Q' is Cl.
- A method for producing olefin. 4. The method for producing a linear α-olefin according to any one of claims 1 to 3, wherein the alkylaluminum compound represented by the formula [2] is ethylaluminum sesquichloride. 5. The method for producing a linear α-olefin according to any one of claims 1 to 4, wherein the alkyl aluminum compound represented by formula [3] is diethylaluminum chloride or triethyl aluminum. .