JPH0853374A - Production of linear alpha-olefin - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject compound useful as a co-monomer for modifying a polyolefin, etc., in high purity by polymerizing an olefin- containing gas in the presence of a specific catalyst and solvent and successively deactivating the catalyst with a deactivator in the presence of a specific oxygen- containing compound. CONSTITUTION:(C) An olefin-containing gas is polymerized in the presence of (A) a catalyst consisting of a zirconium halide compound such as a compound of the formula ZrXaY4-a (X and Y are each Cl, Br or I; a=0-4) and an alkyl aluminum compound such as a compound of the formula Al2R3Q3 (R is a 1-20C alkyl; Q is Cl-, Br or I) or a compound of the formula AlR'bQ'3-b (R' is R; Q' is Q; b=1-3) in (B) an aromatic hydrocarbon solvent such as (chloro)benzene. The reaction product is treated with (E) a deactivator such as water in the presence of (D) an oxygen-containing compound (e.g. an ether compound, O2 or CO) in an amount of >=2mol based on the Zr of the component A to deactivate the component A. Thus, the objective compound is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a linear (straight-chain) α-used as a comonomer for modifying polyolefin.
The present invention relates to a method for producing an olefin, and more particularly to a method capable of efficiently producing a linear α-olefin containing few impurities by suppressing the production of by-products from an aromatic hydrocarbon solvent as a reaction solvent.

[0002]

Demand for linear α-olefins is increasing as a comonomer for modifying polyolefins or as a raw material for synthetic lubricating oils, plasticizers, surfactants, etc. Olefin has been required. Such linear α-olefins are generally produced by oligomerizing ethylene in the presence of a catalyst composed of a mixture of a zirconium halide compound and an alkylaluminum compound. At this time, aromatic hydrocarbons are excellent as reaction solvents, and the catalyst performance can be remarkably improved. However, when an aromatic hydrocarbon solvent is used as a reaction solvent, a trace amount of impurities which become a catalyst poison when a derivative (for example, low-pressure method low-density polyethylene) is further synthesized by using the linear α-olefin obtained therefrom is included. Therefore, there is a problem that the derivative cannot be efficiently synthesized. For example, when an aromatic hydrocarbon solvent such as benzene is used as a reaction solvent, alkylbenzene, which is an aromatic alkylated product, is produced as a by-product and is mixed in the product linear α-olefin. Therefore, when an attempt is made to produce low-density low-density polyethylene, the activity of the polymerization catalyst may be reduced. Therefore, it is practically impossible to use an aromatic hydrocarbon solvent.

On the other hand, a catalyst comprising a mixture of a zirconium halide compound and an alkylaluminum compound,
In producing a linear α-olefin by polymerizing an olefin-containing gas in the presence of an aromatic hydrocarbon solvent,
It has been proposed to prevent or suppress harmful side reactions by using a drug (inactivating agent) that loses the polymerization activity of the catalyst to prevent or suppress harmful side reactions, such as water, alcohol, carboxylic acid, etc. Method using deactivator (Japanese Patent Publication No. 2-3789)
No. 3) is known. In addition, by deactivating the catalyst by adding a deactivator after adding the nitrogen-containing compound,
The halogen contained in the catalyst is the final product α-
Method of suppressing addition to olefin (Japanese Patent Publication No. 4-
No. 46929) is known.

However, even when the method using these deactivators is used, when an aromatic hydrocarbon solvent is used as a reaction solvent, it is unavoidable that an aromatic alkyl compound is produced as a by-product, and the product line is obtained. When an aromatic hydrocarbon solvent is used as a reaction solvent, it may be mixed into the crystalline α-olefin, resulting in a decrease in the activity of the polymerization catalyst when low-pressure low-density polyethylene or the like is produced. It was impossible.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and in the presence of an aromatic hydrocarbon solvent and a catalyst comprising a mixture of a zirconium halide compound and an alkylaluminum compound, ethylene is oligomerized. In the method of producing an α-olefin by deactivating the catalyst with a deactivator in the presence of an oxygen-containing compound in an amount of at least 2 times the molar amount of zirconium in the catalyst,
Since the production of by-products from the aromatic hydrocarbon solvent is suppressed, an excellent aromatic hydrocarbon solvent can be used as a reaction solvent, and linear α containing few impurities can be used.
-The purpose of the present invention is to provide a method capable of efficiently producing olefins.

[0006]

Means for Solving the Problems That is, the present invention is directed to polymerizing an olefin-containing gas in the presence of a catalyst comprising a mixture of a zirconium halide compound and an alkylaluminum compound and an aromatic hydrocarbon solvent to obtain a linear catalyst. State α-
In producing an olefin, the catalyst is deactivated by using a deactivator in the presence of an oxygen-containing compound in an amount of at least 2 times the molar amount of zirconium in the catalyst, and the production of a linear α-olefin. It provides a method.

In the method of the present invention, a catalyst comprising a mixture of a zirconium halide compound and an alkylaluminum compound is used as the catalyst. Here, as the zirconium halide compound, a compound represented by the following formula [1] ZrX _a Y _4-a ... [1] is used. In the formula [1], X and Y may be the same or different,
Each represents chlorine, bromine or iodine. Also, a is 0
Indicates an integer of ˜4. Specific examples of such a zirconium halide compound include ZrCl ₄ and ZrBr.
₄ , ZrI ₄ , ZrBrCl ₃ , ZrBr ₂ Cl and the like can be mentioned, and any one kind or two or more kinds thereof are used. Of these, ZrCl ₄ (zirconium tetrachloride) is preferably used in the present invention.

Next, as the alkylaluminum compound, an alkylaluminum compound represented by the following formula [2] Al ₂ R ₃ Q ₃ ... [2], and / or
An alkylaluminum compound represented by the following formula [3] AlR ′ _b Q ′ _3-b ... [3] is used.
In formula [2], R represents an alkyl group having 1 to 20 carbon atoms,
Q represents chlorine, bromine or iodine. In addition, in the formula [3],
R'has the same meaning as R, and Q'has the same meaning as Q. Moreover, b represents the integer of 1-3.

Alkylalumini represented by the above formula [2]
As the um compound, R is a methyl group, an ethyl group, or a propyl group.
And a butyl group are preferred, and an ethyl group is preferred.
Those that are particularly preferable. Further, it is represented by the above formula [2].
As the alkylaluminum compound, Q is chlorine
Those are preferable. Alkyl aluminum represented by the formula [2]
As the um compound, specifically, for example, Al₂(CH₃)₃
Cl₃, Al₂(CH₃)₃Br₃, Al₂(C₂H_Five)₃Cl
₃, Al₂(C₂H_Five)₃Br₃, Al₂(C₂H_Five)₃I₃, A
l₂(C₂H_Five)₃BrCl₂, Al ₂(n-C₃H₇)₃Cl
₃, Al₂(iso-C₃H₇)₃Cl₃, Al₂(n-C_FourH₉)
₃Cl₃, Al₂(iso-C_FourH₉)₃Cl₃, Al₂(n-C
_FiveH₁₁)₃ , Al₂(n-C₈H₁₇)₃Cl₃, Al₂(C
₂H_Five)₂(CH₃) Cl₃Etc. and any of these
One type or two or more types are used. In the present invention, these
Among them, ethyl aluminum sesquichloride [Al
₂(C₂H_Five)₃Cl₃] Is preferably used.

Next, as the alkylaluminum compound represented by the above formula [3], those in which b is 3 or 2 are preferable, and those in which R'is an ethyl group, a propyl group, a butyl group and an isobutyl group are preferred. Those having an ethyl group are particularly preferable. Further, the alkylaluminum compound represented by the above formula [2] is preferably one in which Q ′ is chlorine. Specific examples of the alkylaluminum compound represented by the formula [3] include Al (CH ₃ ).
_{3, Al (C 2 H 5} ) 3, Al (n-C 3 H 7) 3, Al (i
_{so- C 3 H 7) 3,} Al (n-C 4 H 9) 3, Al (iso- C
_{4 H 9) 3, Al (} n-C 5 H 11) 3, Al (n-C
_{6 H 13) 3, Al (} n-C 8 H 17) 3, Al (C 2 H 5) 2 C
_{l, 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 are used, and any one or more of these is used. Of these, triethylaluminum and diethylaluminum chloride are preferably used in the present invention.

When the alkylaluminum compound represented by the formula [2] and the alkylaluminum compound represented by the formula [3] are used in combination, the ratio of both is usually represented by the formula [3]. Alkyl aluminum compound is 50%
It is desirable to set it to (Al standard) or less, preferably 30% (Al standard) or less.

Further, in the present invention, as the catalyst component, in addition to the mixture of the zirconium halide and the alkylaluminum compound, at least one compound selected from the group consisting of organic sulfur compounds, organic phosphorus compounds and organic nitrogen compounds is used. It is preferable to use them together. Examples of the organic sulfur compound here include thioethers such as dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dihexyl sulfide, dicyclohexyl sulfide, diphenyl thioether, dimethyl disulfide [(CH ₃ ) ₂ S ₂ ], diethyl disulfide,
Dialkyl disulfide compounds such as dipropyl disulfide, dibutyl disulfide, dihexyl disulfide, dicyclohexyl disulfide and ethylmethyl disulfide, thiophene, 2-methylthiophene, 3-methylthiophene, 2,3-dimethylthiophene, 2-ethylthiophene , Thiothiones such as benzothiophene, heterocyclic sulfur compounds such as tetrahydrothiophene and thiopyran, aromatic sulfur compounds such as diphenyl disulfide, methylphenyl disulfide and methylphenyl sulfur, thiourea [(NH ₂ ) ₂ CS], methyl sulfide , Ethyl sulfide, butyl sulfide, and the like.

Next, examples of the organic phosphorus compound include phosphines such as triphenylphosphine, triethylphosphine, tributylphosphine, tripropylphosphine, trioctylphosphine and tricyclohexylphosphine.

Further, as the organic nitrogen compound, for example,
Methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, decylamine, aniline, benzylamine, naphthylamine, dimethylamine, diethylamine, dibutylamine, diphenylamine, methylphenylamine, trimethylamine, triethylamine, Tributylamine, triphenylamine,
Examples thereof include organic amines such as pyridine and picoline.

Among the above organic sulfur compounds, organic phosphorus compounds and organic nitrogen compounds, at least one selected from the group consisting of dimethyl disulfide, thiophene, thiourea, triphenylphosphine, tributylphosphine, trioctylphosphine and aniline. Preference is given to using one compound.

Further, an aromatic hydrocarbon solvent is used in the method of the present invention. Examples of the aromatic hydrocarbon solvent include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, ethylbenzene, and chlorotoluene, and halogen-substituted products thereof, and one or more of them may be used. To use. Among these, benzene, xylene and chlorobenzene are preferable, and benzene is particularly preferable.

As the olefin-containing gas, a gas containing ethylene, a gas containing propylene, a gas containing butene-1 and the like are used, and a gas containing ethylene is particularly preferable. Examples of the gas containing ethylene include an inert gas containing ethylene, purified ethylene gas for polymerization, purified ethylene gas for polymerization such as high-purity ethylene, and the like. Among these, high-purity ethylene is particularly preferable.

In the present invention, the olefin-containing gas is polymerized in the presence of a catalyst comprising a mixture of a zirconium halide compound and an alkylaluminum compound as described above and the aromatic hydrocarbon solvent to form a linear gas. In producing the α-olefin, it is necessary to deactivate the catalyst with a deactivator in the presence of an oxygen-containing compound in an amount of at least 2 times the molar amount of zirconium in the catalyst.

Examples of the oxygen-containing compound include aliphatic ethers such as dimethyl ether, diethyl ether and dipropyl ether, aromatic ethers such as diphenyl ether and phenyl methyl ether, propylene oxide, tetrahydrofuran and furan. Examples thereof include cyclic ethers, molecular oxygen and carbon monoxide. These oxygen-containing compounds may be used alone or in combination with 2
You may use it in combination of 2 or more types. If necessary, a nitrogen-containing compound such as ammonia or amines can be used together with the oxygen-containing compound.

Specific examples of the quenching agent include water, alcohol (for example, monohydric alcohol, polyhydric alcohol, cyclic alcohol, acyclic alcohol, aliphatic alcohol,
(Aromatic alcohol), carboxylic acid, phenols and the like, and those described in JP-A-58-109428 can be used. Among these, water and alcohols such as methanol and ethanol are particularly preferable.

In the present invention, the catalyst may be deactivated by using a deactivator in the presence of an oxygen-containing compound in a molar amount of at least 2 times, preferably at least 4 times the molar amount of zirconium in the catalyst. The timing of adding the oxygen-containing compound is not particularly limited, but the deactivator must be used in the presence of the oxygen-containing compound. That is, there are a method of first adding an oxygen-containing compound and then a deactivator, and a method of simultaneously adding an oxygen-containing compound and a deactivator. Further, the deactivator is added after the reaction of the olefin-containing gas, but in principle, there is no limitation on the addition timing of the oxygen-containing compound. That is, in the method of 1, further, a method of adding an oxygen-containing compound to the catalyst before the polymerization reaction (a method of using a catalyst to which an oxygen-containing compound is added), an oxygen-containing compound during the polymerization reaction, and after the polymerization reaction There are a method of adding a quenching agent and a method of adding a quenching agent after adding an oxygen-containing compound after the polymerization reaction. Among these, the method of is preferable.

In the method of the present invention, the deactivation temperature at the time of deactivating the catalyst by adding a deactivator to the mixture of the catalyst, the aromatic hydrocarbon solvent and the produced α-olefin is usually from room temperature to The temperature is 150 ° C, preferably 110 to 130 ° C. The deactivation pressure is from normal pressure to 5 MPa, preferably from normal pressure to 1 MPa. The deactivation time is 1 minute or less.

In the method of the present invention, when preparing the catalyst solution, there is no particular limitation on the order of mixing the catalyst components and the aromatic hydrocarbon solvent and the method. For example, a zirconium halide compound and an alkylaluminum compound are each or simultaneously dissolved in an appropriate amount of a solvent for preparing a catalyst to prepare a catalyst preparation solution, and the catalyst preparation solution or the catalyst is prepared prior to polymerization. A method of preparing a catalyst solution by adding the aromatic hydrocarbon solvent to a solution prepared by adding at least one compound selected from the group consisting of organic sulfur compounds, organic phosphorus compounds and organic nitrogen compounds, It is suitable. At this time, the catalyst is preferably subjected to a known activation treatment. As the solvent for preparing the catalyst, those exemplified as the aromatic hydrocarbon solvent may be used, and benzene, xylene, and chlorobenzene are particularly preferable.

Usually, the catalyst or catalyst solution thus prepared is brought into contact with the olefin-containing gas in the presence of the aromatic hydrocarbon solvent, and then the oxygen-containing compound and the quenching agent are added, By eliminating the polymerization activity of the solvent, olefin polymerization (oligomerization) can be efficiently performed.

As the reaction conditions for the oligomerization, the reaction temperature is usually 50 to 200 ° C., preferably 100 to 15
0 ° C. The reaction pressure is usually 0.5 MPa or higher, preferably 2.5 MPa or higher. Furthermore, the reaction time is 15 minutes to 2 hours, preferably 30 to 60 minutes.

The catalyst is preferably prepared in an atmosphere of an inert gas such as nitrogen or argon. Also,
It is desirable that the catalyst preparation raw material, the solvent, the reaction raw material and the like are sufficiently dried. It is desirable to avoid water and air during the operations from the preparation of the catalyst to the end of the polymerization reaction.

As described above, the production of by-products from the aromatic hydrocarbon solvent as the reaction solvent is suppressed, and the linear α-olefin containing few impurities can be efficiently produced.

[0028]

EXAMPLES Next, the present invention will be described in detail with reference to Examples. Examples 1 to 3 (1) Preparation of Catalyst (Preparation of Catalyst Solution) 50 mmol of anhydrous zirconium tetrachloride and 472 ml of dried benzene were introduced into a 1 liter flask equipped with a stirrer under an argon atmosphere, and the mixture was stirred for 30 minutes. . Ethyl aluminum sesquichloride ([Al ₂ (C
₂ H _{5) 3} Cl _3] was added 210 mmol and triethyl aluminum 40 mmol, stirred for 3 hours at 70 ° C., to prepare a catalyst solution. Next, in a 500 ml three-necked flask, 50 m of dried benzene was added under an argon atmosphere.
1 and a part of the catalyst solution were introduced. In Examples 1 and 2, a predetermined amount of thiophene as a sulfur compound was further added thereto and stirred at room temperature for 10 minutes to prepare catalyst solutions. Further, in Example 3, a predetermined amount of tetrahydrofuran (THF) as an oxygen-containing compound was further added thereto, and the mixture was stirred at room temperature for 10 minutes to prepare a catalyst solution.

(2) Production of α-olefin (Oligomerization of ethylene) 200 ml of benzene was introduced into a 1 liter autoclave equipped with a stirrer under a dry argon atmosphere. Then, stirring was started and the temperature was raised to the reaction temperature (120 ° C.). After reaching the set temperature, high-purity ethylene gas was pressurized in the autoclave up to the reaction pressure (7 MPa), and the catalyst solution prepared in (1) above was pressure-fed to start the reaction.
Ethylene continued to be introduced in the amount needed to maintain the pressure. After continuing the reaction for 1 hour, the inside of the autoclave was cooled and depressurized, and under the conditions shown in Table 1, the indicated amount of the oxygen-containing compound was poured into the autoclave while stirring. Thereafter, the amount of the deactivator shown in Table 1 was added to deactivate the catalyst. After that, the product was washed with water to remove the spent catalyst, and the product was analyzed by gas chromatography. Table 2 shows the product distribution obtained. Table 1 shows the amount of impurities (alkylbenzene) mixed in 1-decene as a representative of the α-olefins produced.

Comparative Example 1 The procedure of Example 1 was repeated, except that no additives were used. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 1 was repeated except that the oxygen-containing compound was not used. The results are shown in Table 1.

Comparative Example 3 The procedure of Example 2 was repeated except that no oxygen-containing compound was used. The results are shown in Table 1.

Comparative Example 4 The procedure of Example 3 was repeated except that no oxygen-containing compound was used. The results are shown in Table 1.

[0034]

[Table 1]

[Footnote in Table 1] * 1: The products mainly contain C _{4 to} C ₁₈ , but they are shown as typical examples. * 2: alkylbenzene amount contained in the C ₁₀ * 3: ammonia concentration 28%

[0036]

[Table 2]

[0037]

According to the present invention, in a method for producing an α-olefin by oligomerizing ethylene in the presence of a catalyst comprising a mixture of a zirconium halide compound and an alkylaluminum compound and an aromatic hydrocarbon solvent. By deactivating the catalyst with a deactivator in the presence of an oxygen-containing compound in an amount of at least 2 times the molar amount of zirconium in the catalyst, the production of by-products from the aromatic hydrocarbon solvent is suppressed. Therefore, an excellent aromatic hydrocarbon solvent can be used as a reaction solvent. Therefore, according to the present invention, the catalyst performance can be dramatically improved. Moreover, according to the present invention, a linear α-olefin containing few impurities can be efficiently produced.

The various aspects of the present invention are as follows. (1). In producing a linear α-olefin by polymerizing an olefin-containing gas in the presence of a catalyst consisting of a mixture of a zirconium halide compound and an alkylaluminum compound, and an aromatic hydrocarbon solvent, zirconium in the catalyst is produced. A method for producing a linear α-olefin, characterized in that the catalyst is deactivated by using a deactivator in the presence of a 2-fold or more molar amount of an oxygen-containing compound.

(2). The zirconium halide compound is a compound represented by the above formula [1], (1)
A method for producing the described linear α-olefin.

(3). Alkyl aluminum compound
An alkylaluminum compound represented by the above formula [2],
And / or the method for producing a linear α-olefin according to (1) above, which is an alkylaluminum compound represented by the above formula [3].

(4). The method for producing a linear α-olefin according to (3) above, wherein the alkylaluminum compound represented by the formula [2] is ethylaluminum sesquichloride.

(5). The method for producing a linear α-olefin according to (3), wherein the alkylaluminum compound represented by the formula [3] is diethylaluminum chloride or triethylaluminum.

(6). The method for producing a linear α-olefin according to (1) above, wherein the oxygen-containing compound is an ether compound, molecular oxygen or carbon monoxide.

(7). The linear α according to (1) above, wherein the aromatic hydrocarbon solvent is one or more selected from benzene, toluene, xylene, chlorobenzene, ethylbenzene, chlorotoluene, and halogen-substituted compounds thereof. -Method for producing olefins.

(8). The method for producing a linear α-olefin according to (1) above, wherein the oxygen-containing compound is added before the reaction is completed.

Claims (4)

[Claims] 1. When producing a linear α-olefin by polymerizing an olefin-containing gas in the presence of a catalyst composed of a mixture of a zirconium halide compound and an alkylaluminum compound and an aromatic hydrocarbon solvent, A method for producing a linear α-olefin, comprising deactivating the catalyst using a deactivator in the presence of an oxygen-containing compound in an amount of at least 2 times the molar amount of zirconium in the catalyst. 2. A zirconium halide compound represented by the following formula [1] ZrX _a Y _4-a ... [1] (wherein X and Y may be the same or different) And each represents chlorine, bromine, or iodine, and a represents an integer of 0 to 4), The process for producing a linear α-olefin according to claim 1. 3. An alkylaluminum compound having the following formula [2] Al ₂ R ₃ Q ₃ ... [2] (wherein R represents an alkyl group having 1 to 20 carbon atoms, Q is chlorine, bromine or An alkylaluminum compound represented by iodine) and / or the following formula [3] AlR ′ _b Q ′ _3-b ... [3] (wherein R ′ has the same meaning as R above). And Q'has the same meaning as Q. Further, b is an alkylaluminum compound represented by an integer of 1 to 3.) The method for producing a linear α-olefin according to claim 1. 4. The method for producing a linear α-olefin according to claim 1, wherein the oxygen-containing compound is an ether compound, molecular oxygen or carbon monoxide.